description
stringlengths 2.98k
3.35M
| abstract
stringlengths 94
10.6k
| cpc
int64 0
8
|
|---|---|---|
BACKGROUND OF THE INVENTION
This invention relates generally to an improved base construction for various type high intensity arc discharge lamps and more particularly to providing simpler means for permanently securing a screw type base member directly to the outer lamp envelope.
High intensity arc discharge lamps of various types are now globally employed as a source of highly efficient white and colored illumination in both indoor and outdoor applications. Both mercury vapor and metal halide types of said lamps conventionally employ a tubular arc tube of light transmissive vitreous material as an inner light source which is hermetically sealed within an outer vitreous lamp envelope. The arc tube comprises a hermetically sealed envelope, which can be quartz glass having thermionic electrodes at opposite ends in pinch seal regions and further contains a gaseous discharge medium which includes mercury. The gaseous discharge medium can further contain alkali metal and/or alkaline earth metal additives to form an amalgam with mercury. Addition of the latter additives in metal halide lamps has been found to enhance the color of light output as well as increase its efficiency. The general construction of such type lamps is further disclosed in U.S. Pat. Nos. 4,007,397; 4,581,557; and 5,055,740 to include the conventional use of a screw type conductive base member for operation in existing socket fixtures.
A common construction in prior art lamps of this type includes an inner hollow shell member affixed to the outer lamp envelope which is threaded into an outer shell member. A pair of lamp inlead conductors emerging from the outer lamp envelope are terminated by connection to the outer metal shell member with one of said inlead conductors being electrically isolated therefrom in the customary manner. Understandably such requirement for a multi-shell base assembly complicates lamp manufacture as well as increases lamp cost. A need to carefully control the physical tolerances in both size and shape of the individual shell members in such base assembly for the high speed lamp manufacture now being carried out represents still another problem associated with the prior art base construction.
Accordingly, one object of the present invention is to provide a more simple base construction for high intensity arc discharge lamps.
It is another object of the present invention to provide a base construction for high intensity arc discharge lamps which is less subject to control of physical tolerances between the individual base components.
A still further object of the present invention is to reduce material costs for a base construction in such type lamps.
Still another object of the present invention is to provide a relatively simple modification in otherwise conventional lamp manufacture needed for the basing of a high intensity arc discharge lamp.
These and still further object of the present invention will become more apparent upon considering the following detailed description for the present invention.
SUMMARY OF THE INVENTION
A modified base construction is now provided for a high intensity arc discharge lamp which enables a single piece screw type conductive base member to be directly secured to the outer lamp envelope by means of a conductive clip physically attached to the outer lamp envelope. Suitable clip means for this purpose employs a general physical configuration, such as a U-shaped member, enabling direct physical attachment to the customary threaded base end of the outer lamp envelope while further including at least one outwardly projecting tang element to physically engage the conductive base member when joined thereto, Subsequent assembly of a customary screw type base shell to the outer lamp envelope permanently anchors the base shell in place due to frictional forces occasioned between the tang element of the clip member and inner surface of the hollow base shell. Fabrication of the clip member with conventional conductive metals, such as copper, brass or iron alloys, is preferred to withstand elevated operating temperatures at the base end of the outer lamp envelope which can exceed 200° C. or more.
Conventional discharge lamp construction further includes a pair of inlead conductors emerging from the threaded end of the outer lamp envelope for customary termination at the conductive base member. The molded threads of the conventional lamp envelope generally further include one or more longitudinally extending surface depressions therein to secure one of the inlead conductors in place for electrical connection to the base member and with the remaining inlead conductor being electrically isolated therefrom in the customary manner. Accordingly, one of such existing surface depressions in such conventional lamp envelope can further provide a suitable location for physical attachment of the clip member thereat and in a manner enabling the projecting tang element or elements of said clip member to protrude slightly beyond the molded threads of the lamp envelope. Attaching the base shell to the mating threads of the outer lamp envelope completes assembly of the herein modified discharge lamp construction. The emerging inlead conductor being electrically connected directly to the base shell in said lamp embodiment can also be anchored to the clip member for lamp manufacture or assembly, if so desired. For example, one or more openings can be provided in the illustrated U-shaped clip member having the tang construction to accommodate passage of said inlead conductor therethrough. Actual joinder of said inlead conductor itself to the clip member by such means as soldering and the like is also contemplated.
Adoption of the presently improved base construction employing clip means to reliably secure a single piece screw type conductive base member to the threaded outer lamp envelope has benefits for still other high intensity arc discharge lamp configurations. For example, in a different conventional lamp configuration there is employed an inner threaded conductive base shell mechanically crimped to molded dimples at the base end of an unthreaded outer lamp envelope when an outer threaded conductive base shell having mating threads is screwed thereto. Employment of the presently improved base construction understandably eliminates need for such inner base shell as a cost saving while further simplifying the lamp manufacture. A still different conventional arc discharge lamp configuration employs a single piece screw type conductive base member affixed to the threaded end of an outer lamp envelope which includes longitudinally extending surface depressions in which one of the emerging inlead conductors is held in place with a solder deposit that further avoids unscrewing of the base member from the lamp envelope. Adoption of the present base member construction can possibly eliminate any such need for soldering in order to prevent partial or complete separation of the joined lamp components.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view depicting a prior art metal halide arc discharge lamp.
FIG. 2 is a side view of the base construction employed in the FIG. 1 lamp.
FIG. 3 is another side view of the base construction employed in the FIG. 1 lamp further depicting the manner of its assembly together.
FIG. 4 is a perspective view of a representative clip means employed according to the present invention.
FIG. 5 is a side view for a representative arc discharge lamp base construction employing the clip means of FIG. 4.
FIG. 6 is another side view of the FIG. 5 base construction depicting-the manner of assembly together.
FIG. 7 is a cross sectional view of the FIG. 6 base construction depicting representative surface depressions in the threaded end of the outer lamp envelope for physically attaching the FIG. 4 clip means thereto.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a cross sectional side view depicting a representative prior art metal halide discharge lamp 10 employing a two-part base member construction. More particularly the lamp comprises an outer vitreous envelope 12 shown partially secured to a two-part screw-in type conductive base assembly 14 and 14a at an unthreaded end. Inner conductive base shell 14 is shown physically attached to the unthreaded end 15 of the lamp envelope while outer conductive base shell 14a has mating threads 16 for further attachment to the inner base shell when screwed together. An arc tube assembly 18 is physically suspended within the outer envelope 12 by means of a two-part metal mount frame 20 and 22 which is electrically connected in part to lamp terminal means provided in outer base member 14a. In said regard such electrical connection is provided with first inlead conductors 24 and 26 extending outward from a conventional reentrant stem 28 to a pair of metal support rods or posts 30 and 32 forming the lower half 20 of the mount frame. Upper half 22 in said mount frame remains electrically isolated or insulated from the lamp terminal means other than when connected thereto during lamp operation by means of the arc discharge (not shown). Lower mount frame 20 includes a clamp 34 secured to bottom pinch seal region 36 of the arc tube member 18 while a similar clamp 38 is provided in the upper frame 22 and secured to upper pinch seal region 40 of the arc tube member as a structural means for its physical support. Arc tube member 18 includes spaced apart principal discharge electrodes 42 and 44 and a starting electrode 46 along with a suitable gaseous discharge medium including mercury and a metal halide (not shown). As herein shown, all discharge electrodes 42, 44 and 46 are individually connected to second inlead conductors 48, 50 and 52 at the respective pinch seal regions of the arc tube via thin refractory metal foil elements additionally located thereat. Still further electrical interconnection between the second inlead conductors 48, 50 and 52 and the first inlead conductors 24 and 26 is provided in the illustrated lamp embodiment. Inlead conductor 52 is connected to inlead conductor 26 with a curved wire element 54 whereas remaining inlead conductors 48 and 50 are separately connected to inlead conductors 24 and 26, respectively, with conductive metal strips 56 affixed to support rod 32 which is also connected to the latter inlead conductors. Arc tube 18 still further includes a conventional exhaust tip-off 66 disposed intermediate the discharge electrodes.
The herein illustrated prior art lamp embodiment is operated with external ballast means which can still further include housing some of the operating circuitry along with still other operating components within the outer envelope 12 of the lamp construction. For example, the depicted lamp embodiment includes gettering means (not shown) provided in outer envelope 12 to remove gases such as oxygen from undesirably oxidizing the inner lamp components. Additionally, there can be included starting resistor means 68 within the outer envelope which forms a part of the lamp operating circuitry. The lamp is enabled by such operating circuit means to ionize vapor formed within the selected gaseous discharge medium in order to produce an arc discharge between the principal discharge electrodes 42 and 44 providing the output illumination. Initial ionization in the lamp occurs between starting electrode 46 and principal electrodes 42 with a hi-metallic switch element 70 operating to terminate energization of the starting electrode when an arc discharge is established between both principal discharge electrodes.
FIG. 2 provides a still more detailed side view of the prior art base assembly 14 and 14a employed in FIG. 1. Accordingly, the same numerals employed in FIG. 1 are retained in the present drawing to identify common components of said construction. Said base construction includes molded dimples or depressions 68 and 68a at the unthreaded base end 15 of outer lamp envelope 12 for physical attachment of inner base shell 14 thereto. Projecting tab elements 71 and 71a are provided at one end of the inner base shell as a means for doing so. Outer base shell member 14a is thereafter screwed into said inner base shell member 14 by means of its mating thread surface 16. A still further description of said prior art base assembly is depicted in FIG. 3. As therein shown, inner base shell 14 has already been secured to outer lamp envelope 12 in the forgoing manner with outer base shell 14a still remaining to be threaded by means of its mating threads 16 onto said inner base shell employing rotation provided with conventional automated lamp manufacturing equipment.
FIG. 4 is a perspective view depicting a representative clip means 80 for use in the presently improved lamp base construction. As can be seen, such clip means comprises a single metal U-shaped member 82 having spaced apart open ended leg elements 84 and 86 which are joined together at the opposite end with a connecting strip 88 to enable its physical attachment to the base end of a suitable outer lamp envelope (not shown) as more fully described hereinafter. Leg element 84 is formed to include a pair of outwardly projecting tang elements 90 and 92 to provide the means for frictional engagement with a suitable conductive base member (not shown) after being physically attached to the outer lamp envelope. Cooperating openings 94 and 96 are also provided in the clip member which enable an inlead conductor (not shown) emerging from the outer lamp envelope to be secured in place for subsequent termination at the conductive base member. In so doing, the herein illustrated clip member is physically attached to the base end of the outer lamp envelope with leg element 82 facing inwardly for initial passage of the emerging inlead conductor through opening 94 and continued passage of said inlead conductor through opening 96 for final joinder to the conductive base member. As previously indicated, joinder of the inlead conductor to the conductive base member in such manner, such as by soldering and the like, produces a desired electrical connection there-between.
In FIG. 5, a side view is shown of a representative arc discharge lamp base construction employing the clip means of FIG. 4. Accordingly, the depicted base construction utilizes a screw type conductive base shell 100 having an inner hollow opening 102 provided with a threaded surface 104 to be physically joined to mating threads 106 molded into the base end 108 of a vitreous outer lamp envelope 210 suitable for such discharge lamp. While not depicted in the present drawing, such discharge lamp can be of the same metal halide type previously described in FIG. 1 to include an inner arc tube of vitreous light transmissive material having discharge electrodes being sealed at opposite ends of a central cavity in pinch seal regions. The molded threads 106 of the depicted lamp envelope 110 further include a pair of longitudinally extending surface depressions 112 and 114 which participate in affixing-the clip member 80 to the outer lamp envelope in the above described manner. The pair of inlead conductors 116 and 118 emerging from said lamp envelope provide desired electrical interconnection between the inner arc tube (not shown) and the conductive base shell in the same manner also previously pointed out in the FIG. 1 embodiment. In such manner, inlead conductor 116 is secured to clip member 80 for electrical termination with the conductive base shell whereas remaining inlead conductor 118 is electrically isolated from said base shell upon termination at an insulated terminal 120 customarily provided in said base shell.
FIG. 6 provides a still more detailed side view for the FIG, 5 base construction further depicting the manner for physically joining inlead conductor 116 to clip member 80 and thereafter physically attaching said clip member to the outer lamp envelope 110. It can be seen that said inlead conductor first proceeds through the openings 94 and 96 provided in the FIG. 4 clip member for passage to the inner side wall of base shell 100. It can further be seen in the present drawing, that clip member 80 and the physically attached inlead conductor 116 are then inserted into surface depression 112 at the base end 108 of the lamp envelope 110. The depicted partial assembly further positions tang elements 90 and 92 of the clip member to be facing outwardly of the lamp envelope for final frictional engagement with the inner side wall of base shell 100 when physically secured to the lamp envelope. Final assembly of the depicted base construction in the foregoing manner requires only rotary attachment of the base shell to the molded threads 106 provided on the lamp envelope which again can be provided with conventional automated lamp manufacturing equipment,
In FIG. 7 there is shown a longitudinal sectional view taken through lines 7--7 in FIG. 6 to more fully depict representative surface depressions molded into the base end 108 of lamp envelope 110 for suitable attachment of the clip member 80 during lamp manufacture. Both surface depressions 112 and 114 employ a ramp configuration 122 and 122a to facilitate easy entry of the clip member thereinto after having the inlead conductor 116 first secured to said clip member. As can also be seen in the present drawing, such placement of the clip member in surface depression 112 enables at least one of the outwardly facing tang elements 90 and 92 to protrude slightly beyond the circumferential thread elements 106 provided in the illustrated lamp envelope. Upon simply threading the previously illustrated base shell over the projecting tang elements a sufficient frictional force is generated therebetween so as to effectively prevent any subsequent separation of the assembled lamp base construction. Further having the clip member lodged in a surface depression which terminates with the depicted slanting slope (ramp elements 122 and 122a) has also been found to aid in resisting detachment of the assembled base member.
It will be apparent from the foregoing description that a generally improved means has been provided for the base construction of various type high intensity arc discharge lamps, including both mercury vapor and metal halide type lamps. It is contemplated that modifications can be made in the specific lamp configurations than herein illustrated, however, without departing from the spirit and scope of the present invention. For example, these lamps may employ other already known lamp outer envelope shapes and sizes, inner arc tube constructions, specialized ballasting circuitry, and still other lamp variations. Accordingly, it is intended to limit the present invention only by the scope of the appended claims.
|
A modified base construction for a high intensity arc discharge lamp is described enabling a single piece screw type conductive base member to be directly secured to the outer lamp envelope. The simplified base construction employs a conductive clip physically attached to the outer lamp envelope which provides a locking engagement between the assembled lamp parts.
| 7
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims benefit of priority based on provisional application No. 61/772,057 filed on Mar. 4, 2013.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
THE NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT
Not Applicable.
INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
Not Applicable.
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to novel pentacyclic pyridoindolobenz[b,e]azepine derivatives for the treatment of neurological disorders.
Description of the Related Art
Various prior art references in the specification are indicated by italicized Arabic numerals in brackets. Full citation corresponding to each reference number is listed at the end of the specification, and is herein incorporated by reference in its entirety in order to describe fully and clearly the state of the art to which this invention pertains.
Unless otherwise specified, all technical terms and phrases used herein conform to standard organic and medicinal chemistry nomenclature established by International Union of Pure and Applied Chemistry (IUPAC), the American Chemical Society (ACS), and other international professional societies. The rules of nomenclature are described in various publications, including, “Nomenclature of Organic Compounds,” [1], and “Systematic Nomenclature of Organic Chemistry” [2], which are herein incorporated by reference in their entireties.
Neurological disorders comprise several major diseases as described in the Diagnostic and Statistical Manual of Mental Disorders (DSM IV-R) [3]. It is well-established that a particular neurological disorder may involve complex interactions of multiple neuroreceptors and neurotransmitters, and, conversely, a single neuroreceptor may be implicated in several disorders, both neurological and non-neurological. For example, the serotonin receptor is implicated in numerous disorders such as depression, anxiety, pain (both acute and chronic), etc.; the dopamine receptor is implicated in movement disorder, addiction, autism, etc; and the sigma receptors are involved in pain (both acute and chronic), and cancer. Many of the receptors that are found in the brain are also found in other areas of the body, including gastrointestinal (GI) tract, blood vessels, and muscles, and elicit physiological response upon activation by the ligands.
The rational drug design process is based on the well-established fundamental principle that receptors, antibodies, and enzymes are multispecific, i.e., topologically similar molecules will have similar binding affinity to these biomolecules, and, therefore, are expected to elicit similar physiological response as those of native ligands, antigens, or substrates respectively. Although this principle, as well as molecular modeling and quantitative structure activity relationship studies (QSAR), is quite useful for designing molecular scaffolds that target receptors in a “broad sense,” they do not provide sufficient guidance for targeting specific receptor subtypes, wherein subtle changes in molecular topology could have substantial impact on receptor binding profile. Moreover, this principle is inadequate for predicting in vivo properties of any compound; hence, each class of compound needs to be evaluated in its own right for receptor subtype affinity and selectivity, and in in vivo models to establish efficacy and toxicity profiles. Thus, there is a sustained need for the discovery and development of new drugs that target neuroreceptor subtypes with high affinity and selectivity in order to improve efficacy and/or minimize undesirable side effects.
Serotonin and sigma receptors are widely distributed throughout the body. To date, fourteen serotonin and two sigma receptor subtypes have been isolated, cloned, and expressed. Serotonin receptors mediate both excitatory and inhibitory neurotransmission, and also modulate the release of many neurotransmitters including dopamine, epinephrine, nor-epinephrine, GABA, glutamate and acetylcholine as well as many hormones such as oxytocin, vasopressin, corticotrophin, and substance P [4, 5]. During the past two decades, serotonin receptor subtype selective compounds have been a rich source of several FDA-approved CNS drugs. Most of these serotonin receptor subtypes have been focus of research in the past couple of decades and this effort has led to the discovery of important therapeutics like Sumatriptan (5-HT 1B/1D agonist) for the treatment of migraine, Ondansetron (5-HT 3 agonist) for the treatment of radiation or chemotherapy-induced nausea and vomiting, and Zyprexa (5-HT 2A /D 2 antagonist) for the treatment of schizophrenia. Therapeutic targets have been identified for 5-HT 4 (learning and memory) [6], 5-HT 5A (cognition, sleep) [7], 5-HT 6 (learning, memory) [8] and 5-HT 7 (pain and depression) [9, 10], and some selective ligands have been prepared for all of these receptors with the exception of 5-HT 5A . However, no CNS drug has yet emerged out of this effort. Thus, there is a need for selective high affinity agonists and antagonists that target serotonin and dopamine receptors for combating various CNS and peripheral disorders implicated by these neurotransmitter systems.
Among the various CNS disorders, drug addiction continues to be an important target for therapeutic intervention. Drug addiction is a devastating CNS disorder with enormous cost to the individual, family, and society. Presently, there is no cure for drug addiction, and overwhelming majority of patients (nearly 85%) undergoing modern day rehabilitation relapse back into compulsive drug consumption. Relapse is motivated by the intense craving for the drug that is experienced by the drug-withdrawn addict, even after being drug-free for many years. Methamphetamine (meth) (1) and 3,4-methylenedioxyamphetamine (MDMA) (2) are increasingly popular psychostimulant/hallucinogenic drugs with extremely high abuse
liabilities. MDMA, commonly known as ‘Ecstasy’ is one of the most extensively abused drugs worldwide during the past several years. It is a recreational drug very popular among the ‘rave’ users and is legally controlled in most countries of the world under UN Convention on Psychiatric Drugs and other international agreements. It is estimated that about 30% of the Americans between the ages of 16 and 25 have used MDMA at least once in their lifetime and majority of them have become habituated to it. The number of life-time users is about 11.6 million in 2009. The cost of treatment meth and MDMA addictions to the individual, society, and the government runs into millions of dollars in the United States alone and, therefore, the development of an effective medication for the treatment of psychostimulant abuse/addiction remains one of the top priorities of the National Institutes on Drug Abuse.
Progress achieved in this field shows the fundamental contribution of brain 5-HT 1A and 5-HT 2B receptors to virtually all behaviors associated with psychostimulant addiction. Recent data not only show a crucial role of 5-HT 1A receptors in the control of brain 5-HT activity and spontaneous behavior, but also their complex role in the regulation of the psychostimulant-induced 5-HT response and subsequent addiction-related behaviors [10] such as comorbid depression. Likewise, Luc Maroteaux et al., reported that serotonin 5-HT 2B receptor antagonists are required, and do play an important role in the modulation of serotonin release by MDMA in the brain [11]. These recent findings clearly suggest that 5-HT 1A/2B receptor ligands would be useful for the treatment of psychostimulant abuses and comorbidity resulting therefrom.
Rajagopalan [12, 13] and Adams et al. [14] disclosed the pentacyclic scaffolds incorporating the γ-carboline pharmacophore 3-6, where the two phenyl rings are fused at the
‘b’ and ‘f’ positions in the 7-membered D-ring. In particular, the sulfur analog 6b has been shown recently to have atypical antipsychotic properties [15]. However, other pentacyclic analogs, where the E-phenyl ring being fused at other positions in the 7-membered D-ring, have not been disclosed.
BRIEF SUMMARY OF THE INVENTION
Accordingly, the present invention relates to novel pentacyclic γ-carboline scaffold
represented by Formula I, wherein the two phenyl groups are fused at the ‘b’ and ‘e’ positions in the 7-membered D-ring. A and B are independently —(CH 2 ) n —; and ‘n’ varies from 0 to 3. X is —CHR 10 —; —O—, —NR 11 —, —S—, —SO—, or —SO 2 —. Y is a single or a double bond. R 1 to R 11 are various electron donating, electron withdrawing, hydrophilic, or lipophilic groups selected to optimize the physicochemical and biological properties of compounds of Formula I. These properties include receptor binding, receptor selectivity, tissue penetration, lipophilicity, toxicity, bioavailability, and pharmacokinetics. As will be demonstrated later, some of the compounds of the present invention exhibit favorable in vivo biological properties that could not be ascertained from the prior art literature. Compounds of the present invention are useful for the treatment of neurological disorders. Moreover, as mentioned before, the receptor binding and pharmacological properties are very sensitive to the overall molecular topology, and these properties cannot be predicted just from the inspection of molecular structure. The overall geometry of the prior art compound 6a is planar whereas the structure of compound 13a of present invention derived from Formula I has a bent conformation with a dihedral angle of about 110° between the E-ring phenyl group and the 7-membered ring as shown in FIG. 1 . Hence, the biological activities of the compounds derived from these two scaffolds are expected to be different.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1 . Energy-minimized structures of compounds 6a and 13a.
FIG. 2 . General synthetic scheme for pyridoindolobenz[b,e]azepines.
FIG. 3 . Evaluation of DDD-024 in mice meth-seeking behavior model.
FIG. 4 . Evaluation of DDD-024 in mice MDMA-seeking behavior model.
FIG. 5 . Evaluation of DDD-024 in mice depression model.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to pentacyclic compounds of Formula I, wherein
X is —CHR 10 —, —O—, —NR 11 —, —S—, —SO—, or —SO 2 —;
Y is a single bond or a double bond;
A and B are independently —(CH 2 ) n —, and subscript ‘n’ varies from 0 to 3;
R 1 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 5 -C 10 aryl unsubstituted or substituted with electron donating groups (EDG) or electron withdrawing groups (EWG), C 1 -C 15 aroylalkyl, and C 1 -C 10 alkoxycarbonylalkyl, C 1 -C 10 carbamoylalkyl, C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG;
R 2 to R 11 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, hydroxyl, C 1 -C 10 alkoxyl, —NR 12 R 13 , C 1 -C 10 hydroxyalkyl, halogen, trihaloalkyl, cyano, carboxyl, C 1 -C 10 acyl, C 1 -C 10 alkoxyalkyl; C 1 -C 10 alkoxycarbonyl; C 5 -C 10 aryl unsubstituted or substituted with EDG or EWG, and C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG; and
R 12 and R 13 are independently hydrogen or C 1 -C 10 alkyl, and R 12 and R 13 may optionally be tethered together from a ring.
The phrase, ‘electron donating group (EDG)’ and ‘electron withdrawing group (EWG)’ are well understood in the art. EDG comprises alkyl, hydroxyl, alkoxyl, amino, acyloxy, acylamino, mercapto, alkylthio, and the like. EWG comprises halogen, acyl, nitro, cyano, carboxyl, alkoxycarbonyl, and the like.
The first embodiment of the present invention is represented by Formula I, wherein
X is —CHR 10 —;
Y is a single bond or a double bond;
A and B are —(CH 2 ) n —, and ‘n’ is 1 or 2;
R 1 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 5 -C 10 aryl unsubstituted or substituted with electron donating or electron withdrawing groups, C 1 -C 15 aroylalkyl, and C 1 -C 10 alkoxycarbonylalkyl, C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG;
R 2 to R 11 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, hydroxyl, C 1 -C 10 alkoxyl, —NR 12 R 13 , C 1 -C 10 hydroxyalkyl, halogen, trihaloalkyl, cyano, carboxyl, C 1 -C 10 acyl, C 1 -C 10 alkoxyalkyl; C 1 -C 10 alkoxycarbonyl; C 5 -C 10 aryl unsubstituted or substituted with EDG or EWG, and C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG; and
R 12 and R 13 are independently hydrogen or C 1 -C 10 alkyl, and R 12 and R 13 may optionally be tethered together from a ring.
The second embodiment is represented by Formula I, wherein
X is —O—;
Y is a single bond or a double bond;
A and B are —(CH 2 ) n —, and ‘n’ is 1 or 2;
R 1 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 5 -C 15 aryl unsubstituted or substituted with electron donating or electron withdrawing groups, C 1 -C 15 aroylalkyl, and C 1 -C 10 alkoxycarbonylalkyl, C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG;
R 2 to R 11 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, hydroxyl, C 1 -C 10 alkoxyl, —NR 12 R 13 , C 1 -C 10 hydroxyalkyl, halogen, trihaloalkyl, cyano, carboxyl, C 1 -C 10 acyl, C 1 -C 10 alkoxyalkyl; C 1 -C 10 alkoxycarbonyl; C 5 -C 15 aryl unsubstituted or substituted with EDG or EWG, and C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG; and
R 12 and R 13 are independently hydrogen or C 1 -C 10 alkyl, and R 12 and R 13 may optionally be tethered together from a ring.
The third embodiment is represented by Formula I, wherein
X is —S—;
Y is a single bond or a double bond;
A and B are —(CH 2 ) n —, and ‘n’ is 1 or 2;
R 1 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 5 -C 10 aryl unsubstituted or substituted with electron donating or electron withdrawing groups, C 1 -C 15 aroylalkyl, and C 1 -C 10 alkoxycarbonylalkyl, C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG;
R 2 to R 11 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, hydroxyl, C 1 -C 10 alkoxyl, —NR 12 R 13 , C 1 -C 10 hydroxyalkyl, halogen, trihaloalkyl, cyano, carboxyl, C 1 -C 10 acyl, C 1 -C 10 alkoxyalkyl; C 1 -C 10 alkoxycarbonyl; C 5 -C 10 aryl unsubstituted or substituted with EDG or EWG, and C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG; and
R 12 and R 13 are independently hydrogen or C 1 -C 10 alkyl, and R 12 and R 13 may optionally be tethered together from a ring.
The fourth embodiment is represented by Formula I, wherein
X is —NR 11 —;
Y is a single bond or a double bond;
A and B are —(CH 2 ) n —, and ‘n’ is 1 or 2;
R 1 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 5 -C 10 aryl unsubstituted or substituted with electron donating or electron withdrawing groups, C 1 -C 15 aroylalkyl, and C 1 -C 10 alkoxycarbonylalkyl, C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG;
R 2 to R 11 are independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, hydroxyl, C 1 -C 10 alkoxyl, —NR 12 R 13 , C 1 -C 10 hydroxyalkyl, halogen, trihaloalkyl, cyano, carboxyl, C 1 -C 10 acyl, alkoxyalkyl; C 1 -C 10 alkoxycarbonyl; C 5 -C 10 aryl unsubstituted or substituted with EDG or EWG, and C 5 -C 10 arylalkyl unsubstituted or substituted with EDG or EWG; and
R 12 and R 13 are independently hydrogen or C 1 -C 10 alkyl, and R 12 and R 13 may optionally be tethered together from a ring.
The fifth embodiment is represented by Formula I, wherein
X is —CHR 10 —;
Y is a single bond or a double bond;
A is —CH 2 —;
B is —CH 2 CH 2 —;
R 1 is hydrogen, C 1 -C 10 alkyl, C 5 -C 10 arylalkyl; or C 1 -C 15 aroylalkyl; and
each of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is hydrogen.
The sixth embodiment is represented by Formula I, wherein
X is —O—;
Y is a single bond or a double bond;
A is —CH 2 —;
B is —CH 2 CH 2 —;
R 1 is hydrogen, C 1 -C 10 alkyl, C 5 -C 10 arylalkyl; or C 1 -C 15 aroylalkyl; and
each of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is hydrogen.
The seventh embodiment is represented by Formula I, wherein
X is —S—;
Y is a single bond or a double bond;
A is —CH 2 —;
B is —CH 2 CH 2 —;
R 1 is hydrogen, C 1 -C 10 alkyl, C 5 -C 10 arylalkyl; or C 1 -C 15 aroylalkyl; and
each of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is hydrogen.
The seventh embodiment is represented by Formula I, wherein
X is —NR 11 —;
Y is a single bond or a double bond;
A is —CH 2 —;
B is —CH 2 CH 2 —;
R 1 is hydrogen, C 1 -C 10 alkyl, C 5 -C 10 arylalkyl; or C 1 -C 15 aroylalkyl;
each of R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 is hydrogen; and
R 11 is hydrogen or C 1 -C 10 alkyl.
The compounds belonging to Formula I can be synthesized by the well-known Fisher indole synthesis starting from known tricyclic dibenzazepines, dibenzoxazepines, and dibenzothiazepines (7a,b) [14, 15] as outlined in FIG. 2 . Stereospecific reduction of the double bond in B|C ring junction can be accomplished by NaBH 3 CN/TFA or with BH 3 to give the cis- and trans-reduced compounds 11a,b and 12a,b respectively. Compounds of the present invention may exist as a single stereoisomer or as mixture of enantiomers and diastereomers whenever chiral centers are present. Individual enantiomers can be isolated by resolution methods or by chromatography using chiral columns, and the diastereomers can be separated by standard purification methods such as fractional crystallization or chromatography.
As is well known in the pharmaceutical industry, the compounds of the present invention represented by Formula I, commonly referred to as ‘active pharmaceutical ingredient (API)’ or ‘drug substance’, can be prepared as a pharmaceutically acceptable formulation. In particular, the drug substance can be formulated as a salt, ester, or other derivative, and can be formulated with pharmaceutically acceptable buffers, diluents, carriers, adjuvants, preservatives, and excipients. The phrase “pharmaceutically acceptable” means those formulations which are, within the scope of sound medical judgment, suitable for use in contact with the tissues of humans and animals without undue toxicity, irritation, allergic response and the like, and are commensurate with a reasonable benefit/risk ratio. Pharmaceutically acceptable salts include, but are not limited to acetate, adipate, citrate, tartarate, benzoate, phosphate, glutamate, gluconate, fumarate, maleate, succinate, oxalate, chloride, bromide, hydrochloride, sodium, potassium, calcium, magnesium, ammonium, and the like. The formulation technology for manufacture of the drug product is well-known in the art, and are described in “Remington, The Science and Practice of Pharmacy” [16], incorporated herein by reference in its entirety.
The final formulated product, commonly referred to as ‘drug product,’ may be administered enterally, parenterally, or topically. Enteral route includes oral, rectal, topical, buccal, ophthalmic, and vaginal administration. Parenteral route includes intravenous, intramuscular, intraperitoneal, intrasternal, and subcutaneous injection or infusion. The drug product may be delivered in solid, liquid, or vapor forms, or can be delivered through a catheter for local delivery at a target. Also, it may be administered alone or in combination with other drugs if medically necessary.
Formulations for oral administration include capsules (soft or hard), tablets, pills, powders, and granules. Such formulations may comprise the API along with at least one inert, pharmaceutically acceptable ingredients selected from the following: (a) buffering agents such as sodium citrate or dicalcium phosphate; (b) fillers or extenders such as starches, lactose, sucrose, glucose, mannitol, and silicic acid; (c) binders such as carboxymethylcellulose, alginates, gelatin, polyvinylpyrrolidone, sucrose and acacia; (d) humectants such as glycerol; (e) disintegrating agents such as agar-agar, calcium carbonate, potato or tapioca starch, alginic acid, certain silicates and sodium carbonate; (f) solution retarding agents such as paraffin; (g) absorption accelerators such as quaternary ammonium compounds; (h) wetting agents such as cetyl alcohol and glycerol monostearate; (i) absorbents such as kaolin and bentonite clay and (j) lubricants such as talc, calcium stearate, magnesium stearate, solid polyethylene glycols, sodium lauryl sulfate. and mixtures thereof; (k) coatings and shells such as enteric coatings, flavoring agents, and the like.
Liquid dosage forms for oral administration include pharmaceutically acceptable emulsions, solutions, suspensions, syrups and elixirs. In addition to the API, the liquid dosage forms may contain inert diluents, solubilizing agents, wetting agents, emulsifying and suspending agents, sweetening, flavoring, and perfuming agents used in the art.
Compositions suitable for parenteral injection may comprise physiologically acceptable, sterile aqueous or nonaqueous isotonic solutions, dispersions, suspensions or emulsions, and sterile powders for reconstitution into sterile injectable solutions or dispersions. The compositions may also optionally contain adjuvants such as preserving; wetting; emulsifying; dispensing, and antimicrobial agents. Examples of suitable carriers, diluents, solvents, vehicles, or adjuvants include water; ethanol; polyols such as propyleneglycol, polyethyleneglycol, glycerol, and the like; vegetable oils such as cottonseed, groundnut, corn, germ, olive, castor and sesame oils, and the like; organic esters such as ethyl oleate and suitable mixtures thereof; phenol, parabens, sorbic acid, and the like.
Injectable formulations may also be suspensions that contain suspending agents such as ethoxylated isostearyl alcohols, polyoxyethylene sorbitol and sorbitan esters, microcrystalline cellulose, aluminum metahydroxide, bentonite, agar-agar and tragacanth, or mixtures of these substances, and the like. Prolonged absorption of the injectable pharmaceutical form can be brought about by the use of agents delaying absorption, for example, aluminum monostearate and gelatin. Proper fluidity can be maintained, for example, by the use of coating materials such as lecithin, by the maintenance of the required particle size in the case of dispersions, and by the use of surfactants. In some cases, in order to prolong the effect of the drug, it is desirable to slow the absorption of the drug from subcutaneous or intramuscular injection. This can be accomplished by the use of a liquid suspension. The rate of absorption of the drug then depends upon its rate of dissolution which, in turn, may depend upon crystal size and crystalline form. Alternatively, delayed absorption of a parenterally administered drug form is accomplished by dissolving or suspending the drug in an oil vehicle.
Injectable depot forms are made by forming microencapsulated matrices of the drug in biodegradable polymers. Depending upon the ratio of drug to polymer and the nature of the particular polymer employed, these compositions release the active ingredient(s) only, or preferentially, in a certain part of the intestinal tract, optionally, in a delayed manner. Thus, the rate of drug release and the site of delivery can be controlled. Examples of embedding compositions include, but are not limited to polylactide-polyglycolide poly(orthoesters), and poly(anhydrides), and waxes. The technology pertaining to controlled release formulations are described in “Design of Controlled Release Drug Delivery Systems,” [17] incorporated herein by reference in its entirety.
Formulations for topical administration include powders, sprays, ointments and inhalants. These formulations include the API along with suitable non-irritating excipients or carriers such as cocoa butter, polyethylene glycol or a suppository wax which are solid at room temperature but liquid at body temperature and therefore melt in the rectum or vaginal cavity and release the active compound.
Compounds of the present invention can also be administered in the form of liposomes. Any non-toxic, physiologically acceptable and metabolizable lipid capable of forming liposomes can be used. The present compositions in liposome form can contain, in addition to a compound of the present invention, stabilizers, preservatives, excipients and the like. The preferred lipids are natural and synthetic phospholipids and phosphatidyl cholines (lecithins) used separately or together. Methods to form liposomes are known in the art and are described in “Liposomes,” [18], which is incorporated herein by reference in its entirety.
The compounds of the present invention can also be administered to a patient in the form of pharmaceutically acceptable ‘prodrugs.’ Prodrugs are generally used to enhance the bioavailabilty, solubility, in vivo stability, or any combination thereof of the API. They are typically prepared by linking the API covalently to a biodegradable functional group such as a phosphate that will be cleaved enzymatically or hydrolytically in blood, stomach, or GI tract to release the API. A detailed discussion of the prodrug technology is described in “Prodrugs: Design and Clinical Applications,” [19] incorporated herein by reference.
The dosage levels of API in the drug product can be varied so as to achieve the desired therapeutic response for a particular patient. The phrase “therapeutically effective amount” of the compound of the invention means a sufficient amount of the compound to treat disorders, at a reasonable benefit/risk ratio applicable to any medical treatment. It will be understood, however, that the total daily usage of the compounds and compositions of the present invention will be decided by the attending physician within the scope of sound medical judgment. The specific therapeutically effective dose level for any particular patient will depend upon a variety of factors including the disorder being treated, the severity of the disorder; activity of the specific compound employed; the specific composition employed, age, body weight, general health, sex, diet of the patient; the time of administration, route of administration, and rate of excretion of the specific compound employed, and the duration of the treatment. The total daily dose of the compounds of this invention administered may range from about 0.0001 to about 1000 mg/kg/day. For purposes of oral administration, more preferable doses can be in the range from about 0.001 to about 5 mg/kg/day. If desired, the effective daily dose can be divided into multiple doses for optimal therapeutic effect.
The following examples illustrate specific embodiments and utilities of the invention, and are not meant to limit the invention. As would be apparent to skilled artisans, various modifications in the composition, operation, and method are possible, and are contemplated herein without departing from the concept and scope of the invention as defined in the claims.
EXAMPLE 1
Synthesis of Compound of Formula I, Wherein X is CHR 10 , Y is a Double Bond, R 1 is CH 3 , and R 2 to R 10 are Hydrogens (13a) (DDD-029)
Step 1.
Dibenz[b,e]azepine (1.95 g, 10 mmol) in ethanol (25 mL), and acetic acid (10 mL) was gently stirred and heated to dissolved all the solids. Thereafter, the solution was cooled to ambient temperature and treated with a concentrated, aqueous solution of NaNO 2 (1.03 g, 15 mmol) in water (5 mL) added dropwise over a period of 5 minutes. The reaction was stirred at ambient temperature for 30 minures and treated with water (30 mL). The solid was collected by filtration, washed with water, and dried to give 1.9 g (89%) of the N-nitroso compound. The material was used as such for the next step.
Step 2.
A stirring mixture of nitroso compound from Step 1 (336 mg, 1.5 mmol) and N-methyl-4-piperidone hydrochloride (270 mg, 1.8 mmol) in ethanol (4.5 mL) and acetic acid (1.5 mL) was treated with zinc dust (393 mg, 6.0 mmol) added in three equal portions allowing 5-10 minutes between the additions. The reaction was then stirred at ambient temperature for 2 hours. The reaction mixture was cooled to about 0-5° C., diluted and carefully treated with 10% NaOH (2 mL). The reaction mixture was extracted with dichloromethane (3×30 mL). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and the filtrate evaporated in vacuo. The crude material was purified by flash chromatography (silica gel, gradient elution, 0-10% methanol/chloroform over 90 minutes) to furnish 200 mg (43%) of the hydrazone.
Step 3.
A suspension of the hydrazone from Step 2 (400 mg, 1.3 mmol) in toluene (3 mL) was treated with 1 M solution of hydrogen chloride in diethyl ether (2.6 mL, 2.6 mmol) and p-toluenesulfonic acid (300 mg, 1.6 mmol), and the entire mixture was heated under reflux for 2 hours. The reaction mixture was cooled to ambient temperature, treated with 10% NaOH (4 mL), and extracted with dichloromethane (3×30 mL). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and the filtrate evaporated in vacuo. The crude product was purified by flash chromatography (silica gel, gradient elution, 0-10% methanol/chloroform over 90 minutes) to give 140 mg (37%) of the desired product 13a. HRMS (ESI) m/z calcd. for C 20 H 21 N 2 (M+H) + 289.1699, found, 289.1698.
EXAMPLE 2
Synthesis of Compound of Formula I, Wherein X is O, Y is a Double Bond, R 1 is CH 3 , and R 2 to R 9 are Hydrogens 13b (DDD-024)
Step 1.
To a well stirred solution of compound dibenz[b,e]oxazepine (6.98 g, 32.7 mmol) in THF (30 mL) and AcOH (9 mL), a concentrated solution of NaNO 2 (7.03 g, 101.9 mmol) in water (12 mL) was added dropwise at ambient temperature. The reaction was stirred at ambient temperature for 20 min and treated with water (100 mL). The product was filtered, washed with water, and dried to give 7.67 g (97%) of the nitroso compound.
Step 2.
To a stirred solution of nitroso compound from step 1 (14.6 g, 61.1 mmol) and N-methyl 4-pyridone (9.04g, 79.9 mmol) in ethanol (150 mL) and acetic acid (20 mL) at 55° C., was added zinc dust (12.0 g, 183.5 mmol) in three equal portions allowing 10 mins between the additions. The reaction was stirred for another 5 minutes and filtered hot. The solid washed with ethanol, and the resultant solution was heated to reflux for 30 minutes, and thereafter the solvent was removed in vacuo. The residue was treated with 8 mL of acetic acid, and heated to reflux for about 16 hours. The solvent was removed in vacuo, and the residue was dissolved in methylene chloride (500 mL). The solid impurity was removed by filtration, and the filtrate was washed with 10% NaOH solution. The combined organic layer was washed with water and brine, dried over anhydrous sodium sulfate, filtered and the filtrate taken to dryness in vacuo. The crude product was purified by flash chromatography on silica gel using 0-5% MeOH/chloroform as the eluent to give 3.0 g (16%) of the desired product 13b. HRMS (ESI) m/z calcd. for C 19 H 19 N 2 O (M+H) + 291.1492, found, 291.1484.
EXAMPLE 3
Synthesis of Compound of Formula I, Wherein X is O, Y is a Single Bond with Cis-fused B|C Rings, R 1 is CH 3 , and R 2 to R 9 are Hydrogens 14a,b (DDD-030)
A stirrerd cold solution of compound 13b from Example 2 (2 mmol) in trifluoroacetic acid (6.5 mL) at −5° C., was carefully treated with solid sodium cyanoborohydride (0.125 g, 2.4 mmol). The reaction mixture was then stirred at ambient temperature for 3 h, treated with 6N HCl solution, and heated under reflux for 30 minutes. The solution was cooled to ambient temperature, and excess trifluoroacetic acid is removed in vacuo. The residue was rendered alkaline with 25% NaOH solution (12 mL), and the solution was extracted with chloroform. The combined organic layers are washed with water and brine, and dried over anhydrous sodium sulfate, filtered, and the filtrate evaporated in vacuo. The crude compound was purified by flash column chromatography on silica gel using 0-5% MeOH/Chloroform gradient elution. HRMS (ESI) m/z calcd. for C 19 H 21 N 2 O (M+H) + 293.1648, found, 293.1647.
Example 4
Synthesis of Compound of Formula I, Wherein X is O, Y is a Single Bond with Trans-fused B|C rings, R 1 is CH 3 , and R 2 to R 9 are Hydrogens 15a,b (DDD-031)
The compound 13b from Example 2 (1 mmol) was treated with borane-THF (10 mL, 1.0 M) at ambient temperature, and the mixture is heated under reflux for 1 hour by which time the reaction mixture became clear. After cooling to ambient temperature, the solution was treated with water to quench excess reagent borane reagent. The solvents were removed under reduced pressure, and the residue was treated with conc. HCl (7 mL). The mixture was heated to reflux for 3 hours and evaporated to dryness in vacuo, and treated with 10% NaOH solution (10 mL). The product was then extracted with EtOAc, washed with water and brine, dried over anhydrous sodium sulfate, filtered, and the filtrate evaporated to dryness under reduced pressure. The crude product was purified by flash chromatography on silica gel using 0-5% MeOH/Chloroform gradient elution. HRMS (ESI) m/z calcd. for C 19 H 21 N 2 O (M+H) + 293.1648, found, 293.1647.
EXAMPLE 5
Receptor Binding Data of Compounds 6a, 13a, and 13b
The receptor binding data of compounds 6a, 13a, and 13b are given in Table 1. As can be clearly noted, the receptor binding profiles between 13a, and 13b are substantially different from each other as well as from the prior art compound 6a. Most noteworthy is the fact that neither of the two compounds 13a and 13b binds significantly to any of the dopamine receptors. Compound 13a displays strong binding to 5-HT 1D , 5-HT 2B , and H 1 , and moderate binding at 5-HT 1A , 5-HT 6 , and 5-HT 7 . Compound 13b binds strongly to 5-HT 1A ; and moderate binding to 5-HT 1D , HT 2c , binding 5-HT 6 , 5-HT 7 , and σ 2 .
TABLE 1
Receptor Binding Data, K i (nM).
Receptor
6a
13a
13b
Serotonin
5-HT 1A
596
375
32
5-HT 1B
1363
715
738
5-HT 1D
85
29
385
5-HT 1E
4045
>10,000
>10,000
5-HT 2A
24
736
927
5-HT 2B
87
57
195
5-HT 2C
10
>10,000
247
5-HT 3
>10,000
>10,000
>10,000
5-HT 5A
750
>10,000
1905
5-HT 6
155
273
189
5-HT 7
100
212
258
Dopamine
D 1
>10,000
>10,000
>10,000
D 2
835
>10,000
>10,000
D 3
>10,000
1496
>10,000
D 4
>10,000
>10,000
>10,000
D 5
581
>10,000
>10,000
α-Adrenergic
α 1A
2371
>10,000
5863
α 1B
3310
>10,000
>10,000
α 1D
595
>10,000
5033
α 2A
228
1800
1459
α 2B
413
2187
>10,000
α 2C
173
770
507
β-Adrenergic
β 1
>10,000
>10,000
>10,000
β 2
>10,000
>10,000
>10,000
β 3
>10,000
>10,000
>10,000
Histamine
H 1
50
48
733
H 2
81
>10,000
4732
H 3
>10,000
>10,000
Sigma
σ 1
6143
>10,000
220
σ 2
2234
520
1815
Opioid
δ
>10,000
>10,000
310
κ
2179
>10,000
>10,000
μ
>10,000
>10,000
>10,000
Muscarinic
M 1
4465
>10,000
>10,000
M 2
>10,000
>10,000
>10,000
M 3
3761
>10,000
>10,000
M 4
>10,000
>10,000
>10,000
M 5
5167
>10,000
>10,000
Transporters
Dopamine
>10,000
>10,000
>10,000
Norepinephrine
>10,000
>10,000
1955
Serotonin
2190
2190
413
EXAMPLE 6
Mice Meth-seeking Behavioral Study with Compound 13b (DDD-024)
DDD-024 was initially tested for effects on the reinstatement of meth seeking in a small pilot group of rats with a history of chronic meth self-administration. Rats self-administered meth (0.02 mg/50 μl bolus; approximately 0.06 mg/kg) for two weeks, followed by daily extinction sessions, whereby responding did not result in reinforcement. Rats received a vehicle (10% DMSO) or DDD-024 (10 mg/kg) injection (i.p.) just before each reinstatement session, which consisted of a meth priming injection (1 mg/kg, i.p.) and presentation of meth-associated cues (tone and light) upon each lever press. Results: DDD-024 significantly reduced the number of lever presses, reflecting attenuation of meth seeking behavior ( FIG. 3 ).
EXAMPLE 7
Mice MDMA Seeking Behavioral Study with Compound 13b (DDD-024)
In this in vivo study, locomotor activity was measured in a circular corridor with four infrared beams placed at every 90° (Imetronic, France). Counts were incremented by consecutive interruption of two adjacent beams (i.e. mice moving through one-quarter of the corridor). DDD-024 was tested in MDMA-induced motor behavior at 5, 10 and 20 mg/kg, ip, in mice (129SV/PAS background, 8 week old, Charles River Laboratories). The animals were injected with vehicle and individually placed in the activity box for 30 min during 3 days consecutively for habituation before experiments. Mice received vehicle or DDD-024 (5-20 mg/kg, i.p.) injection 30 min before MDMA injection (10 mg/kg). Results: DDD-024 completely blocked the increase in motor activity elicited by MDMA at 20 mg/kg, i p. in mice and partially at 10 mg/kg reflecting attenuation of MDMA-seeking behavior ( FIG. 4 ).
EXAMPLE 8
In Vivo Depression Model Study with Compound 13b (DDD-024)
DDD-024 was tested in the forced swim test using three groups of rats (n=10 each for vehicle, positive control (imipramine), and DDD-024. Each subject in the control group received 10 mg/kg of imipramine, and those in the test group received 5, 10, and 20 mg/kg of DDD-024 (i.p.). After 1 hour, the rats were individually placed in a 500 mL container of water (22° C.) filled to a height of 10 cm. Rats were observed for immobility and time taken for immobility was recorded, as well as recording performance on video. Immobility is the measure of the absence of active, escape-oriented behaviors such as swimming, jumping, rearing, sniffing, or diving. Results: DDD-024 is comparable to imipramine in its antidepressive activity at the 10 mg/kg dose ( FIG. 5 ).
REFERENCES
1. Fox, R. B.; Powell, W. H. Nomenclature of Organic Compounds: Principles and Practice , Second Edition. Oxford University Press, Oxford, 2001.
2. Hellwinkel, D. Systematic Nomenclature of Organic Chemistry: A Directory of Comprehension and Application of its Basic Principles . Springer-Verlag, Berlin, 2001.
3. American Psychiatric Association: Diagnostic and Statistical Manual of Mental Disorders, 4 th Edition. Washington, D.C., Association, A.P., 1994.
4. Roth, B. L. Ed. The Serotonin Receptors. Human Press, Totowa, N.J., 2006.
5. Nichols, D. E.; Nichols, C. D. Serotonin Receptors. Chem. Rev. 2008, 108, 1614.
6. Micale, V.; Leggio, G. M.; Mazzola, C.; Drago, F. Brain Res. 2006, 112, 207.
7. Jongen-Relo, A. L.; Bespalov, A. Y.; Rueter, L. E.; Freeman, A. S.; Decker, M. W.; Gross, G.; Schoemaker, H.; Sullivan, J. P.; Van Gaalen. M. M.; Wicke, K.; Zhang, M.; Amberg, W.; Garcia-LaDona, J. Soc. Neurosci. Annual Meet, Atlanta, Ga. 2006, 526, 29.
8. King, M. V.; Marsden, C. A.; Fone, K. C. A role for the 5-HT 1A , 5-HT 4 and 5-HT 6 in learning and memory. Trends Pharmacol. Sci. 2008, 29, 482.
9. Brenchat, A. et al. Pain 2010, 149, 483-494.
10. Mnie-Filali, O.; Lambas-Senas, L.; Zimmer, L.; Haddjeri, N. Drug News Perspect. 2007, 20, 613.
11. Doly, S., Valjent, E., Setola, V., Callebert, J., Herve, D.; Launay, J.-L., and Maroteaux, L. J. Neurosci. 2008, 28, 2933.
12. Rajagopalan, P. U.S. Pat. No. 4,438,120; 1984.
13. Rajagopalan, P. U.S. Pat. No. 4,219,550; 1980.
14. Adams, C. W. U.S. Pat. No. 3,983,123; 1976.
15. Bandyopadhyaya, A.; Rajagopalan, D. R.; Rath, N. P., Herrold, A., Rajagopalan, R., Napier, C. T., Tedford, C. E., and Rajagopalan, P. Medicinal Chemistry Communications 2012, 3, 580-583.
16. Nandakumar, M. V.; Verkade, J. G. Pd 2 dba 3 /P(i-BuNCH 2 CH 2 ) 3 N: Tetrahedron 2005, 61, 9775-9782.
17. Pharmaceutical Manufacturing. In Remington: The Science and Practice of Pharmacy . Lippincott Williams & Wilkins, Philadelphia, 2005, 691-1058.
18. Weissig, V. Liposomes: Methods and Protocols Volume 1: Pharmaceutical Nanocarriers . Humana Press, New York, 2009.
19. Li, X. Design of Controlled Release Drug Delivery Systems. McGraw-Hill, New York, 2006.
20. Rautio, J. et al. Prodrugs: Design and Clinical Applications. Nature Reviews Drug Discovery 2008, 7, 255-270.
|
The present invention discloses pyridoinolobenz[b,e]azepine derivatives of Formula 1,
wherein X is —O—, —S—, —SO—, or —SO 2 —. Y is a single bond or a double bond. A and B are independently —(CH 2 ) n —; and ‘n’ varies from 0 to 3. R 1 to R 9 are various electron donating, electron withdrawing, hydrophilic, or lipophilic groups selected to optimize the physicochemical and biological properties of compounds of Formula I.
| 2
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This patent application claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 61/647,388, filed May 15, 2012, which is incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The subject invention is directed to the field of medical devices, and more particularly to devices for use in protecting patient-connected structures such as tubes and wires, including but not limited to IV tube sets, catheters and sensor wires.
[0004] 2. Description of Related Art
[0005] Various patient-connected structures find use in medical facilities, in operating rooms, patient rooms, and the like. Such structures include, for example, intravenous (I.V.) infusion sets, electrical leads for electrocardiogram (EKG), electroencephalogram (EEG), oxygen sensors, wound drains, suction tubing, urinary catheter tubing, feeding tubes and still other structures.
[0006] While placement of such structures is necessary to treat injuries or symptoms, to alleviate pain and discomfort that a patient is enduring and, in many cases, keep the patient alive, such structures and the connections thereof are susceptible to tampering and damage, particularly in cases of uncooperative patients, and more particularly in cases of mentally-ill patients.
[0007] Applicant recognizes that it would be advantageous to provide devices in a clinical setting that could be employed to protect the aforementioned structures from tampering, damage and improper removal, thereby protecting the patient's wellbeing to the extent possible.
SUMMARY OF THE PREFERRED EMBODIMENTS
[0008] In accordance with one aspect of the present invention, a medical conduit protection device is provided having an elongate body having a wall, defining a lumen therein, and having first and second opposed ends, the body being adapted and configured to receive, within the lumen thereof, one or more elongate medical conduits. The device also includes a first tether provided on the first end of the body, the first tether being adapted and configured to secure the first end of the body to a patient-end anchor point (such as a patient or a location relatively near to a patient, such as a bed rail) and a second tether provided on the second end of the body, the second tether being adapted and configured to secure the second end of the body to an external anchor point. The medical conduit protection device inhibits tampering with or damage to the one or more medical conduits within the lumen of the body by transferring externally-applied strain away from the one or more medical conduits within the lumen thereof.
[0009] The body can be a substantially continuous tubular structure, adapted and configured to receive one or more medical conduits therethrough, from the first end to the second end thereof. The body can be formed from a resilient material which is resistant to plastic deformation. Alternatively, the body can be formed from a nonwoven fabric. The body can be provided in any needed dimensions practicable, such as with a diameter of between about 2.0 centimeters and about 5.0 centimeters, for example.
[0010] In accordance with a further aspect of the invention, the subject medical conduit protection devices can include one or more closure elements adapted and configured for inhibiting access to the one or more medical conduits within the lumen thereof.
[0011] In accordance with the invention, the subject medical conduit protection devices can include at least one closure element provided in connection with the body, for inhibiting access to the lumen thereof. The at least one closure element can be a reversibly attached closure element. Further, the at least one closure element can be adapted and configured to require a separate tool for removal thereof. The at least one closure element can be a one-way closure element. The at least one closure element can be a concentrically rotatable tubular element arranged over the body.
[0012] In accordance with a further aspect of the invention, the body can include at least one inflatable element, the at least one inflatable element being adapted and configured to impart structural rigidity to at least a portion of the body.
[0013] Additionally or alternatively, the body can include at least one semi-rigid element, the at least one semi rigid element being adapted and configured to impart structural rigidity to at least a portion of the body. The at least one semi-rigid element can be a helical spine provided in connection with the wall of the body.
[0014] In accordance with the invention, the subject medical conduit protection devices can include an alarm adapted and configured to sound when detecting tampering with the medical conduit protection device.
[0015] In accordance with the invention, the subject medical conduit protection devices can additionally or alternatively include a safety release feature, adapted and configured to release when a force exceeding a predetermined value is applied to the medical conduit protection device. An alarm can be provided in connection with the safety release feature, adapted and configured such that when the force exceeding the predetermined value is applied to the medical conduit protection device, the alarm is sounded.
[0016] The safety release features can include, but are not limited to one or more lines of weakness, severable connection, releasable connection and/or elastic elements.
[0017] In accordance with a further aspect of the invention, a method of protecting medical conduits from damage or tampering is provided, including the steps of providing a medical conduit protection device, the medical conduit protection device being adapted and configured for attachment at a first end to a patient-end anchor point and at a second end to an external anchor point apart from the patient, arranging the medical conduit protection device about one or more medical conduits so as to inhibit access to the one or more medical conduits, and to distribute externally-applied forces away from the one or more medical conduits, securing the first end of the protection device to the patient-end anchor point, securing the second end of the protection device to an anchor point apart from the patient, and connecting the one or more medical conduits at the first end to the patient or a location near the patient and at the second end to medical equipment.
[0018] In accordance with still a further aspect of the invention, a medical conduit protection device is provided, having an elongate body having a wall, defining a lumen therein, and having first and second opposed ends, the body being adapted and configured to receive, within the lumen thereof, one or more elongate medical conduits, the first end of the body being adapted and configured to be secured directly to a patient-end anchor point, the medical conduit protection device inhibiting tampering with or damage to the one or more medical conduits within the lumen of the body by shielding from damage the one or more medical conduits within the lumen thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] So that those skilled in the art to which the subject invention appertains will readily understand how to make and use the medical conduit protection devices, systems and related methods of the subject invention without undue experimentation, exemplary embodiments thereof are described in detail below along with the related methods, with reference to the drawings, wherein:
[0020] FIG. 1 is a schematic side view of a medical conduit protection device in accordance with a first embodiment of the subject invention, which includes a tether at each opposed end, and one or more closure elements disposed along the body thereof, only one of which being illustrated for simplicity;
[0021] FIG. 2 is a cross-sectional view of the medical conduit protection device of FIG. 1 , taken along line A-A of FIG. 1 ;
[0022] FIG. 3 is a side view of a medical conduit protection device in accordance with a second embodiment of the invention, wherein a patient-end tether is provided as an adjustable cuff;
[0023] FIG. 4 is a detail view of a patient-end tether of the medical conduit protection device of FIG. 3 ;
[0024] FIG. 5 is a detail view of a far end of the medical conduit protection device of FIG. 3 , illustrating a longitudinal slit in the body thereof;
[0025] FIG. 6 is a detail view of a far end of the medical conduit protection device of FIG. 3 , illustrating one example of a tether for connection to an external anchor point;
[0026] FIG. 7 is a detail view of a patient-end tether of the medical conduit protection device of FIG. 3 , as applied to a patient's arm;
[0027] FIG. 8 is a detail view of the medical conduit protection device of FIG. 3 , further illustrating a longitudinal slit in the body thereof;
[0028] FIG. 9 is a side view of a medical conduit protection device in accordance with a third embodiment of the invention, wherein a relatively large diameter body is provided, in conjunction with one more closures arranged circumferentially about the body in one or more locations along the axis of the body;
[0029] FIG. 10 is a side view of a medical conduit protection device in accordance with a fourth embodiment of the invention, wherein rotatable closure elements are provided for inhibiting access to conduits held within a lumen of the device;
[0030] FIG. 11 is a cross sectional view of the medical conduit protection device of FIG. 10 , taken across line B-B of FIG. 10 ;
[0031] FIG. 12 is an isometric view of a medical conduit protection device in accordance with a fifth embodiment of the invention, wherein a helical structural element is provided in connection with the body of the device;
[0032] FIG. 13 is a cross sectional view of the medical conduit protection device of FIG. 12 , taken across line C-C of FIG. 12 ;
[0033] FIG. 14 is an isometric view of a medical conduit protection device in accordance with a sixth embodiment of the invention, wherein inflatable channels are provided in connection with the body of the device in a longitudinal and circumferential pattern to enhance structural rigidity thereof;
[0034] FIG. 15 is an isometric view of a medical conduit protection device in accordance with a seventh embodiment of the invention, wherein inflatable channels are provided in connection with the body of the device in a diagonal pattern to enhance structural rigidity thereof;
[0035] FIG. 16 is a partial side isometric view of a medical conduit protection device in accordance with an eighth embodiment of the invention, which is provided with a safety release feature, in which connections between two segments of a body are connected by severable or otherwise releasable connections;
[0036] FIG. 17 is a partial side isometric view of a medical conduit protection device in accordance with a ninth embodiment of the invention, which is provided with a safety release feature, in which connections between two segments of a continuous body are folded over one another and connected by severable or otherwise releasable connections;
[0037] FIG. 18 is a partial side isometric view of a medical conduit protection device in accordance with an tenth embodiment of the invention, which is provided with a safety feature, in which a segment of a body is formed of a resilient material to permit limited stretching of the body of the device;
[0038] FIG. 19 is a partial side isometric view of a medical conduit protection device in accordance with an eleventh embodiment of the invention, which is provided with a safety release feature, in which a line of weakness is provided in the body;
[0039] FIG. 20 is a side view of a medical conduit protection device in accordance with a twelfth embodiment of the invention, which is provided with an alarm to dissuade tampering with the device;
[0040] FIG. 21 illustrates a medical conduit protection device in accordance with the invention in use, secured between an IV pole and a bed rail;
[0041] FIG. 22 is a side view of a medical conduit protection device in accordance with a thirteenth embodiment of the invention, wherein attached tethers are not provided at the ends thereof; and
[0042] FIG. 23 is an isometric view of a medical conduit protection device in accordance with a thirteenth embodiment of the invention in which a lumen of the body of the device is contiguous with a lumen formed in a cuff of a patient-end tether thereof, and in which a portion of the cuff is made from a transparent material to permit monitoring of an insertion site of patient-connected medical conduits.
DETAILED DESCRIPTION
[0043] The present invention relates to a medical tubing and wire (in general, “medical conduits”) protection devices, and the related systems and methods. As used herein, the term “medical conduits” can include, but should not be construed as being limited to intravenous tubing, other tubing such as drains and catheters, wires or other patient-connected structures. Moreover, Applicant specifically conceives that the subject devices can advantageously be applied to protect structures or devices which may not necessarily be “conduits.” Nevertheless, the term “medical conduit(s)” is used herein for simplicity.
[0044] In a clinical setting, patients who are unable or unwilling to cooperate and adhere to recommendations regarding limiting movement and not disrupting medical tubes or wires are often encountered. Such patients, for example, may include pediatric, demented, delirious, psychiatric or otherwise uncooperative patients. In such patients, maintaining the patency of the various medical tubes and wires may prove difficult as such patients often attempt to tamper with or remove IV-lines, catheters or sensors. Such behavior, naturally, can jeopardize such patients' wellness.
[0045] The subject medical conduit protection devices, example embodiments of which are discussed herein and illustrated in the appended figures, are configured to protect patient-attached medical conduits. It should be noted, however, that devices in keeping with the invention could be applied in still other situations, in which protection of structures is desired, which are not necessarily attached to, near, or for the benefit of a patient. Moreover, the subject devices may advantageously find use in a veterinary setting. In patients who might be expected to present the aforementioned difficulties or already have proven difficult, the device can be placed around vulnerable tubes and wires and the each end secured in such a way that forces, which would otherwise be placed on these tubes and wires (conduits), would be transferred to the protection device instead. So, for example, one end of the device can be attached to a patient's limb, with the IV catheter inserted in it, and with the other end of the device secured to an IV pole, for example. Such an arrangement advantageously allows the IV line to pass as it normally would, with its function unaffected, while any movement of the limb that would otherwise tension the conduits and risk violation thereof is be transferred to the protection device instead. Furthermore, depending on the precise implementation, the area of the conduits that would be vulnerable to kinking, bending, cutting, or biting by the patient would be covered by the protective surface of the device and thus protected.
[0046] Devices in accordance with the invention, in general, support medical conduits and protect such conduits from tampering and damage. In one aspect, devices in accordance with the invention substantially or completely surround one or more medical conduits, and thus prevent damage to these tubes from longitudinal or transverse pulling, intentional kinking, assaults with hands or sharp objects, or biting, for example. Advantageously, in collecting a plurality of medical conduits within one device can also serve to enhance safety in a clinical environment my reducing the usual array of patient-attached structures to a single device when practicable, simplifying the environment surrounding the patient, thereby reducing the tripping and/or entanglement hazard that multiple individual conduits often create.
[0047] In accordance with one aspect of the invention, it is preferred that a body of the subject devices be formed from a material that resists cutting, kinking, biting, and other physical assaults. Depending on the implementation, the body of the subject devices can be relatively close to that of the contained conduits, closely bundling such conduits. In such embodiments, as well as in other embodiments described herein, a longitudinal opening (e.g. slit) can be provided to permit transverse insertion of medical conduits. Such an arrangement is advantageous in that the conduits can be gathered and collected within subject protection devices while the conduits are already attached to the patient, while additional conduits can be easily added to the others at a later time. Alternatively, the body of the subject devices can be dimensioned to be substantially larger than that of the contained conduits, which can facilitate insertion of the medical conduits from an end, along the length of the body, if desired. Such an arrangement advantageously reduces potential for tampering, as there are no closures that would be susceptible to damage.
[0048] In accordance with the invention, the subject devices can be provided in any practicable dimensions. However, it is believed that protection devices having an inner diameter, that is, of a lumen running the length of the protection devices, of between about 2.0 and 5.0 centimeters. and a length of between about 0.5 and 2.0 meters. The length of the subject protection devices, in general, should be sufficient to at least protect a vulnerable length of the medical conduits, typically a section of such conduits nearest the patient, and need not necessarily extend a majority of the length of the medical conduits.
[0049] Further, as will be appreciated by the reader, the subject devices, depending on their precise configuration, can be deployed in any of a variety of lengths, for example in embodiments that are provided with a relatively soft wall, the wall can be gathered at one or both ends thereof, thus reducing the overall effective length of such devices, as needed.
[0050] The subject protection devices are preferably further provided with connections or tethers at each end thereof for securing the protection devices in a stable and safe manner. For example, a patient-end tether can be configured as a soft cuff, for the safety and comfort of the patient, while a tether at a far end can be a simple tie, such as a lace or a cord for example.
[0051] The body and tethers of the subject protection devices are preferably provided with sufficient strength so as to be able to effectively resist tension due to longitudinal pulling or transverse application of force. In accordance with a further aspect of the invention, however, the subject devices can be provided with one or more safety features that yield at a predetermined level of force, releasing the device at an end or along the body thereof. In such implementations, incorporation of an alarm feature, which would sound in case of application of excessive force, can be included.
[0052] The subject protection devices can be configured such that a natural or relaxed state of the material from which it is made automatically surrounds the medical conduits to be protected. For example if the body is formed from a resilient tubular material having a single lengthwise slit formed therein, the body can be deformed to reveal the lumen and permit lateral insertion of medical conduits, the material then relaxing into a closed configuration around the conduits once the deforming force is removed. Alternatively or additionally, one or more closure elements can be provided in connection with the body of the subject devices. Such closure elements can be of any suitable configuration, including but not limited to lace ties, straps, belts-and-buckles, hook-and-loop fasteners, adhesive tape, one or more zippers such as a lengthwise zipper, for example, an interlocking dovetail, a continuous press-to-seal closure (akin to those applied to some plastic sandwich bags), interlocking teeth or otherwise mechanically interlocking features and so on. Such features, it should be noted, can be provided at discrete positions along a length of the devices, and/or as a continuous closure along the length of the devices.
[0053] Turning now to the drawings, there is illustrated in FIG. 1 , a schematic side view of a medical conduit protection device 100 in accordance with a first embodiment of the subject invention, which includes tethers 120 , 130 at each opposed end. As illustrated, a first tether 120 includes a cuff portion 123 and a connection 121 to the body 110 , and the second tether 130 includes a strap portion 133 and a connection 131 to the body 110 . It is to be noted however, that tethers in accordance with the invention, can be secured directly to the body by any suitable construction method including, but not limited to, stitching, heat, solvent or ultrasonic welding, or other methods, depending on the materials used.
[0054] The one or more closure elements 140 are disposed along the body 110 thereof, which body 110 includes a longitudinal slit 115 that permits access to the lumen 180 defined therein. As best illustrated in the cross-sectional view of FIG. 2 , medical conduits 1990 can be arranged within the lumen 180 .
[0055] FIGS. 3-8 illustrate a medical conduit protection device 200 in accordance with a second embodiment of the invention, wherein a first or patient-end tether 220 is provided as an adjustable cuff 223 . As best seen in FIGS. 4 and 7 , the first tether to 220 also includes a closure having a belt 221 and a buckle 225 for safe and comfortable securing to a patient's arm 1870 . As can be seen in FIG. 4 , the slit 215 of the body 210 permits reception of one or more medical conduits 1990 a, the medical conduits continuing out of the lumen 280 at a first end 217 thereof. Similarly, as shown in FIG. 5 , the medical conduits 1990 a also exit the body tube 210 at the opposite, second end 219 thereof. As seen, for example, in FIG. 6 , the second tether 230 includes a pair of lace ties for securing to an external anchor point such as an IV pole.
[0056] FIG. 9 is a side view of a medical conduit protection device 300 in accordance with a third embodiment of the invention, wherein a relatively large diameter body 310 is provided, in conjunction with one more closures 318 arranged circumferentially about the body 310 at locations along the axis of the body 310 . As with the foregoing embodiments, a first tether 320 and a second tether 330 are provided, each being attached to the body 310 in respective areas 323 , 333 . The body 310 is provided with a relatively large diameter lumen 380 and is, in one preferred embodiment, formed from a relatively compliant material, but preferably one that does not stretch significantly such as a nonwoven material such as Tyvek®, for example. It is particularly conceived that use of such a material advantageously provides all of the benefits of the invention at a relatively low manufacturing cost. If constructed relatively simply from such a material, the tethers 320 , 330 can also be made from such material and the whole device 300 can be made to be recyclable, among other advantages.
[0057] As illustrated, the medical conduit protection device 300 does not include a longitudinal opening, but only first and second and openings to access the lumen 380 . However, it is to be understood that a longitudinal closure can be applied in conjunction with features described in connection with this embodiment.
[0058] FIGS. 10-11 illustrate a medical conduit protection device 400 in accordance with a fourth embodiment of the invention, wherein rotatable closure elements 440 are provided for inhibiting access to conduits held within a lumen 480 of the device 400 . As with foregoing embodiments, first and second tethers 420 , 430 are provided at respective ends of the body 410 . As can be seen best in the cross-sectional view of FIG. 11 , the body 410 is provided with a longitudinal slit 415 to permit transverse insertion of medical conduits into the lumen 480 . In this case, two rotating closure elements 440 are provided concentrically around the body 410 . The rotating closure elements 440 have respective slits 445 formed therein. When the slit 445 aligns with the slit 415 , medical conduits can be inserted into or removed from the lumen 480 . When the rotating closure elements 440 the are rotated about the longitudinal axis of the body 410 , the slit 445 no longer aligns with the slit 415 , and access to the lumen 480 is inhibited. If so desired, one or more rotating closure elements 440 can be provided such that they cover all or substantially all of the length of the body 410 , thereby further inhibiting axis to the lumen 480 .
[0059] FIGS. 12 and 13 illustrate a medical conduit protection device 500 in accordance with a fifth embodiment of the invention, wherein a helical structural element 512 is provided in connection with the body 510 of the device. Such an arrangement advantageously imparts structure to the device 500 while also physically shielding contents of the lumen 580 from external influences. Additionally, the device 500 is longitudinally compressible such that the device takes up minimal space in storage and during transportation. In the illustrated embodiment, as best seen in the cross-sectional view of FIG. 13 , the body can include an inner layer of material 510 b as well as an outer layer of material 510 a. The structural element 512 can be formed of any suitable material, including, but not limited to metals or semi-rigid polymeric materials.
[0060] FIG. 14 is an end isometric view of a medical conduit protection device 600 in accordance with a sixth embodiment of the invention, wherein inflatable channels 613 , 614 are provided in connection with the body 610 of the device 600 in a longitudinal and circumferential pattern to enhance structural rigidity of the body 610 , and to physically shield the contents of the lumen from tampering.
[0061] FIG. 15 illustrates a medical conduit protection device 700 in accordance with a seventh embodiment of the invention, wherein inflatable channels 713 , 714 are provided in connection with the body 710 of the device 700 in a pattern of dual oppositely winding helices about the circumference of the body 710 (simply, “diagonal” channels), to enhance structural rigidity of the body 710 .
[0062] FIG. 16 illustrates a medical conduit protection device 800 in accordance with an eighth embodiment of the invention, which is provided with a safety release feature, in which connections between two segments 810 a, 810 b of a body 810 are connected by severable or otherwise releasable connections 816 . Such releasable connections 816 can be, for example, stitches or staples the that release upon application of a predetermined longitudinal force to the body 810 , based on the material properties that are selected.
[0063] Similarly, FIG. 17 illustrates a medical conduit protection device 900 in accordance with a ninth embodiment of the invention, which is provided with a safety release feature, in which connections between two segments of a continuous body 910 are folded over one another and connected by severable or otherwise releasable connections 816 . While the two segments 810 a, 810 b of the body 810 of the device illustrated in FIG. 16 would separate from one another upon application of sufficient force, the overlapped section of the device 900 illustrated in FIG. 17 would separate, the body 910 would remain contiguous.
[0064] FIG. 18 illustrates a medical conduit protection device 1000 in accordance with a tenth embodiment of the invention, which is provided with a safety feature, in which a segment 1017 of the body 1010 is formed of a resilient material, such as an elastomeric material for example, to permit limited stretching of the body 1010 of the device 1000 .
[0065] FIG. 19 illustrates a medical conduit protection device 1100 in accordance with an eleventh embodiment of the invention, which is provided with a safety release feature, in which a line of weakness 1117 is provided in the body 1110 . As embodied, if a longitudinal force exceeding a predetermined value is applied to the body 1110 , the body 1110 will first separate along the line of weakness 1117 . Advantageously, an alarm feature can be integrated with such a line of weakness so that the alarm is triggered if excessive force is applied to the body 1100 , such as a severable conductive element spanning between the two segments, for example.
[0066] FIG. 20 illustrates a medical conduit protection device 1200 in accordance with a twelfth embodiment of the invention, which is provided with an alarm 1260 to dissuade tampering with the device 1200 . The device 1200 includes a body 1210 having a longitudinal slit 1215 . A plurality of closure elements 1240 are provided which, in the illustrated embodiment, connect to the body 1210 by way of conductive (e.g. metal) snaps. Accordingly, various conductive elements 1218 provided on the body 1210 can together complete an electrical circuit with electrical connections 1263 and the alarm 1260 . In accordance with the illustrated embodiment, the closure elements 1240 can be made of any suitable material as long as they are provided with a conductive path, such as a wire, to complete the electrical circuit illustrated. Although other circuit arrangements can be implemented, in the case of a series of arrangement such as that illustrated, a break in any one of the connections would cause the alarm to sound.
[0067] If so desired, the closure elements 1240 can be formed from something as simple as the metallized sheet connected to the body 1210 by way of conductive elements which can be, if desired, one-way connectors that do not permit removal without destruction of at least a portion thereof, thus enhancing tamper resistance and tamper evidence of the subject devices.
[0068] FIG. 21 illustrates a medical conduit protection device 1300 , in use, in accordance with the invention, secured between an IV pole 1371 and a bed rail 1372 . The device 1300 includes a body 1310 and tethers 1320 , 1330 which are respectively secured to the bed rail 1372 and the IV pole 1371 . Also illustrated is an IV pouch 1373 , from which a line extends into and through a lumen of the body 1310 .
[0069] FIG. 22 is a side view of a medical conduit protection device 1400 in accordance with a thirteenth embodiment of the invention, wherein a relatively large diameter body 1410 is provided, in conjunction with one more closures 318 arranged circumferentially about the body 1410 at locations along the axis of the body 1410 , similarly to the embodiment of FIG. 9 .
[0070] Unlike the foregoing embodiments, neither a first tether nor a second tether are provided. Instead, a patient end of the protection device 1400 may be attached directly to the patient as needed, such as by medical tape or other dressing. Further, a far end can simply be draped over the conduits to be protected, and remain in place, either by the inherent structural properties of the device, by friction, by application of a separate tie or restraint, or other force, depending on the precise implementation. Further, it is to be understood that only one of the end tethers can be eliminated, if desired. In such embodiments, the subject protection devices will not distribute applied external forces as fully as with the foregoing embodiments, but tampering with or damage to the attached conduits, and other advantages, can still be achieved.
[0071] FIG. 23 is an isometric view of a medical conduit protection device 1500 in accordance with a thirteenth embodiment of the invention, in which a lumen 1580 of the body 1510 of the device is contiguous with a lumen 1582 formed in a cuff 1521 of a patient-end tether 1520 thereof. Such a configuration permits passage of and protection of patient-connected medical conduits within the medical conduit protection device 1500 up to and including protection of the site on a patient where such medical conduits are attached to or inserted into the patient's body.
[0072] Furthermore, as illustrated, although optional, a portion 1521 b of the cuff 1521 is made from a transparent material to permit monitoring of an insertion site of patient-connected medical conduits. As such, a healthcare professional is able to more easily monitor the insertion site for any movement of conduits, bleeding, infection or infiltration of any medicament into surrounding tissues.
[0073] As illustrated, ties 1523 a, 1523 b are optionally provided on the non-transparent part 1521 a of the cuff 1521 so as to facilitate attachment to the patient. However, other securing features can be provided in place of or in addition to such ties 1523 a, 1523 b.
[0074] In accordance with the invention many from materials can be utilized in the manufacture of the subject devices. Materials can include but are not limited to woven fabrics, nonwoven fabrics, plastics, metallized plastics, elastomers, laminated sheets, composite sheets, rigid tubes, semi-rigid tubes and others. The subject devices can be fabricated by way of any suitable technique including, but not limited to, heat welding, solvent welding, stitching, adhesives, staples and the like.
[0075] If so desired, magnetic elements can be provided for closure of the body openings and/or for connection of the subject devices to external points such as an IV pole. Further, if desired, one or more strain gauges can be applied to the bodies of the subject devices or to the tethers, for example. Additionally or alternatively, if desired, the subject devices can be provided with further features for safety including, but not limited to, an integrated panic button electrically connected to the alarm and/or a releasable ripcord to quickly open up the subject devices, should a problem arise needing rapid attention, for example.
[0076] The alarm features of the subject devices can include more sophisticated detection circuitry than simply requiring completion of a series circuit to maintain an alarm in the off state. Such circuits can include measurement of minute changes in resistance, changes in capacitance of various elements that may be provided on such devices, and/or monitoring the status of one or more strain gauges integral to the subject devices, for example. Further, location information based on detection of proximity sensors in a hospital room, on the floor of a ward, or elsewhere in a building can be incorporated, for example, to permit higher variance of detected impedance when walking or otherwise moving. Conversely, if the patient is in bed, the alarm circuitry can be configured so as to have reduced tolerance of detected disturbances (such as a duration and/or magnitude of changes in parameters such as capacitance or resistance). In this way, it may be possible to accurately differentiate between a patient who is simply moving around to go to the bathroom and a patient who is actively tampering with the subject devices.
[0077] Further, if an alarm feature is provided in connection with devices in accordance with the invention that have one or more inflatable portions, one or more pressure gauges can be utilized to detect a fluctuation or larger changes in pressure—higher or lower than an initial pressure—in the chambers of such devices which may indicate tampering.
[0078] While the devices and related methods of subject invention have been shown and described with reference to selected embodiments, those skilled in the art will readily appreciate that changes and/or modifications may be made thereto without departing from the spirit and scope of the subject invention. Moreover, it should be understood that elements or features described in connection with any embodiment disclosed herein can be advantageously applied to other embodiments described herein, if practicable and not mutually exclusive with other features of such embodiments.
|
A medical conduit protection device has, for example, an elongate body having a wall defining a lumen for one or more elongate medical conduits. The device also includes first and second tethers provided on opposed ends of the body for securing the device to a point on or near a patient, and an external point. The medical conduit protection device inhibits tampering with or damage to the one or more medical conduits within the lumen of the body by shielding, gathering, transferring externally-applied strain away from, or otherwise protecting the one or more medical conduits within the lumen thereof.
| 0
|
CLAIM OF PRIORITY
[0001] This application claims priority from U.S. Provisional Patent Application Ser. No. 61/414,188, filed Nov. 16, 2010, which is incorporated herein in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a liquid handling system including a pump and a liquid level detector and more particularly to a pump for pumping liquid from a tank to a remote location.
BACKGROUND OF THE INVENTION
[0003] Liquid handling systems for moving and storing liquids generally require a pump for moving liquid from one location to another and means for determining the level of a liquid in a tank or other liquid storage vessel. One such liquid handling system is a condensate pump for use with a heating, ventilation, and air-conditioning (HVAC) system. A conventional condensate pump has a tank or reservoir for collecting condensate from the evaporator of the HVAC system, and a centrifugal pump for pumping the condensate liquid from the tank to a remote location for disposal. The centrifugal pump may be submerged in the liquid inside the tank or may be located outside the tank, typically in a location that is lower than the liquid level in the tank.
[0004] When the centrifugal pump is submerged in the liquid, the centrifugal pump is positioned at the lowest point in the tank in order to assure that the centrifugal pump can remove most of the liquid from the tank. An electric motor is typically mounted above the tank and is connected to the impeller of the centrifugal pump by means of a shaft. Likewise, the control circuitry is typically mounted adjacent the motor. The electric motor spins the impeller within a volute-shaped housing of the centrifugal pump, and through centrifugal force, the impeller expels the liquid from the volute-shaped housing through one or more pump outlets that are tangent to the impeller's direction of rotation. The centrifugal pump may be plumbed to convey the liquid from the pump outlet to an elevation higher than that of the tank. Often the plumbing circuit connected to the pump outlet includes a check valve to prevent liquid from flowing back into the tank when the pump is shut off. In order to control the operation of the motor and therefore the operation of the centrifugal pump, the control circuitry must include means for determining the level of liquid in the tank. Such means for determining the level of liquid in the tank may include mechanical means, such as floats, or may include electric means, such as capacitance plates submerged in the liquid in the tank.
[0005] In condensate pumps where the centrifugal pump is positioned below the tank, the bottom of the tank may be fitted with a drain or screen-drain, the location of which is at the lowest point of the tank to receive the liquid by way of a gravity feed. The drain fitting is plumbed to the inlet of the centrifugal pump to convey the liquid to the pump's impeller.
[0006] The centrifugal pump system described above, whether submerged in the liquid or connected to a drain from the tank, may be plagued with difficulties as a result of air or other gas trapped inside the volute-shaped housing of the centrifugal pump. Once the tank is filled with liquid, the centrifugal pump must start against head pressure created by liquid located above the pump in the tank and in the pump's outlet plumbing. As long as the volute-shaped housing is filled with liquid, the pump can start, expel liquid, and draw in new liquid from the tank. A problem may occur if the liquid has entrained air or gas. On the suction side of the pump (the pump inlet), trapped gas will tend to expand and separate from the liquid. This trapped gas, being less dense than the liquid, will be forced away from the outlet of the pump by the denser and higher pressure at the impeller's periphery, and the trapped gas will tend to collect at the suction or neutral pressure center of the impeller. If the fluid flow is great enough, the trapped gas will be expelled through the pump outlet along with the liquid. Consequently, the centrifugal pump can be caught in three distinct modes of operation:
1. In a normal pumping mode, the liquid completely fills the inlet and outlet of the centrifugal pump, and the centrifugal pump continuously intakes liquid through the pump inlet and expels the liquid through the pump outlet. 2. In a second pumping mode of operation, gas expands out of the inflowing liquid, creates gas bubbles inside the volute-shaped housing, and minor cavitation results during the pumping operation. Because of the low volume of gas, some liquid flow continues, and the gas is discharged through the outlet of the volute-shaped housing. In this situation, pumping efficiency is reduced and audible noise is increased because of the cavitation. 3. In a third pumping mode, gas expands out of the inflowing liquid and creates a gas bubble at the inlet of the centrifugal pump. Liquid trapped at the discharge outlet of the pump and around the periphery of impeller creates a high pressure restriction. Between the liquid head pressure from the tank and the liquid head pressure of the outlet discharge plumbing, the centrifugal pump cannot move the gas bubble that is trapped in the pump's volute-shaved housing. Because the gas bubble cannot be cleared from the volute-shaped housing, liquid flow does not occur, and the pump simply spins gas or a gas/liquid mixture. This condition is sometimes confused with cavitation but in fact is a simple balance of liquid pressure and gas pressure within the volute-shaped housing. Often the bubble of gas will remain in the impeller's volute-shaped housing when the centrifugal pump is stopped and will continue to block liquid flow through the pump when the pump is restarted.
[0010] As previously indicated, in order to control the operation of the centrifugal pump for a condensate pump, the condensate pump must be able to determine accurately the liquid level in the tank and in the pump's volute-shaped housing. In a conventional condensate pump, a float monitors and detects the water level within the pump's tank. In response to movement of the float within the tank, associated float switches and a float control circuitry control the operation of the electric motor driving the impeller of the centrifugal pump, trigger alarms, or shut down the HVAC system if necessary. The condensate pump float is in contact with the water in the tank and is subject to fouling from debris and algae buildup. A molded float has seams, which may fail causing the float to sink or malfunction. The float switch that is used to control the on/off operation of the electric motor is often a specialized and costly bi-stable snap-action switch. A conventional condensate pump, which incorporates a safety HVAC shut off switch and/or an alarm switch in addition to the motor control switch, may have a separate float or linkage to operate the HVAC shutoff switch or the alarm switch further complicating the condensate pump. Further, a conventional condensate pump often requires a float mechanism retainer to prevent shipping damage, and the float mechanism retainer must be removed prior to pump use.
[0011] The prior art has also adopted capacitive sensors as liquid level detectors to determine the level of the water in the tank of the condensate pump to replace the mechanical float for controlling the operation of the pump motor, for triggering alarms, or for shutting down the HVAC system if necessary. In some conventional liquid level detectors, at least one of the capacitance plates of the capacitive sensors is in contact with the water in the tank in order to produce a detectable change in capacitance as the water contacts or exposes the capacitance plate of the capacitive sensor. In another prior art capacitive sensor, the capacitance plates are mounted outside of the tank and not in contact with the water in the tank.
[0012] In order to determine accurately the water level, such prior art external capacitive sensors have a first capacitance plate extending the height of the tank and one or more additional capacitance plates position at anticipated transition points along the height of the tank in order to determine when the water level has reached one of the transition points. Such additional capacitance plates are deemed necessary in order to offset the effects of deposits that may form on the inside of the tank adjacent to the external capacitive sensor thereby affecting the capacitance value.
SUMMARY OF THE INVENTION
[0013] In order to solve the problems associated with the presence of gas in a centrifugal pump, the present invention provides a coaxial inlet and outlet configuration for the centrifugal pump. The centrifugal pump with its integral electric motor is mounted below the tank. The pump inlet of the centrifugal pump is located at the center of the volute-shaped housing and is connected to the small end of a funnel. The large end of the funnel is connected to the bottom of the tank so that liquid in the tank is fed through the funnel to the pump inlet by gravity. The pump outlet of the centrifugal pump is coaxially positioned within the funnel and communicates with the periphery of the volute-shaped housing. Such a coaxial inlet and outlet configuration with a funnel feed inhibits gas from being trapped at the inlet (center) of the volute-shaped impeller housing. The volute-shaped impeller housing with its funnel inlet and coaxial outlet can be molded or cast as a single piece without the need for additional machining operations. Moreover, the funnel connected to the pump inlet is configured to produce a flow of water into the volute-shaped impeller housing in a direction counter to the rotation of the impeller thereby further inhibiting gas from being trapped at the inlet to the volute-shaped impeller housing.
[0014] In order to detect the level of liquid in the tank and thereby control the operation of the electric motor of the centrifugal pump, an external capacitive sensor is mounted externally on one of the walls of the tank. Particularly, the external capacitive sensor comprises a printed circuit board that extends along the height of the tank. The printed circuit board has a shield foil on the outside of the printed circuit board to shield the capacitive sensor from external electromagnetic noise and interference. The shield foil is connected to circuit ground. The shield foil may also be configured as part of a guard ring circuit to decrease the impedance of the shield foil and thereby providing greater shielding against external electromagnetic noise and interference. The printed circuit board also has one or more sensor foils (capacitance plates) positioned on the printed circuit board between the printed circuit board and the external wall of the tank. The sensor foils are connected to a control circuit that determines the liquid level based on the capacitance values measured at the sensor foils. In addition, a pump sensor terminal (capacitance plate) is positioned inside the volute-shaped impeller housing or in the inlet of the volute-shaped impeller housing for determining the presence or absence of liquid within the volute-shaped impeller housing.
[0015] In one embodiment of the capacitive sensor, the sensor foil may include a single foil extending the height of the tank. In another embodiment of the capacitive sensor, the sensor foil may include a series of sensor foils extending along the height of the tank and divided from each other vertically to create separate sensor foils with recognizable transition points between the vertically separated sensor foils. Further, the sensor foil or foils may be configured in a discontinuous pattern, such as a hexagonal pattern, to create discontinuities within each sensor foil and thereby recognizable discontinuities in the sensed capacitance.
[0016] As the liquid in the tank rises, the sensor foils, either as a single continuous foil or as a series of separate vertically spaced foils, provide recognizable capacitance values, which in turn are resolved by the control circuit as particular liquid levels within the tank. From the sensed liquid level, the control circuit can control the operation of the motor of the centrifugal pump to start the centrifugal pump when the tank has filled with liquid to a predetermined level, to stop the motor of the centrifugal pump when the tank has emptied to a predetermined level, to shut off the source of liquid into the tank, such as by shutting off an HVAC system, and to sound an alarm if the liquid reaches a critical high level in the tank.
[0017] If the control circuit determines that the volute-shaped impeller housing has dried out based on the capacitance value measured at the pump's sensor terminal within the centrifugal pump or near the pump inlet of the centrifugal pump, the control circuit can start the centrifugal pump in a priming mode. The priming mode rapidly turns the motor of the centrifugal pump on and off in an attempt to knock any air bubbles off of the impeller blades before the pumping operation begins.
[0018] Further objects, features and advantages will become apparent upon consideration of the following detailed description of the invention when taken in conjunction with the drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a front perspective view (front and right side) of a condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0020] FIG. 2 is a front perspective view (front and left side) of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0021] FIG. 3 is a front elevation view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0022] FIG. 4 is a top plan view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0023] FIG. 5 is a bottom plan view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0024] FIG. 6 is a right side elevation view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0025] FIG. 7 is a left side elevation view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0026] FIG. 8 is a section view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention as seen along line 8 - 8 of FIG. 3 .
[0027] FIG. 9 is a section view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention as seen along line 9 - 9 of FIG. 3 .
[0028] FIG. 10 is a section view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention as seen along line 10 - 10 of FIG. 3 .
[0029] FIG. 11 is an exploded perspective view of the condensate pump having a centrifugal pump with a coaxial inlet and outlet in accordance with the present invention.
[0030] FIG. 12 is a front elevation view of the centrifugal pump with a coaxial inlet and outlet for the condensate pump in accordance with the present invention.
[0031] FIG. 13 is a top plan view of the centrifugal pump with a coaxial inlet and outlet for the condensate pump in accordance with the present invention.
[0032] FIG. 14 is a right side elevation view of the centrifugal pump with a coaxial inlet and outlet for the condensate pump in accordance with the present invention.
[0033] FIG. 15 is a section view of the centrifugal pump with a coaxial inlet and outlet for the condensate pump in accordance with the present invention as seen along line 15 - 15 of FIG. 12 .
[0034] FIG. 16 is an exploded perspective view of centrifugal pump with a coaxial inlet and outlet for the condensate pump in accordance with the present invention.
[0035] FIG. 17 is a front elevation view of a capacitive sensor for the condensate pump in accordance with the present invention.
[0036] FIG. 18 is a back elevation view of a capacitive sensor for the condensate pump in accordance with the present invention.
[0037] FIG. 19 is a side elevation view of a capacitive sensor for the condensate pump in accordance with the present invention.
[0038] FIG. 20 is a schematic diagram of a control circuit for the condensate pump having the capacitive sensor in accordance with the present invention.
[0039] FIG. 21 is a schematic diagram of a negative amplifier (configured as an integrator) for a shielding electrode (guard ring) for the capacitive sensor in accordance with the present invention.
[0040] FIG. 22 is a schematic diagram of a positive amplifier (configured as a guard ring) for the capacitance sensor in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0041] Turning to FIGS. 1 and 2 , a condensate pump 10 is shown comprising a tank (or reservoir) 12 , a base 26 , and a centrifugal pump 28 with an integrated electric motor 40 . The tank 12 and the base 26 are molded as a single part. The base 26 houses the centrifugal pump 28 and the integrated electric motor 40 below the tank 12 .
[0042] As shown in FIGS. 1 and 2 , the tank 12 is generally rectangular in shape and has a tank bottom 14 , a tank top 16 , a tank front 17 , a tank back 18 , and tank sides 20 . The tank 12 has a tank inlet 22 in the tank top 16 for receiving liquid, such as condensate water from an HVAC system. The tank 12 has a tank outlet 24 ( FIG. 11 ) in the bottom 14 of the tank 12 that is generally rectangular in shape. The centrifugal pump 28 with the integrated electric motor 40 is fastened by means of screws 48 to the underside of the bottom 14 of the tank 12 .
[0043] With reference to FIGS. 12-16 , the centrifugal pump 28 comprises a volute-shaped impeller housing 30 with a pump inlet 32 ( FIG. 15 ) in the center of the volute-shaped housing 30 and a pump outlet 34 at the periphery of the volute-shaped housing 30 . An impeller 36 with impeller blades 38 is mounted for rotation within the volute-shaped impeller housing 30 ( FIG. 16 ). The integrated electric motor 40 drives the impeller 36 .
[0044] The tank outlet 24 ( FIG. 11 ) and the pump inlet 32 are connected together by means of a funnel 42 ( FIG. 11 ). The funnel 42 has a large top opening 44 that is connected to the tank outlet 24 ( FIG. 11 ). The funnel 42 at its opposite end has a small opening 46 that is connected to the pump inlet 32 of the volute-shaped impeller housing 30 ( FIGS. 13 and 15 ). The funnel 42 has a substantially vertical side 56 and a facing angled side 58 ( FIGS. 14 and 15 ). The facing angled side 58 directs the flow of water into the volute-shaped impeller housing in a direction counter to the rotation of the impeller thereby inhibiting gas from being trapped at the pump inlet 32 . The volute-shaped impeller housing 30 , the pump inlet 32 , the pump outlet 34 , and the funnel 42 can all be molded as a single piece.
[0045] With reference to FIGS. 10-16 , the pump outlet 34 from the periphery of the volute-shaped impeller housing 30 is positioned coaxially within the funnel 42 and extends upwardly through the tank outlet 24 into the tank 12 ( FIG. 10 ). The pump outlet 34 is connected to an outlet connector 50 by means of a transition tube 54 and a check valve 52 ( FIG. 11 ). The outlet connector 50 is connected to tubing (not shown) for carrying the condensate water away to a disposal location.
[0046] The positioning of the funnel 42 above of the pump inlet 32 in combination with the gravity fed condensate water from the tank 12 reduces the amount of air bubbles that are sucked into the volute-shaped impeller housing 30 through the pump inlet 32 . The large opening 44 of the funnel 42 allows air bubbles near the pump inlet 32 to bubble up through the funnel 42 and escape into the condensate water in the tank 12 . Consequently, the chances of the centrifugal pump 28 becoming airlock or cavitating are substantially reduced.
[0047] In order to control the operation of the electric motor 40 and therefore the centrifugal pump 28 , a capacitive liquid level sensor 100 is positioned externally to the tank 12 and a pump sensor terminal 110 ( FIG. 13 ) is positioned adjacent the pump inlet 32 . Both the capacitive liquid level sensor 100 and the pump sensor terminal 110 are connected to a control circuit 112 ( FIG. 20 ) for controlling the operation of the motor 40 , the operation of water level display LEDs 114 ( FIGS. 17 and 20 ), and the operation of an HVAC shutoff relay 128 ( FIG. 20 ).
[0048] As shown in FIGS. 8 , 11 , and 17 - 20 . the pump sensor terminal 110 ( FIG. 13 ) is positioned adjacent the pump inlet 32 and is connected to the control circuit 112 by means of a collector line 120 . The capacitive sensor 100 comprises a circuit board 102 that is positioned externally to one of the tank sides 20 and extends along the majority of the height of the tank 12 . A shield foil 104 ( FIG. 17 ) covers the side of the circuit board 102 that faces away from the tank 12 . The foil shield 104 may be continuous or patterned in order to adjust the value of the capacitance at sensor foils 106 and 108 . The shield foil 104 is connected to the circuit ground to minimize electromagnetic noise and interference from external sources. In order to provide additional shielding against electromagnetic noise interference from external sources, guard ring circuits, such as guard ring circuits 160 and 162 shown in FIGS. 21 and 22 , may be employed to lower the impedance of the shield foil 104 . The operation of the guard ring circuits 160 and 162 will be described in greater detail below.
[0049] With reference to FIGS. 18 and 20 , one or more sensor foils, such as first (lower) sensor foil 106 and second (upper) sensor foil 108 cover the other side of the circuit board 102 that faces the tank side 20 . The sensor foils 106 and 108 each represent a capacitance plate of a capacitor for which the liquid inside the tank 12 forms part of the capacitor's dielectric. Consequently, as the liquid inside the tank 12 rises and falls, the capacitance value of the sensor foils increases and decreases thereby providing a representation of the level of the liquid inside the tank 12 . In the embodiment of the capacitive sensor 100 shown in FIGS. 17-20 , the sensor foils 106 and 108 are configured in a hexagonal pattern with the individual hexagonal foils in the first foil 106 interconnected by foil connector lines 116 and the individual hexagonal foils in the second foil 108 interconnected by foil connector lines 118 ( FIG. 20 ).
[0050] As can be seen with reference to FIGS. 8 , 17 , and 18 , the first foil 106 extends from a position near the bottom 14 of the tank 12 to a gap 124 positioned about halfway up the height of the tank 12 . After the gap 124 , the second foil 108 extends from the gap 124 to near the top 16 of the tank 12 . As the liquid in the tank 12 rises above the bottom 14 of the tank 12 , the dielectric value for the first sensor foil 106 changes, and as a result, the capacitance value for the first sensor foil 106 changes accordingly (while the capacitance value for the second sensor 108 remains substantially constant). Once the liquid in the tank 12 bridges the gap 124 and then engages the second foil 108 , the discontinuity between the first foil 106 and the second foil 108 is recognized by the control circuit 112 so that the halfway reference point of the tank is established and used as a calibration point for the control circuit 112 . As the liquid in the tank 12 continues to rise along the height of the second foil 108 , the capacitance value for the second foil 108 continues to change accordingly (while the capacitance value for the first sensor 106 remains substantially constant).
[0051] In addition to establishing the calibration point by means of the gap 124 between the sensor foils 106 and 108 , the calibration point positioned between the top and the bottom of the tank can also be established by mechanical means such as having a tank wall thickness below the calibration point greater than the tank wall thickness above the calibration point or vice versa. Because the wall of the tank represents part of the dielectric that also includes the liquid in the tank, an abrupt change in the tank wall thickness serves to establish an abrupt change in capacitance value, the calibration point, when the water in the tank reaches the transition point between the thick wall of the tank and the thinner wall of the tank.
[0052] Turning to FIG. 20 , the control circuit 112 controls the operation of the pump motor 40 , the liquid level display LEDs 114 , an alarm 126 , and the HVAC shutoff relay 128 . The functions of the control circuit 112 are implemented by a microprocessor 130 . The inputs to the control circuit 112 include the first sensor foil line 132 , the second sensor foil line 134 , and the collector line 120 . Each of the lines 132 , 134 , and 120 connects a capacitance value for the first sensor foil 106 , the second sensor foil 108 , and the pump sensor terminal 110 to the control circuit 112 . In order to determine the capacitance value for the first sensor foil 106 , the second sensor foil 108 , and the pump sensor terminal 110 , the microprocessor 130 has a drive pin 136 that drives a first foil input pin 138 through an RC timing circuit that includes the capacitance value of the first sensor foil 106 . The microprocessor drive pin 136 also drives a second foil input pin 140 through an RC timing circuit that includes the capacitance value of the second sensor foil 108 . Likewise, the microprocessor drive pin 136 drives a pump sensor input pin 142 through an RC timing circuit that includes the capacitance value of the pump sensor terminal 110 .
[0053] Particularly, when the microprocessor 130 initiates a sense cycle, the microprocessor 130 starts a counter for each of the input pins 138 , 140 , and 142 , and then the microprocessor 130 begins driving each of the input pins 138 , 140 , and 142 positively through their respective RC timing circuits. Once each of the input pins 138 , 140 , and 142 reaches a predetermined threshold value its respective counter is suspended. Once all of the input pins 138 , 140 , and 142 have reached their respective predetermined threshold values, the microprocessor drive pin 136 reverses polarity and begins discharging the capacitance in the RC timing circuits. At the same time, each of the counters resumes counting. When each of the input pins 138 , 140 , and 142 reaches a zero value, each of the counters is stopped. The count on each of the counters is thereby proportional to the capacitance value for the first sensor foil 106 , the second sensor foil 108 , and the pump sensor terminal 110 , which is in turn indicative of the level of the liquid in the tank 12 . The charge/discharge sequence is employed to minimize any residual dc build up on the capacitance plates or in the circuit components.
[0054] While the microprocessor 130 can determine the capacitance value for the first sensor foil 106 (input pin 138 ), the second sensor foil 108 (input pin 140 ), and the pump sensor terminal 110 (input pin 142 ) in parallel fashion as described above, the microprocessor 130 can also determine the capacitance value for the first sensor foil 106 (input pin 138 ), the second sensor foil 108 (input pin 140 ), and the pump sensor terminal 110 (input pin 142 ) in serial fashion. In the serial sensing case, the input pins that are not being sensed are driven to ground and act as an additional shields and ground references for the capacitance plate attached to the input pin that is being sensed. Further, in the serially sensing case, sensing the capacitance values for the first sensor foil 106 (input pin 138 ), the second sensor foil 108 (input pin 140 ), and the pump sensor terminal 110 (input pin 142 ) requires only a single counter implemented by software in microprocessor 130 .
[0055] Based on the level of the liquid in the tank 12 , the microprocessor activates the liquid level display LEDs using a multiplex scheme to give a visual indication of the liquid level in the tank 12 . Further, when the liquid in the tank reaches a certain height, the microprocessor 130 starts the motor 40 in order to empty the tank 12 . The microprocessor 130 also controls the speed of the motor 40 by varying the pulse width of a speed control signal line 146 to the MOSFET speed control switch 144 . Once the level of the liquid in the tank 12 drops below a predetermined level, the microprocessor 130 shuts off the motor 40 until the next pumping cycle is required to empty the tank 12 . If the level of liquid in the tank 12 rises above a certain predetermined emergency level, the microprocessor 130 can control the operation of an HVAC shutoff relay 128 to stop the HVAC system and thereby cut off further flow of condensate water into the tank 12 . At the same time, the microprocessor 30 can trigger the alarm 126 .
[0056] In the circumstance where the condensate pump 10 has not received any condensate water for an extended period of time and where all of the condensate water in the tank 12 and in the volute-shaped impeller housing 30 has evaporated, the air within the dried out volute-shaped impeller housing 30 may be trapped by the initial reintroduction of condensate water into the pump inlet 32 . The microprocessor 130 determines that the volute impeller housing 30 has dried out by reference to the capacitance value of the pump sensor terminal 110 . Once the microprocessor 130 has determined that the volute impeller housing 30 is dry and that air bubbles may be present inside the volute-shaped impeller housing 30 , the microprocessor 130 initiates a priming mode startup for the motor 40 . In the priming mode, the motor 40 is rapidly turn on and off by the microprocessor 130 in an attempt to dislodge air bubbles that may be attached to the impeller blades 38 of the impeller 36 ( FIG. 16 ).
[0057] Turning to FIGS. 21 and 22 , guard ring circuits 160 and 162 serve to shield the sensor foils, such as sensor foil 106 , from electromagnetic noise and interference. As previously described, the sensor foils, such as sensor foil 106 , are driven positively and negatively by the drive pin 136 of microprocessor 130 . With respect to guard ring circuit 160 shown in FIG. 21 , an inverting amplifier 150 drives the shield foil 104 with an opposite polarity to that of the charging voltage of drive pin 136 . The capacitance between shield foil 104 and sensor foil 106 then becomes the capacitor of an integrator. By adjusting the capacitance between the shield foil 104 and the sensor foil 106 , interfering signals superimposed on the sensor foil 106 may be canceled. The guard ring circuit 162 shown in FIG. 22 , has an operational amplifier 152 connected as a voltage follower. In this voltage follower configuration, leakage currents that might flow to or from the sensor foil 106 are nullified by the surrounding shield foil 104 , which is driven to the same electrical potential as the sensor foil 106 .
[0058] While this invention has been described with reference to preferred embodiments thereof, it is to be understood that variations and modifications can be affected within the spirit and scope of the invention as described herein and as described in the appended claims.
|
A liquid handling system having a tank with a centrifugal pump for pumping the liquid out of the tank is disclosed. The centrifugal pump is located beneath tank and has a coaxial inlet-outlet. Capacitive sensors are used to detect the level of liquid in the tank, and control circuits are connected to the capacitive sensors and control the operation of the pump.
| 5
|
This application is a continuation of application Ser. No. 10/692,144, filed Oct. 23, 2003, status allowed.
FIELD OF THE INVENTION
The invention relates to the field of publish/subscribe (pub/sub) messaging. In particular the invention relates to the field of multicast pub/sub messaging.
BACKGROUND OF THE INVENTION
Publish/subscribe data processing systems have become very popular in recent years as a way of distributing data messages. Publishers are typically not concerned with where their publications are going, and subscribers are typically not interested in where the messages they receive have come from. Instead, a message broker typically assures the integrity of the message source, and manages the distribution of the message according to the valid subscriptions registered in the broker.
Publishers and subscribers may also interact with a network of brokers, each one of which propagates subscriptions and forwards publications to other brokers within the network. Therefore, when the term “broker” is used herein it should be taken as encompassing a single broker or multiple brokers working together as a network to provide brokering services.
An overview of a typical pub/sub system (e.g. WebSphere(R) MQ Integrator available from IBM Corporation) is described with reference to FIG. 1 . Such a system comprises a number of publishers 10 , 20 , 30 publishing messages to a broker 70 on particular topics (e.g. news, weather, sport). Subscribers 40 , 50 , 60 register their interest in such topics via subscription requests received at the broker 70 . For example, subscriber 40 may request to receive any information published on the weather, whilst subscriber 50 may desire information on the news and sport.
Note, broker 70 might be an identifiable process, set of processes or other executing component, or instead might be “hidden” inside other application code. The logical function of the broker will however exist somewhere in the network.
When broker 70 receives a message on a particular topic from a publisher, the broker determines from its list of subscriptions to whom that message should be sent. The broker then transmits the message to such subscribers.
A problem with typical pub/sub is scalability. One copy of a message is sent by the broker to each subscriber who has registered an interest in the topic to which the message relates. Thus if one hundred subscribers desire to receive information on the topic of sport, one hundred copies of each message relating to sport are sent out. Thus the whole network of subscribers might be flooded.
For this reason, multicast pub/sub was invented. This scales much better since the network determines the minimum/most efficient number of message copies necessary in order to fulfil subscribers' requests.
Unlike point-to-point TCP/IP socket-based pub/sub (where each subscriber listens on its own IP address for messages), subscribers in a multicast system listen on specific multicast addresses. Any number of subscribers may listen on the same multicast address.
In a pub/sub system, there is potentially an infinite number of topics. However the range of multicast addresses available is limited. Further, most systems typically support only a subset of this limited range. Thus there is the very real problem of how to map the “topic space” to the available multicast addresses.
One well-known pub/sub system (Tibco's Rendez-Vous) avoids the problem by having all subscribers listen on a single multicast address (whatever their subscription requests). Thus each subscriber receives all publications. Software on each subscriber is then used to filter out information on topics in which the subscriber has no interest. Such a system places a very heavy workload on the network and also the subscribers themselves.
Thus there is a need in the industry for an efficient way of mapping the limited range of multicast addresses available to an infinite topic space and for communicating a single multicast address per subscription request.
SUMMARY OF THE INVENTION
Accordingly the invention provides a message broker for managing subscription requests in a multicast messaging system comprising a plurality of publishers publishing information to the broker and a plurality of subscribers subscribing to information received from one or more publishers, the broker comprising: means for receiving a subscription request pointing to topic information in which the requesting subscriber is interested, the topic information defining a specific topic within a topic hierarchy; means for parsing said request to determine if said request includes a wildcard; and means, responsive to determining that said request does include a wildcard, for instructing the requesting subscriber to listen on a multicast address associated with the topic in the topic hierarchy which precedes said wildcard.
Note, if no topic precedes a wildcard (e.g. *\weather), then the root topic is implicitly the preceding topic. Thus the above is meant to encompass this situation.
Note, subscription requests may include an explicit topic hierarchy (e.g. news\politics\leaders\Tony Blair). Alternatively a hierarchy may be implicit within the subscription request—e.g. if a subscription requests all information about the weather, then the implicit hierarchy might be “*\weather”.
Preferably it is possible to assign the multicast address to the preceding topic. The multicast address may be inherited from a parent topic.
Wildcard subscription requests were, prior to the solution provided by the present invention, problematic. They begged the question as to which multicast address a subscriber requesting a wildcard subscription should be told to listen on in order to receive the desired information.
The invention solves this problem by the broker returning a single multicast address that is associated with the best-matching topic string up to the wildcard in the subscription (i.e. the address associated with topic information immediately preceding the wildcard).
According to one aspect, there is provided a method for managing subscription requests in a multicast messaging system, the messaging system comprising a plurality of publishers publishing information to a broker and a plurality of subscribers subscribing to information received from one or more publishers, the method comprising the steps of: receiving a subscription request pointing to topic information in which the requesting subscriber is interested, the topic information defining a specific topic within a topic hierarchy; parsing said request to determine if said request includes a wildcard; and responsive to determining that said request does include a wildcard, for instructing the requesting subscriber to listen on a multicast address associated with the topic in the topic hierarchy which precedes said wildcard.
According to another aspect, the invention provides a computer program for managing subscription requests in a multicast messaging system, the messaging system comprising a plurality of publishers publishing information to a broker and a plurality of subscribers subscribing to information received from one or more publishers, the computer program comprising program code means adapted to perform, when said program is run on a computer, the steps of: receiving a subscription request pointing to topic information in which the requesting subscriber is interested, the topic information defining a specific topic within a topic hierarchy; parsing said request to determine if said request includes a wildcard; and responsive to determining that said request does include a wildcard, for instructing the requesting subscriber to listen on a multicast address associated with the topic in the topic hierarchy which precedes said wildcard.
According to another aspect, the invention provides a multicast messaging system for managing subscription requests, the system comprising: a message broker; a plurality of publishers publishing information to the broker; a plurality of subscribers subscribing to information received from one or more publishers, the subscribers comprising: means for registering subscription requests with the broker, the broker comprising: means for receiving a subscription request pointing to topic information in which the requesting subscriber is interested, the topic information defining a specific topic within a topic hierarchy; means for parsing said request to determine if said request includes a wildcard; and means, responsive to determining that said request does include a wildcard, for instructing the requesting subscriber to listen on a multicast address associated with the topic in the topic hierarchy which precedes said wildcard.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred embodiment of the present invention will now be described, by way of example only, and with reference to the following drawings:
FIG. 1 shows an overview of a typical publish/subscribe messaging system according to the prior art;
FIG. 2 depicts an example topic tree;
FIG. 3 shows the topic tree of FIG. 2 with exemplary multicast addresses assigned in accordance with a preferred embodiment of the present invention;
FIG. 4 a illustrates pertinent components of a message broker according to a preferred embodiment; and
FIG. 4 b is a flowchart illustrating the processing of the present invention in accordance with a preferred embodiment.
DETAILED DESCRIPTION
When a broker in a multicast system receives a subscription request from a subscriber, the broker instructs that subscriber of the multicast address they should listen on in order to receive publications pertaining to their request.
As previously discussed, the number of multicast addresses is very limited, whilst the number of topics available may be far greater. It is therefore very unlikely that there will be sufficient multicast addresses to assign unique addresses across an entire topic space. There is also the difficulty that publishers can invent new topics on-the-fly.
The first problem therefore is how the broker should assign multicast addresses to its topic space.
The topic space is preferably defined by the publications/subscription requests received at the broker. Each such request is parsed into a representation against which publications can be matched. For the sake of simplicity, the topics in a topic space may be thought of as forming a tree structure, with each topic forming a node within this structure. Part of the tree structure is typically created at system setup based on the broker's knowledge as to the kind of messages that it is likely to receive. As new subscription requests are received/new types of publication are received, so the tree grows. Subscribers are associated with relevant nodes in order that they can receive information pertaining to their subscription requests.
FIG. 2 depicts an example topic tree. From this figure it can be seen that the main topic about which information is published is “news”. This topic can be divided into three categories—politics news, foreign news and sports news. Each category can then be further subdivided. (For example, information is published on the tennis stars Pete Sampras, Andre Agassi and Monica Seles.)
When a publication is received at the broker, it is parsed against the tree structure in order to match subscription requests registered with the broker. Such requests may specify exactly which part of the topic tree a particular subscriber is interested in. For example, a subscriber may submit the following subscription to the broker: “news\politics\Labour\Jack Straw”.
In order to instruct the subscriber which multicast address they should listen on in order to receive news on Jack Straw, the broker should preferably have assigned multicast addresses to the topic space.
According to a preferred embodiment of the present invention, each topic of the tree is assigned, as an attribute, a multicast address (e.g. an IP address). If the attribute is not set, then the particular topic, preferably inherits from its parent. Dynamically created topics (which will not show up in a management tool) also preferably inherit from a parent topic. Addresses may of course have to be reused in order to cover the complete topic space. Thus filtering may be necessary at the subscriber to remove unwanted topic information. Such filtering is however greatly reduced compared with previous solutions.
Another way of saving on mulitcast addresses is to assign addresses to levels of the tree (as opposed to assigning addresses to individual topic nodes). Again filtering may be required at the subscriber.
Using the scheme/variations thereof, described in the previous two paragraphs, allows network administrators to easily determine how far (in a network topology sense) topics are to be transmitted. In other words, network administrators may configure how many routers and gateways publications are transmitted through. For example, it is possible to configure a router to accept certain multicast addresses, but not others.
Network administrators may also configure exactly which nodes inherit from their parent, which nodes reuse addresses etc.
FIG. 3 shows the topic space of FIG. 2 with exemplary multicast addresses assigned in accordance with a preferred embodiment of the present invention. It will be appreciated that the addresses used in FIG. 3 are by way of example only—they are not meant to be real multicast addresses.
From this figure, it can be seen, for example, that the root topic (news) is assigned address 1. Politics has an address of 1.2 and its subcategory of leaders has an address of 1.2.1. Another of politics subtopics “Labour has an address of 1.2.2. The topics which descend from Labour (i.e. Tony Blair and Jack Straw) do not however have addresses assigned. Thus these topics inherit their parents address (i.e. 1.2.2). Further the Conservative topic has the same address as the Labour topic. This conserves multicast addresses.
Thus returning to the previous example subscription request of “news\politics\labour\Jack Straw”, the originator of this request will be told to listen on multicast address 1.2.2 (i.e. the address associated with the Labour topic since the Jack Straw topic does not have its own address). This subscriber will thereby receive all publications about Jack Straw. The subscriber will of course also receive other information about the Labour Party (including that about Tony Blair as part of the Labour Party). Further the subscriber will receive information about the Conservative party (including that about Ian Duncan-Smith and John Major). However the amount of unwanted material should be manageable and can be filtered out by software running on the subscriber.
Using the scheme proposed above it is relatively clear which multicast address a subscriber, specifying explicitly the topic of interest, should be told to listen on. Unfortunately subscribers do not always use such explicit requests. Wildcards subscriptions are frequently used. For example, the following request may be received: “news\sport\tennis\*” (where * denotes a wildcard). Such a subscription is a request for all news about the topic of tennis. Thus according to the topic space defined in FIGS. 2 and 3 , the subscriber should receive publications about tennis stars—i.e. about Sampras, Agassi, Seles and information about any other tennis stars received by the broker.
Note a wildcard does not have to appear at the end of the subscription request string. For example, the following request might be received: “news\*\*\John Major”. Such a request should return information relating to John Major as a member of the Conservative Party and John Major as a fan of cricket.
Wildcard subscription requests were, prior to the solution provided by the present invention, problematic. They begged the question as to which address a subscriber requesting a wildcard subscription should be told to listen on in order to receive the desired publications.
Returning to the first wildcard subscription example of “news\sport\tennis\*”. One possible solution is to tell the subscriber to listen on each address covered by the wildcard. With the example given, the subscriber would be told to listen on addresses 1.4.1, 1.4.1.1, 1.4.1.1.1, 1.4.1.1.2 and 1.4.1.1.3 (i.e. the addresses associated with the topic nodes in the tennis subtree). Thus the subscriber would have to listen on 5 addresses and consequently 5 copies of a message fulfilling the subscriber's request would have to be propagated over the network. It will be appreciated that with a large number of subscription patterns including wildcards (as frequently occurs in a production pub/sub system), the situation would quickly become unmanageable. This is especially true with a large number of subscribers.
The invention preferably solves this problem by the broker returning a single multicast address that is associated with the best-matching topic string up to the first wildcard in the subscription. For example, with the wildcard subscription request of “news\sport\tennis\*”, the broker returns the multicast address associated with the tennis topic (i.e. 1.4.1). By way of a further example, with a wildcard subscription request of “news\politics\*\Tony Blair”, the broker returns the address associated with the politics topic (i.e. 1.2).
In this way, the required aim is achieved. Subscribers listen on a single address (even when their subscription request includes a wildcard) and thus the network should not be flooded. By listening on the single address, the subscriber receives all the information that they would have received had they listened on multiple addresses (as described in the inferior solution above). They may of course receive some information that they do not want, but this can be filtered out subscriber-side. Since network traffic is reduced, this tradeoff is considered worthwhile.
FIG. 4 a illustrates pertinent components of a message broker according to a preferred embodiment of the present invention. FIG. 4 b is a flowchart illustrating the processing of the present invention in accordance with a preferred embodiment. FIGS. 4 a and 4 b should be read in conjunction with one another.
The message broker 70 comprises a matching engine 100 . It is the matching engine 100 which receives the subscription requests (step 200 ) and parses each one at step 210 (using parser component 105 ). A topic string received as a subscription request is parsed into a “prefix” and a “remainder”. The “prefix” constitutes everything up to and not including the first wildcard (assuming a wildcard exists). The “remainder” may be empty.
At step 220 , the node in the topic tree defined by the prefix (i.e. the node representing the topic immediately preceding the wildcard) is located (if it already exists) or is added into the topic tree (if it doesn't). If the node is added in, then this node inherits its parent's multicast address.
The subscriber can then be associated with the node in the topic tree which is defined by the prefix (step 230 ) (the parser component may also action this).
At step 240 , the subscriber is instructed, via instructor component 130 , how to receive the information it requests (see below).
Address assignor component 120 assigns multicast addresses to the nodes in the topic tree. The methodology applied to assign these addresses can be configured by a network administrator.
The address assigned by the assignor component 120 is used by the instructor component 130 to instruct the subscriber as to which is the appropriate multicast address to listen on. (In other words once a subscriber has been associated with a node in the tree structure, the instructor component 130 interrogates the tree to determine the multicast address associated with that node.)
It will be appreciated that, via this method, subscribers may receive information in which they are not interested. For example a subscriber wishing to receive information about Tony Blair (via the subscription news\politics\*\Tony Blair) will be told via component 130 to listen on the multicast address associated with politics (i.e. 1.2). This subscriber will thus receive information not only about Tony Blair but relating to all other topics descending from the politics topic node (e.g. Labour\Jack Straw, Conservative\Ian Duncan-Smith etc.) As previously mentioned, filtering can be done at the subscriber to remove such unwanted information and this is a worthwhile tradeoff for increased network efficiency. Further whilst messages will be transmitted by the broker on all of the multicast addresses communicated to the subscribers, the number of transmissions is bounded by the depth of the topic tree. Thus the situation is manageable.
Although this description has used a single asterisk to denote a full component in the tree, the same technique can be used for any wildcard character recognised in any (single or multiple) place. For example, a subscriber to the topic “news\pol*s\*\????Blair” would be given the address of the “news” topic.
Note, in the example above, a subscriber will be told to listen on the address associated with the news node.
Note, if a wildcard does not exist in a subscription request, then the request is not broken into a “prefix” and a “remainder” and the subscriber is simply associated with the node defined by request. For example, a request of news\politics\labour would result in the requesting subscriber being associated with the labour node in the topic tree (i.e. being told to listen on address 1.2.2).
|
The invention relates to a message broker for managing subscription requests in a multicast messaging system. The messaging system comprises a plurality of publishers publishing information to the broker and a plurality of subscribers subscribing to information received from one or more publishers. The broker is able to receive a subscription request pointing to topic information in which the requesting subscriber is interested, the topic information defining a specific topic within a topic hierarchy. The broker is able to parse the request to determine if the request includes a wildcard and if the request does include a wildcard, the broker instructs the requesting subscriber to listen on a multicast address associated with the topic in the topic hierarchy which precedes the wildcard.
| 7
|
BACKGROUND OF THE INVENTION
This invention relates to improvements in game tables on which a game similar to billiards may be played with balls on a cushioned surface.
Billiard like games are old and well known in the art. Such games and the apparatus therefor are a constant source of amusement and challenge for game participants. While the most common form of billiard table is rectangular, other forms have been disclosed. The patent to Arney, U.S. Pat. No. 803,520, shows a five-sided game table having the shape of a regular polygon. The design patent to Cannon D 86,218 shows a six-sided game table having an elongated hexagonal shape. Rectangular game tables having one side of a normal rectangle substituted by two angularly related sides are also known in the art. Such tables are disclosed by Snedaker in U.S. Pat. No. 928,160, Lee in U.S. Pat. No. 1,693,116, and Trost in U.S. Pat. No. Des. 66,386. A further alteration of the normally rectangular billiard game table is shown by Reesch in U.S. Pat. No. 208,539 wherein an elliptically shaped table is disclosed.
SUMMARY OF THE INVENTION
The table of the present invention has a generally rectangular shape with the exception that a parabola is substituted for one of the sides. The parabola adds interest and challenge to games played on the table in that the path of a ball or other object ricocheting off the parabolic side is difficult to forsee. Additionally, fixed obstacles on the table provide surfaces off from which the game pieces may rebound. These obstacles are located along the perimeter of the table as well as in the central playing area. The playing surface itself has a felt-like finish, as do bumper edges which form the perimeter. Counting discs threaded on rails outside of the playing surface are used for keeping score during game play. These and other aspects of the invention will be apparent from the following description taken in conjunction with the several drawing figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the device in position for play on a supporting surface.
FIG. 2 is a plan view of the device.
FIG. 3 is a sectional view taken along lines 3--3 of FIG. 2 showing the playing surface, the perimeter walls, and the counting discs.
FIG. 4 is a plan view of an alternative embodiment of the device.
FIG. 5 is a sectional view taken along line 5--5 of FIG. 4 showing a perforated playing surface above an air plenum chamber.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIG. 1, there can be seen generally the game table 10 resting on a supporting surface 12. It will be understood that the supporting surface 12 forms no part of the present invention and is shown here only as a convenient and ordinary means of support for the table 10 in playing position. The game table 10 comprises a main playing surface 14 bounded around its perimeter by walls 16. Within the central area of the playing surface 14 are two fixed obstacles 18 and 20. Located outside of the playing area are two rails 22 located on opposite sides of playing surface 14. Threaded onto these rails 22 are a plurality of counting discs 24. Equal numbers of counting discs are provided on each of the two rails 22.
Turning now to FIG. 2, it can be clearly seen that the walls 16 which define the perimeter of the playing surface 14 comprise three straight wall sections 26, 28 and 30, and two curved wall sections 32 and 34. The wall sections 26 and 28 meet at approximately a 90° angle and the wall sections 26 and 30 meet at approximately a 90° angle. Where these angles are exactly 90°, sides 28 and 30 are parallel to one another. The wall sections 32 and 34 are curved in the preferred embodiment and are parabolic in shape. The focus of this parabolic shape is along the line which connects obstacles 18 and 20 on the central playing area. It will be seen that two additional fixed obstacles 36 and 38 are located along the perimeter of the playing area. These obstacles are preferably at the intersections of the ends of the parallel sides 28 and 30 with the ends of the parabolic sides 32 and 34, respectively. Two balls 40 and 42 are shown on the playing surface. It will be seen that the counting discs 24 may be slid along the rails 22 for scoring purposes during game play.
Turning now to FIG. 3, some of the constructional features of the invention can be more readily seen. The playing surface 14 and the perimeter defining walls 16 are seen as comprising a shell 44 with attached inclined sidewalls 46. This shell with the sidewalls may be made of plastic and vacuum formed into the required configuration. Other materials, such as metal or a wood-like product, may be used in which instances the attachment of the walls to the playing surface will be effected by means compatible with the particular material used. The shell 44, the walls 46 and the obstacles 18, 20, 36 and 38 are covered with a nap or felt-like layer 48. This layer gives the desired rolling resistance to the balls which are used in game play. The inward inclination of the perimeter walls provides the desired rebound or bounce for the balls after contact therewith.
Having now described the game apparatus, a typical game which may be played therein is as set forth below. The game is played by two players, each of whom has a different colored ball. The object of the game is to strike one's own ball so that it strikes an opponent's ball after having rebounded off from a wall or an obstacle. Each time a player is able to accomplish this, a point is scored, and that player is given another turn. It will be appreciated that while a rebound from one of the straight walls is not too difficult to predetermine, the curved walls compound the difficulty in trying to strike an opponent's ball. The eventual path of a player's ball may be further influenced by the fixed obstacles both in the central playing area and along the sides.
The scoring discs are used to keep the player's score, and the first player to score eleven points wins. Compensation for players of unequal proficiency in game play may be made by requiring the more accomplished player to rebound his ball twice from a wall or obstacle before his opponent's ball may be struck.
Turning now to FIGS. 4 and 5, an alternative embodiment is shown in which a playing surface 50 is provided and comprises a sheet of smooth rigid material 52, such as plastic, in which is formed an array of pinholes 54. Side walls comprising straight walls sections 56 and parabolic wall sections 58 surround the playing surface and fixed obstacles 60 and 61 are attached thereto. A plenum chamber 62 is formed beneath the playing surface 50 by lower walls 64 which follow the perimeter outline of the playing surface and bottom wall 65. An electric fan 66 supplies air by way of inlets 68 to the chamber 62. Air which is forced into chamber 62 escapes by way of pinholes 54 and provides a buoyant cushion for a puck 70 resting on the surface 50. The portion of the puck 70 which is resting on the surface 50 is cup-shaped and this shape aids in collecting air released through the pinholes 54. The collected air reduces the sliding friction which would otherwise severly retard a sliding motion of the puck 70 across the surface 50. By way of example only, the spacing between adjacent holes 54 can be 1" and the diameter of the puck can be 2" thus insuring that at any position on the playing surface, the puck is capturing air released from several of the holes 54. Games which can be played with the device of FIGS. 4 and 5 are similar to those which can be played with the device of FIGS. 1-4. It will be appreciated that the air escaping from the plenum 62 and captured by the puck 70 allows the puck to respond to an impact with a reaction which is smooth snd unimpeded, while at the same time being snappy.
Having thus described the invention, variations in the game apparatus and in game play will occur to those skilled in the art and these variations are intended to be within the scope of the invention as defined in the appended claims.
|
A playing surface for a billiard type of game comprises three straight ball rebound sides and one parabolic ball rebound side extending upwardly, inwardly and around the periphery of the playing surface. The playing surface and all sides have a nap or felt covering. A number of fixed obstacles on the surface are located at strategic locations to compound playing difficulty. Counting discs are threaded to rails outside of the playing surface, attached to the rebound sides and are used to keep score.
| 8
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation-In-Part of co-pending application Ser. No. 10/538,277 filed on Jun. 10, 2005, which is a National Phase of PCT/MX2003/000108 filed on Dec. 11, 2003, which designated the United States, and for which priority is claimed under 35 U.S.C. §120, and under 35 U.S.C. 119(a) to Patent Application No. PA/A/2002/01231 filed in Mexico on Dec. 13, 2002, all of which are hereby expressly incorporated by reference into the present application.
BACKGROUND OF THE INVENTION
[0002] Currently, in the pharmacological treatment of Diabetes Mellitus, there is use of insulin and groups of hypoglycemic agents such as the Sulfonylureas, the Biguanides, α-glucosidase inhibitors and Thiazolidinedione derivatives, whose action mechanism works by either stimulating the secretion of insulin or increasing the action of this hormone on the bodily tissues. The half-life of these drugs varies from 1.5 to 48 hours. Although all these drugs, by different action mechanisms, regulate the concentration of blood glucose and/or the secretion of insulin, the duration of their effect is a short period of time and none of them carries out the regeneration of the β-pancreatic cells that produce insulin and that allow the restoration of the function of this hormone. On the other hand, both exogenous insulin and hypoglycemic agents can cause side effects, such as: hypoglycemia, diarrhea, abdominal upsets, nausea and anorexia (Davis, S. and Granner, D., Insulin, Oral Hypoglycemic Agents and the Pharmacology of the Endogenous Pancreas. In: The Pharmacological Basis of Therapeutics. Eds.: Hardman, J. G., Limbird, L. E., Molinoff, P. B., Ruddon, R. W., Goodman, R., 8 th Ed. pp. 1581-1614, 1996).
[0003] None of the medication used currently for the treatment of Diabetes Mellitus regenerates either damaged tissues or cells of endogenous secretion, including the β-pancreatic cells, as the Silymarin and Carbopol compound does. Both in vitro and in vivo, it has been demonstrated that Silymarin has a protective and regenerative activity on the hepatic cells against the damage produced by different toxic substances such as: phalloidin, α-amanitin, alcohol, galactosamine, heavy metals, carbon tetrachloride, toluene, xylene or by certain drugs such as: acetaminophen, indomethacin, isoniazid and tolbutamide (Wellington, K., Harvis, B., Silymarin: A review of its clinical properties in the management of hepatic disorders. Biodrugs. 15: 465-489, 2001) since it has been shown to stabilize the cellular membrane and protect it against free radicals, i.e., it has antioxidative properties by producing an increase in the hepatic glutathione content (free radical scavenger) (Valenzuela, A., Garrido, A. Biochemical basis of the pharmacological action of the flavonoid silymarin and of its structural isomer silibinin. Biol. Res. 27:105-112, 1994).
[0004] In humans, Silymarin has been used to treat hepatic diseases such as cirrhosis, poisoning by the fungus Amanita phalloides and exposure to toxic substances (Wellington, K., Harvis, B., Silymarin: A review of its clinical properties in the management of hepatic disorders. Biodrugs. 15: 465-489, 2001).
[0005] It has been suggested that free radicals play an important role in the etiology of Diabetes Mellitus, since high serum levels of malondialdehyde (end product of lipoperoxidation) in patients with this disease (Paolisso G, De Amore, A, Di Maro G, D'Onofrio F: Evidence for a relationship between free radicals and insulin action in the elderly. Metabolism, 42:659-66, 1993). Such levels of malondialdehyde are in direct relation to the degree of complications present in patients with Diabetes Mellitus. Defense mechanisms against free radicals include glutathione and antioxidant enzymes such as superoxide dismutase, glutathione peroxidase and catalase. Soto et al. (Soto C, Pérez B, Favari L, Reyes J: Prevention of alloxan-induced diabetes mellitus in the rat by silymarin. Comp. Biochem. Physiol. 119C:125-129, 1998) reported that Silymarin increases the pancreatic and hepatic glutathione content and therefore its level in blood.
[0006] The authors of the aforementioned work also found that Silymarin impeded the elevation of free radicals in the pancreas during the induction of Diabetes Mellitus, which led to a reduction of the blood glucose which is found to be high in this disease.
[0007] Taking into consideration the background described, the compound of Silymarin and Carbopol was used as an antidiabetic agent which it is sought to be protected through this application, since it presented an unknown effect as a pancreatic regenerator and controller of the serum concentration of the glucose, which is not regulated in diabetic patients.
SUMMARY OF THE INVENTION
[0008] The present invention is drawn to a method of recovering endocrine pancreatic function in a patent in need thereof, by orally administering to the patient an effective amount of a composition comprising silymarin and carbopol, capable of regenerating damaged pancreatic cells.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] This patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the office upon request and payment of the necessary fee.
[0010] FIG. 1 shows the results of treatment Diabetes Mellitus treatment with Alloxan only.
[0011] FIG. 2 shows the results of treatment with the Silymarin and Carbopol compound administered jointly with the Alloxan.
[0012] FIG. 3 shows the results of a 3-day Silymarin treatment with Alloxan:
A. The islet of Langerhans with Alloxan treatment for 3 days B. The islet of Langerhans with Alloxan and Silymarin treatment for 3 days C. Control Sample D. The exocrine tissue with Alloxan and Silymarin treatment for 3 days
[0017] FIG. 4 shows the results of a 7-day Silymarin treatment with Alloxan:
A. The islet of Langerhans with Alloxan treatment for 7 days B. The exocrine tissue with Alloxan and Silymarin treatment for 7 days C. Control Sample
[0021] FIG. 5 shows the results of a 14-day Silymarin treatment with Alloxan:
A. The islet of Langerhans with Alloxan treatment for 14 days B. The islet of Langerhans with Alloxan and Silymarin treatment for 14 days C. The exocrine tissue with Alloxan and Silymarin treatment for 14 days D. Control Sample
[0026] FIG. 6 shows a 21-day Silymarin treatment with Alloxan:
A. The exocrine tissue with Alloxan treatment for 21 days B. The islet of Langerhans with Alloxan and Silymarin treatment for 21 days C. The exocrine tissue with Alloxan and Silymarin treatment for 21 days
[0030] FIG. 7 shows cuts of the pancreatic tissue with Alloxan (insulin) treatment are shown at different times:
A. 7 days B. B. 14 days C. 21 days D. Control Sample
[0035] FIG. 8 shows cuts of the pancreatic tissue with Alloxan and Silymarin (insulin) treatment are shown at different times:
A. 3 days B. 7 days C. 14 days D. 21 days E. Control Sample
[0041] FIG. 9 shows cuts of the pancreatic tissue with Alloxan (BrdU) treatment are shown at different times:
A. 7 days B. B. 14 days
[0044] FIG. 10 shows cuts of the pancreatic tissue with Alloxan and Silymarin (BrdU) treatment are shown at different times:
A. 7 days B. 14 days C. 21 days
DESCRIPTION OF THE INVENTION
[0048] This invention corresponds to the use of Silymarin with Carbopol as a regenerator of the pancreatic tissue and cells of endogenous secretion damaged by Diabetes Mellitus, which suppresses the inconvenient side effects that are presented with the administration of drugs currently used in the treatment of Diabetes Mellitus.
[0049] The compound of Silymarin and Carbopol is obtained by the following steps:
a) Dissolution at 0.5% of Carbopol in deionized water in a magnetic agitator for one hour. b) Addition of Silymarin in a percentage of 5 to the foregoing dissolution and subjected to agitation for a minimum period of one hour until a homogenous mixture is obtained.
[0052] The homogenous mixture may be presented with any vehicle in formulations for oral administration, such as: solution, suspension, emulsion, hard gelatin capsules, soft gelatin capsules, immediate release tablets, sustained release tablets, prolonged release tablets, controlled release tablets.
[0053] An illustrative but not limitative example to demonstrate the pancreatic regenerative activity of the Silymarin and Carbopol compound is found in the one that was administered orally at a dose of 200 mg/Kg, either simultaneously with the diabetogenic agent Alloxan or separately.
[0054] The treatment of the Silymarin and Carbopol combined with Alloxan was done in two ways. In the first case, a dose of 200 mg/Kg of the Silymarin and Carbopol compound was administered orally at 6, 24 and 48 hours (two days) after the first dose. In the second case, in addition to the dose mentioned in the first case, the administration was prolonged every 24 hours after the first dose for five more days (seven days). In both cases, the dose of Alloxan was 150 mg/Kg, which was administered subcutaneously one hour after the first dose of the Silymarin and Carbopol compound.
[0055] Another example that was also used to demonstrate the pancreatic regenerative activity of the Silymarin and Carbopol compound is in the one that proved the effect of this compound separately with the diabetogenic agent Alloxan, i.e. first the Alloxan was administered and then after 20 days the daily treatment with the Silymarin and Carbopol was begun at the same doses as those already mentioned in the first two cases above, for a period of time from 4 to 7 weeks.
[0056] The demonstration of the antidiabetic effect of this Silymarin and Carbopol compound is described in the examples mentioned below.
Example 1
Determination of Serum Glucose
[0057] The determination of blood glucose was carried out by the Baner method. This consisted in taking 50 μl of serum to which 3.0 ml of ortho-toluidine reagent were added which reacts with aldohexoses and forms glucosamine and a Schiff base, the green color developed has a maximum absorption at 620 nm and is proportional to the quantity of glucose present.
[0058] In the case of the combined administration of the Silymarin and Carbopol compound with Alloxan, the determination of serum glucose was done before the administration of the drugs and at 3, 5, 15 and 30 days after the treatment. For the case where the treatment of the Silymarin and Carbopol compound was begun 20 days after the administration of the Alloxan, the determination of the serum glucose was done before the administration of any drug, 20 days after the application of the Alloxan and after each week subsequent to the start of the treatment with the Silymarin and Carbopol compound.
[0059] The results showed that in Diabetes Mellitus (treatment with Alloxan only) there was an increase of between 100 and 400% in the serum levels of the glucose compared with the normal values, which range from 80 to 120 mg/dl. The Silymarin and Carbopol compound administered jointly with the diabetogenic agent Alloxan prevented the increase in the concentration of serum glucose that was presented with the administration of Alloxan alone. The results obtained from the treatment with the Silymarin and Carbopol compound started twenty days after the administration of the Alloxan showed that the values of the serum glucose concentration that were significantly high, approximately 400% above the normal value (before starting the treatment with the Silymarin and Carbopol compound) gradually decreased to reach the normal levels in an average time of seven weeks.
[0060] The treatment with the Silymarin and Carbopol compound administered alone did not modify the serum glucose concentration.
Example 2
Determination of the Concentration of Blood Insulin by the ELISA Method (Enzyme Linked Immuno Sorbent Assay)
[0061] This determination was carried out in 10 μl of serum, which was incubated for two hours with monoclonal antibodies aimed against separate antigenic determinants in the insulin molecule. During the incubation, the insulin of the sample reacted with anti-insulin antibodies and with peroxidase-conjugated anti-insulin antibodies. After this time, flushing was done to remove the antibody that failed to combine with the insulin molecules of the sample. 200 μl of 3,3,5,5′-tetramethylbenzidine was then added and the samples remain with this reagent for 30 minutes in order to be able to detect the conjugated compound, which is colored and can be quantified spectrophotometrically. The reaction was finalized by the addition of 50 μl of sulfuric acid and it was read at 450 nm in an ELISA reader in order to be able to determine the insulin concentration in each of the samples.
[0062] In the case of the combined administration of the Silymarin and Carbopol compound and Alloxan, the determination of serum insulin was done before the administration of the drugs and at 3, 5, 15 and 30 days after the treatment. For the case where the treatment of the Silymarin and Carbopol compound was begun 20 days after the administration of the Alloxan, the determination of the serum insulin was done before the administration of any drug, 20 days after the application of the Alloxan and at the end of the treatment with the Silymarin and Carbopol compound (when the glucose levels were found to be in the range of the normal values).
[0063] The results showed that in Diabetes Mellitus (treatment with Alloxan only) there was a decrease of between 80 and 90% in the serum levels of insulin compared with the normal value, which is 1 ηg/ml. It was observed that the joint treatment of the Silymarin and Carbopol compound and Alloxan impeded the reduction of the insulin serum levels and kept them within the range of the normal value. In the case of the treatment with the Silymarin and Carbopol 20 days after the administration of Alloxan, the insulin serum level was seen to increase to the range of the normal values. These normal values of serum insulin corresponded with those of glucose (example 1).
Example 3
Histopathological Analysis of the Pancreatic Tissue
[0064] This analysis was done in transversal fragments of pancreas approximately 0.7 cm long corresponding to the head of the organ. Subsequently, by the paraffin embedding technique, 5 μm sections where then obtained, which were stained with the dyes hematoxylin and eosin (HE). This technique consists in: 1) dehydration of the tissue, which is done by passing the tissue through different concentration of alcohol (from 25 to 100%) and then to an alcohol-toluene, toluene-paraffin and paraffin mixture. Once the tissues are dehydrated, blocks are formed with paraffin. 2) Sectioning of the tissue. This is done in a microtome, which is adjusted to the right section thickness of 4 to 6 μm and is placed in a slide. 3) Staining of the sections. This was done with the dyes hematoxylin and eosin.
[0065] In the case of the combined administration of the Silymarin and Carbopol compound and Alloxan, the histopathological analysis was done at 3, 5, 15 and 30 days after the treatment. For the case where the treatment of the Silymarin and Carbopol compound was begun 20 days after the administration of the Alloxan, the histopathological analysis was done 20 days after the application of the Alloxan and at the end of the treatment with the Silymarin and Carbopol compound (when the glucose levels were found to be in the range of the normal values, i.e. between 80 and 120 mg/dl).
[0066] In Diabetes Mellitus (treatment with Alloxan only) damage occurred in the pancreatic tissue that was observed as cellular disorganization with loss of the islets of Langerhans. Also observed were zones of necrosis, of cellular lysis, hemorrhagic zones, infiltration of lymphocytes, lysis of erythrocytes, as well as an increase in the adipose tissue that forms the capsule of the lobule.
[0067] The treatment with the Silymarin and Carbopol compound administered jointly with the Alloxan prevented the tissue damage in the pancreas that occurred in the Diabetes Mellitus, i.e. the tissue presented no alteration. The administration of the Silymarin and Carbopol compound, 20 days after the administration of the Alloxan, regenerated the pancreatic tissue, i.e. all the damage observed in the Diabetes Mellitus was completely reverted and a completely normal tissue was observed.
Example 4
Immunohistochemical Analysis for Insulin and Glucagon in the Islets of Langerhans by Confocal Microscopy
[0068] This analysis is carried out on sections of pancreatic tissue (corresponding to the head of the pancreas). Once the sections have been obtained (described in example 3) they are placed on a slide and the tissue is then deparaffinated and rehydrated. It is begun in pure xylol, with two changes of 10 minutes each. The samples are then passed to a mixture of ethanol-xylol for 10 minutes and afterward to alcohols of different percentages: 100, 90, 80 and 70% for five minutes each. Finally, they are passed to a PBS solution (phosphate buffered solution) for 30 minutes in order to then carry out the immunostaining process. This is begun with the incubation of the samples in a PBS-Triton solution for 10 minutes at an ambient temperature (20-22° C.), they are flushed with PBS without triton and the samples are blocked with albumin in PBS. The samples are flushed with PBS for 1 to 5 minutes. A mixture is then made of primary antibodies anti-insulin and anti-glucagon in PBS and they are left to incubate for approximately 12 hours. At the end of this time, they are flushed with PBS and incubated in a mixture of secondary antibodies coupled with fluorochromes, fluorescein and rhodamine, for one hour at ambient temperature and they are then mounted in a specific medium to preserve the fluorescence. The samples are analyzed by confocal microscopy. In Diabetes Mellitus (treatment with Alloxan only) ( FIG. 1 ) a destruction occurred of the pancreatic islet and only fragments of this were observed with a very scarce presence of insulin (β) y glucagon (α). In the treatment with the Silymarin and Carbopol compound administered jointly with the Alloxan ( FIG. 2 ), the destruction of the pancreatic islet was prevented and this presented an image very similar to that of an islet in normal conditions, i.e. all the cells that form it were shown to be preserved. In most of these, insulin (β) is present, produced from the β cells and only in those of the periphery was the glucagon (α) observed, produced from the α cells.
[0069] The administration of the Silymarin and Carbopol compound twenty days after the Alloxan reversed the damage observed in the Diabetes Mellitus, i.e. it caused regeneration of the destroyed pancreatic islet presenting an islet with normal characteristics (described in the previous paragraph), which implies the recovery of the functioning of the β-pancreatic cells and therefore the production of insulin.
[0070] This methodology is equivalent to applying it on the human body on any type of Diabetes, since the action level of this composition is at the level of the dysfunction or destruction of the β pancreatic cells and their mechanisms against the cellular damage due to free radicals.
Example 5
Determination of the Activity of the Pancreatic Antioxidant Enzymes
[0071] A determination was made of the pancreatic activity of the antioxidant enzymes: superoxide dismutase, glutathione peroxidase and catalase. To do such determination, the pancreas was weighed, it was homogenized with a phosphate buffer 50 mM, it was centrifuged at 3000 rpm, and the supernatant was separated. The activities of the aforementioned enzymes was determined in this.
[0072] Superoxide dismutase.—This quantification was done by the method of Prasad et al. (1992). Superoxide ions are formed by xanthine and xanthine oxidase. These ions react with the tetrazolium blue and they form a colour compound that can be spectrophotometrically quantified at 560 nm. A unit of superoxide dismutase can inhibit the formation of this compound by 50%.
[0073] Glutathione peroxidase.—This quantification was done by the method of Prasad et al. (1992). This enzyme catalyzes the breakdown of H 2 O 2 by the NADPH. Its activity is measured by the velocity of absorbance change during the conversion of NADPH to NADP + and this may be spectrophotometrically registered at 300 nm.
[0074] Catalase.—This quantification was carried out by the Aebi method (1995). This enzyme catalyzes the breakdown of H 2 O 2 and the decomposition velocity of the oxygenated water is measured spectrophotometrically at 240 nm.
[0075] In the Diabetes Mellitus (treatment with Alloxan only) there was a decrease of between 70 and 75% in the activity of the three enzymes studied: superoxide dismutase, glutathione peroxidase and catalase.
[0076] The combined administration of the Silymarin and Carbopol compound and Alloxan showed an increase in the activity of the pancreatic antioxidant enzymes, since this was no different than the control (normal) values.
[0077] The administration of the Silymarin and Carbopol compound twenty days after the Alloxan reverted the damage observed in the Diabetes Mellitus in the activity of the three enzymes studied and even values of enzymatic activities higher than normal values were observed (see table).
[0000]
Treatment
Alloxan (20 days
Silymarin administered
Enzymatic
after its
20 days after the
activity
administration)
application of the Alloxan
Glutathione Peroxidase
0.016 ± .002
0.052 ± 0.002
μM NADPH/min/mg prot
Superoxide Dismutase
4.3 ± 0.02
46.5 ± 0.50
U/mg protein.
Catalase
0.01 ± 0.002
0.04 ± 0.00
k/sec/mg of protein
Example 6
Effects of Silymarin in Rats with Diabetes Mellitus Induced by Alloxan
[0078] An analysis of the effects of Silymarin was made with respect to the proliferation of β-pancreatic cells in early stages of a 3-to-21-day Silymarin treatment of rats with Diabetes Mellitus induced by Alloxan.
[0079] The methodology included the determination of glucose during treatment. At the end of the treatment, BrdU (5-bromo-2-deoxyuridine) was administered since BrdU is a marker of cells that are being divided. The amount administered was 50 mg/Kg, i.p.
[0080] BrdU.—BrdU is used as a proliferation detection technique and acts as a DNA analogue thus substituting the DNA's timidine base and only marking the cells that are being divided.
[0081] In the subsequent 18 to 20 hours, the animal was sacrificed. The pancreas was then extracted and put in absorbed formaldehyde in a pH level of 7.0. The tissue was included in paraffin and then 5 μm cuts were made. Immunohistochemical studies were carried out through fluorescence and peroxidase methods to study the proliferation of β-pancreatic cells. The fluorescence painting was observed in a confocal microscope (Zeiss). The cell count was then made with BrdU or insulin marking through the painting with peroxidase in an optical microscope (Zeiss).
[0082] The results of the treatment are illustrated in FIGS. 3 through 10 .
[0083] In FIG. 3 , the following is shown in a 3-day Silymarin treatment with Alloxan:
E. The islet of Langerhans with Alloxan treatment for 3 days F. The islet of Langerhans with Alloxan and Silymarin treatment for 3 days G. Control Sample H. The exocrine tissue with Alloxan and Silymarin treatment for 3 days
[0088] Red marks BrdU with cells proliferating. Green marks insulin with peroxidase with cells producing insulin. Brown marks BrdU-insulin colocation with cells proliferating and producing insulin.
[0089] In FIG. 4 , the following is shown in a 7-day Silymarin treatment with Alloxan:
D. The islet of Langerhans with Alloxan treatment for 7 days E. The exocrine tissue with Alloxan and Silymarin treatment for 7 days F. Control Sample
[0093] Red marks BrdU. Green marks insulin. Brown marks BrdU-insulin collocation.
[0094] In FIG. 5 , the following is shown in a 14-day Silymarin treatment with Alloxan:
E. The islet of Langerhans with Alloxan treatment for 14 days F. The islet of Langerhans with Alloxan and Silymarin treatment for 14 days G. The exocrine tissue with Alloxan and Silymarin treatment for 14 days H. Control Sample
[0099] In FIG. 6 , the following is shown in a 21-day Silymarin treatment with Alloxan:
D. The exocrine tissue with Alloxan treatment for 21 days E. The islet of Langerhans with Alloxan and Silymarin treatment for 21 days F. The exocrine tissue with Alloxan and Silymarin treatment for 21 days
[0103] In FIG. 7 , cuts of the pancreatic tissue with Alloxan (insulin) treatment are shown at different times:
E. 7 days F. B. 14 days G. 21 days H. Control Sample
[0108] In FIG. 8 , cuts of the pancreatic tissue with Alloxan and Silymarin (insulin) treatment are shown at different times:
F. 3 days G. 7 days H. 14 days I. 21 days J. Control Sample
[0114] In FIG. 9 , cuts of the pancreatic tissue with Alloxan (BrdU) treatment are shown at different times:
C. 7 days D. B. 14 days
[0117] In FIG. 10 , cuts of the pancreatic tissue with Alloxan and Silymarin (BrdU) treatment are shown at different times:
D. 7 days E. 14 days F. 21 days
[0121] With an analysis of the results outlined above, the effects of Silymarin ascertain the differentiation of the undifferentiated cells of the pancreas and those of intestinal origin.
|
The present invention refers to a new compound containing Silymarin with Carbopol for the treatment of Diabetes Mellitus. This compound morphologically and structurally regenerates the damage that occurs in the pancreatic tissue in Diabetes Mellitus, and regenerates the insulin-producing pancreatic cells (β cells). It therefore regulates the serum levels of this hormone. Furthermore, it restores and maintains the normal concentrations of the blood glucose.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 11/457,197, filed Jul. 13, 2006, which claims the benefit under 35 U.S.C. §119(e) of the U.S. Provisional Application 60/705,370 filed Aug. 4, 2005. Each of these applications is incorporated by reference in its entirety and for all purposes.
BACKGROUND OF THE INVENTION
The invention relates to a pharmaceutical formulation for oral administration comprising an effective amount of prednisolone acetate in a pharmaceutically acceptable, aqueous, suspension-stabilizing vehicle.
Corticosteroids are used to treat patients with inflammatory and immune diseases. Prednisolone is a corticosteroid that has been formulated into capsules, tablets and liquid preparations for oral delivery. The base form of prednisolone and the salt form, prednisolone sodium phosphate, are commercially available in oral liquid formulations. However, the bitter taste of the commercial compositions is described extensively in the medical literature and contributes to poor patient compliance with medical instructions for the use of the drug. U.S. Pat. No. 4,448,774 describes aqueous solutions comprising a steroid selected from the group of prednisolone, prednisolone sodium phosphate, prednisone and methyl prednisolone. The solution described in the patent is described as being preferable to previously known formulations because no alcoholic solvent is required and it is not a suspension. Suspensions of prednisolone are reported to be problematic because they are not stable and over time the active agent settles out of the formulation and gives variable dosage amounts. U.S. Pat. No. 5,763,449 describes the use of a combination of three well known taste masking agents to achieve a pleasant tasting liquid pharmaceutical composition. Prednisolone and prednisolone sodium phosphate are disclosed as bitter tasting drugs that may be used in the formulation.
Another form of prednisolone, prednisolone acetate, is commonly used for medicinal purposes. However, because of its poor aqueous solubility, prednisolone acetate is used in topical, parenteral and opthamalogical formulations, not oral formulations. The use of the acetate form could provide a taste advantage because it is insoluble in the aqueous environment of the mouth, and therefore prevents the interaction of the bitter-tasting molecules of the prednisolone with the taste buds.
The present disclosure is to a novel, organoleptic, oral, liquid suspension of prednisolone acetate that is an improvement over previously disclosed and commercialized oral prednisolone dosage forms.
SUMMARY OF THE INVENTION
The present invention is to a pharmaceutical composition for oral delivery comprising a pharmaceutically effective amount of prednisolone acetate, pharmaceutically acceptable vehicle and a thickening agent. The present composition contains between about 0.5 mg/mL to about 7 mg/mL of prednisolone acetate. More preferably the concentration of prednisolone acetate is between about 1 mg/mL to about 5 mg/mL. The most preferred compositions of the present invention will deliver 5 mg/5 mL prednisolone acetate or 15 mg/5 mL prednisolone acetate.
The inventive formulation has prednisolone acetate dispersed in an oral formulation comprising a vehicle and a thickening agent. The aqueous vehicle may be comprised of glycerin, and the preferred thickening agent is carbomer.
The prednisolone acetate of the present invention is within a fine range of particle size. The median particle size of the prednisolone acetate is between about 1 μm to 30 μm, particularly between about 5 μm to 10 μm, and more particularly between 6 μm to 8 μm. Ninety percent of the prednisolone acetate in the inventive composition has a median particle size of greater than 1 μm and less than 30 μm.
The inventive composition further comprises pharmaceutically acceptable excipients. The excipients include wetting agents, spreading agents, stabilizers, sweeteners and flavoring agents. The inventive composition is organoleptically pleasing.
The novel formulation has a pH of between about 4.0 to about 5.9, more preferably of between about 4.6 to about 5.4, most preferably 4.8 to 5.2.
The inventive composition is comprised of from about 29 to about 64% water (w/w), up to about 50% glycerin (w/w), up to about 20% sorbitol (w/w), up to about 10% propylene glycol (w/w), up to about 3% surfactant (w/w) and up to about 1% of a thickening agent (w/w).
The pharmaceutical composition of the invention comprises the following ingredients a) 0.1% poloxamer 188; b) 50% glycerin; c) 5% sorbitol crystalline; d) 5% propylene glycol; e) 0.065% disodium edetate; f) 0.2% sucralose; g) 0.44% carbomer; h) 0.04% butylparaben; and i) sodium hydroxide to a pH of between about 4.8 to about 5.2.
The inventive formulation may be used to treat a patient in need of an effective amount of the active pharmaceutical vehicle, prednisolone.
Among the medical conditions that may be treated by the formulation of the present invention are endocrine disorders, rheumatic disorders, collagen diseases, dermatologic diseases, allergic states, respiratory diseases, hemaologic disorders, neoplastic diseases, edema, gastrointestinal diseases or nervous diseases using an effective amount of the orally delivered prednisolone acetate composition.
DETAILED DESCRIPTION OF THE INVENTION
In describing embodiments of the present invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. It is to be understood that each specific element includes all technical equivalents, which operate in a similar manner to accomplish a similar purpose. The above-described embodiments of the invention may be modified or varied, and elements added or omitted, without departing from the invention, as appreciated by those skilled in the art in light of the above teachings. Each reference cited herein is incorporated by reference as if each were individually incorporated by reference.
The formulation of the present invention is a palatable, oral formulation of prednisolone acetate. Prednisolone acetate has been used in ophthalmic and parenteral medicinal products, but has not previously been used in oral liquid preparations. Prednisolone acetate is practically insoluble in water. The low solubility presents a formulary challenge during product development of an aqueous liquid oral preparation. However, the use of the acetate form provides a taste advantage because the active does not dissolve in the aqueous environment of the mouth, and therefore prevents the interaction of the bitter-tasting molecules of the prednisolone with the taste buds.
The present invention is an aqueous suspension having a thickening component and a vehicle, or carrier, component and may include other pharmaceutically acceptable excipients. The vehicle is pharmaceutically acceptable, aqueous and suspension-stabilizing. Prednisolone acetate is evenly dispersed in the semi-solid aqueous vehicle. The suspension has a homogeneity so that the active ingredient is uniformly dispersed but undissovled in the vehicle. The formulation consists of mutually compatible components at room temperature. The suspension has a crystalline stability in that the prednisolone particles stay within a target particle size range over time.
The vehicle component serves as the external phase of the suspensions. The vehicle may be comprised of water, glycerin, propylene glycol and mixtures thereof. The vehicle component may contain glycerin up to about 50%. The vehicle may also comprise propylene glycol up to about 20% or from about 3% to about 10%. Purified water comprises the bulk of the vehicle component comprising from about 29% to about 64% of the formulation.
Purified water makes up the bulk of the vehicle component, comprising from about 29% to 64% (w/w) of the formulation. Water concentration can be less than about 50% (w/w) or even less than about 43% (w/w).
Thickening agents are pharmaceutically acceptable excipients that add a desired viscosity and flow to a formulation. Carbomers are synthetic high molecular weight polymers of acrylic acid. In one embodiment, carbomer 943P (Carbopol 974P) has been found to be a suitable thickening, or gelling agent, providing good sensory appeal and texture. The rheology of the carbomer provides for a high yield value, low shear thinning quality, in non-thixotropic liquid formulations.
The viscosity of the carbomer gel is pH dependent. Carbomer gels exhibit maximum viscosity at about pH 7.0. More acidic or basic pH's will cause the carbomer to lose viscosity. However, prednisolone acetate is most stable at slightly acidic pH's, and will degrade to undesirable breakdown products at the higher pH. At neutral pH's, prednisolone acetate will undergo oxidation and hydrolysis and form undesirable and less active degradation products. At a pH of 4.6 to 5.4, prednisolone acetate is stable in the formulation and the carbomer may retain its viscosity. The carbomer comprises up to about 1% (w/w) of the inventive formulation. In particular, we have found that the carbomer of the inventive formulation should be between about 0.40% to about 0.50%, more particularly, about 0.40% to about 0.48%.
The oral formulation of prednisolone acetate is a spill-resistant formulation. Spill resistant oral formulations are more extensively described in, for example, U.S. Pat. Nos. 6,071,253, and 6,102,254, herein incorporated by reference.
The pharmaceutical suspension comprising of the invention has prednisolone acetate uniformly dispersed in an aqueous vehicle, the active ingredient remaining in suspension without agitation during the product shelf-life. The shelf life may be up to about six, twelve, eighteen, twenty-four months, thirty months, or thirty-six months. The suspension has antimicrobial activity, is pharmaceutically effective and meets applicable regulatory requirements as would be understood by a person of ordinary skill. The viscosity may be about 5,000 to about 15,000 cps, about 5,000 to about 14,800 cps, about 9,000 to about 11,000 cps, or about 9,500 to about 10,500 cps. In inventive pharmaceutical suspensions there is no crystalline growth during a heat-cool study for three days at a temperature range of about 8° C. to about 45° C. The active ingredient particles may be crystals that neither dissolve or grow substantially when the sample is heated e.g. to 45° C. and cooled to room temperature repeatedly.
The formulation is dosed by volume, and specific gravity values were used to estimate the prednisolone acetate concentration in the composition. The 5 mg/mL dose was calculated, based on specific gravity to be 0.097% (w/w), which is equivalent to 0.087% (w/w) of the prednisolone base form. The 15 mg/mL dose was calculated to be about 0.293% (w/w), which is equivalent to 0.262% of prednisolone base form.
The particle size of the active pharmaceutical ingredient may have important effects on the bioavailability of a formulation. Smaller particle sizes have increased surface area and will dissolve faster than larger particles. However, decreasing the particle size may cause some agglomeration of the particles, and the increased surface area can result in faster degradation of the compound due to oxidation and hydrolysis. In the inventive formulation, a fine particle size was found to achieve the desired bioavailablity. The prednisolone acetate of the inventive formulation has a median particle size of approximately from about 1 μm to about 30 μm, more preferably about 5 μm to about 20 μm, most preferably from about 6 μm to about 8 μm. The particle size may be achieved using such methods air-jet milling, ball milling, mortar milling or any other method known in the art for decreasing particle size. For example, the prednisolone acetate particles of the disclosed formulation were micronized using a stainless steel, air-jet mill with a grinding chamber diameter of four inches (Sturtevant, Hanover, Mass., U.S.A., model no. SDM-4.)
The size of the particles may be measured using a light scattering device, sedimentation methods, centrifugal force measurements, or any method known to one skilled in the art. By means of an example, the Matersizer 2000 manufactured by Malvern Instruments, Ltd., Malvern U.K., may be used to measure the particle size.
Pharmaceutical excipients are pharmaceutically acceptable ingredients that are essential constituents of virtually all pharmaceutical products. Excipients serve many purposes in the formulation process. The inventive pharmaceutical suspensions may comprise at least one additional component selected from the group consisting of excipients, surface active agents, dispersing agents, sweetening agents, flavoring agents, coloring agents, preservatives, oily vehicles, solvents, suspending agents, dispersing agents, wetting agents, emulsifying agents, demulcents, buffers, salts, spreading agents, antioxidants, antibiotics, antifungal agents and stabilizing agents.
Spreading agents may be added to the vehicle component. Polyols, such as malitol, mannitol, polyethylene glycol and sorbitol may be added to the vehicle components to adjust the spreadability in the spoon bowl upon pouring. The present embodiment may contain sorbitol, in a concentration of less than 5%.
The suspensions of the present invention may also contain Edetate Disodium (EDTA). EDTA is a chelating agent that forms a stable water-soluble complex with alkaline earth and heavy metal ions. It is useful as an antioxidant synergist, sequestering metal ions that might otherwise catalyze autoxidation reactions. EDTA may also have synergistic effects as an antimicrobial when used in combination with other preservatives (Handbook of Pharmaceutical Excipients 4 th Ed.).
The suspension formulations may require a crystal conditioning surfactant, i.e. a wetting agent. The hydrophobic properties of prednisolone acetate may benefit from a wetting agent to disperse the steroid in the formulation. A concentration of from about 0.05% to about 0.5% poloxamer 188 was found to be effective at wetting the prednisolone acetate without excessive foaming and dispersion of the suspension.
The present formulation is an improvement over previously described prednisolone suspensions because the ingredient remains suspended indefinitely, without agitation; that is without stirring or shaking. The dispensed dose is always uniform over the shelf life of the product. The formulation of the invention can not be shaken easily, so the particles remain suspended without shaking.
The suspension has antimicrobial activity. Propylparaben (up to about 0.04%) and butylparaben (0.018% to about 0.18%) are suitable. Other antimicrobial excipients may also be used. These suspensions are alcohol-free.
The organoleptic ingredients improve the taste and appearance and do not negatively affect the suspension stability. The organoleptic agents in the following examples include coloring and flavoring agents, sweeteners and masking agents.
Mutual compatibility of the components means that the components do not separate in preparation and storage for up to the equivalent of two years at room temperature (as indicated by three month intervals of accelerated stability testing at 40° centigrade and at 75% relative humidity). Storage stability means that the materials do not lose their desirable properties during storage for the same period. Preferred compositions do not exhibit a drop in viscosity of more than 50% or an increase in viscosity of more than 100% during that period.
The following examples further illustrate the invention, but should not be construed as limiting the invention in any manner.
Example 1
The Prednisolone Acetate Oral Suspension was Formulated to Contain the Following Ingredients
TABLE I
Composition of Oral Prednisolone Acetate Suspension
5 mg/5 mL
INGREDIENTS
(w/w %)
15 mg/mL
Prednisolone Acetate
0.097
0.293
Poloxamer 188
0.1
0.1
Glycerin
50
50
Sorbitol Crystalline
5
5
Propylene Glycol
5
5
Edetate Disodium
0.065
0.065
Sucralose
0.2
0.2
Artificial Cherry Flavor
0.15
0.15
Bell Flavor Masking Agent
0.2
0.2
Carbomer 934
0.44
0.44
Butylparaben
0.04
0.04
Purified water
to 100%
to 100%
NaOH
pH 4.6-5.4
pH 4.6-5.4
Example 2
Comparison of different Prednisolone Actives for Sensory Evaluation
A small sample of volunteers compared the different formulations of prednisolone for taste and flavor. Results are given in Table 2.
TABLE 2
Sensory Perception following different
samples of Prednisolone Formulations
Product Description
Initial Taste
After Taste
Commercially Available
Slightly sweet,
Persistent, very
Prednisolone
intense wild
bitter
5 mg/5 ml
cherry
Commercially Available
Moderately sweet,
Delayed moderately
Prednisolone sodium
mild raspberry
bitter unpleasant
phosphate
taste persists for
5 mg./5 ml
long time
Taro Prednisolone
Pleasantly sweet,
Delayed slightly
Phosphate Experimental
cherry flavored
bitter, Intensity
Syrup 5 mg/5 mL
increases with time
Prednisolone Acetate
Pleasantly sweet,
No bitterness
Suspension 5 mg/mL
cherry flavored
perceived
Example 3
pH Screen Stability
Stability testing was performed on 1.0 kg portions of a 5.0 kg experimental batch of 5 mg/5 mL prednisolone acetate. NaOH was added to the portions to give various pH values (Batch A-E) and packaged in 4 ounce amber PETG bottles. The samples were left at the environmentally stressed conditions of 40° centigrade or 50° centigrade for one month. HPLC methods were used to measure the percent of prednisolone acetate retained in the bottle. The control sample used was a 5 mg/5 mL prednisolone acetate suspension exposed at room temperature and sampled after 4 months. The data is summarized in Table 3.
As demonstrated by the results shown in Table 3, in the pH range of 5.0 to 6.2, the micronized prednisolone acetate is more stable at the lower pH values.
TABLE 3
Stability of Prednisolone Acetate Oral Suspension (varying pH)
Batch
(%)Prednisolone
(%)Prednisolone
(%)Prednisolone
No.
pH
Acetate 1 (RT)
Acetate 1 (40° C.)
Acetate 1 (50° C.)
A
5.02
96.7
96.7
95.2
B
5.39
96.1
96.1
93.0
C
5.71
95.4
95.4
81.7
D
5.90
92.8
92.8
44.3
E
6.22
87.3
87.3
67.4
Example 4
Suspension Dissolution
Dissolution tests are a qualitative tool that provides information about the biological availability of a drug formulation. Experimentally, suspension formulations are considered to disintegrate equivalently to tablet formulations, therefore dissolution testing is done comparing suspensions to tablets. A standard dissolution test (USP Apparatus 2 (paddle)) was followed to compare the prednisolone acetate suspension to a commercially available 5 mg tablet of prednisolone. As shown in FIG. 1, the dissolution curves of the suspensions were very similar to the dissolution curve for the tablet following a 15 minute period.
TABLE 4
Dissolution of Prednisolone Acetate
Suspensions v. Prednisolone Tablets
Prednisolone Acetate Suspension
Prednisolone Tablets
TIME
15 mg/5 ml
5 mg/5 ml
5 mg
5
48
45
69
15
85
82
93
30
95
93
96
45
97
95
98
60
97
96
98
Example 5
Twenty three volunteers (male and female non- or ex-smokers) were orally administered a single 5 mg dose of prednisolone in the morning after a ten hour overnight fast. The study design was a randomized, 6-sequence, 3-period, crossover design. Either 5 mL of a 5 mg/mL prednisolone acetate suspension, or one 5 mg tablet of a commercially available product, was administered. Blood samples were taken at determined intervals. Pharmacokinetic parameters used to evaluate and compare the relative bioavailability, and therefore bioequivalence, of the two formulations of prednisolone after a single oral dose administration under fasting conditions were C max , AUC T , AUC ∞ , K el and T 1/2el .
C max —Maximum Concentration. AUC T —Area under the Concentration-time Curve Using the Trapezoidal Method to the Last Measurable Concentration; AUC ∞ —Area under the Concentration-time Curve extrapolated to infinity; K el —Elimination Rate Constant; T 1/2el —Terminal Half-Life.
Bioequivalence was determined using the 90% confidence interval for the exponential of the difference between the tablet and the suspension. The test met the 80.00-125% confidence interval limits with a statistical power of at least 80%.
TABLE 5
Bioequivalency: Prednisolone 5 mg/5 mL Suspension versus 5 mg/5 mL
Syrup versus 5 mg Tablets Following a 5 mg administration/Fasting
State (100% prelims N = 23/23)
Prednisolone 5 mg/ml
Prednisolone 5 mg
Suspension
Tablet
Coefficient
Coefficient
PARAMETER
MEAN
of Variation
MEAN
of Variation
C max (ng/mL)
160.90
15.8
176.27
18.7
T max (hours)
1.33
41.6
1.00
33.2
AUC T (ng · h/mL)
821.73
20.2
812.39
17.7
AUC ∞ (ng · h/mL)
852.23
19.6
846.53
17.1
K el (hour −1 )
0.2681
13.4
0.2629
9.7
T 1/2el (hours)
2.63
12.6
2.66
10.0
For Tmax, the median is presented.
In describing embodiments of the present invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. It is to be understood that each specific element includes all technical equivalents, which operate in a similar manner to accomplish a similar purpose. The above-described embodiments of the invention may be modified or varied, and elements added or omitted, without departing from the invention, as appreciated by those skilled in the art in light of the above teachings. Each reference cited herein is incorporated by reference as if each were individually incorporated by reference.
|
The present invention relates to novel oral suspension formulation comprising prednisolone acetate, a pharmaceutically acceptable vehicle and a thickening agent. The present invention further provides a method of treating patients in need of prednisolone with the novel formulation.
| 0
|
BACKGROUND OF THE INVENTION
The invention relates to overlock sewing machines in general, and more particularly to improvements in mechanisms for severing threads in overlock sewing machines
Overlock sewing machines are used for overedging, for cutting and overedging, for seaming and overedging, for roll hemming, for overlocking of several material layers and cross seams and/or for a number of other special operations of utilitarian and/or decorative nature. For example, an overlock sewing machine can be used for overedging and simultaneous formation of a two-thread chain stitch next to the edge. A so-called safety stitch, for example, of the type SSa-2 according to stitch type 516 (US Federal Standard No. 751a) consists of an edge stitch (stitch type 504) and a parallel stitch (stitch type 401) of the aforementioned US Federal Standard No. 751a.
During sewing, the warp thread of the parallel stitch is guided by a hook or shuttle which is caused to oscillate transversely of the direction of stitching. The hook cooperates with thread guide means and with a thread looping unit which rotates in synchronism with movements of the hook. The guide means includes a substantially U-shaped carrier for a device which tensions the yarn, and the carrier has guide slots for the thread as well as an eyelet through which the thread passes to be deflected in a predetermined direction, namely toward the hook. The legs of the U-shaped carrier flank two rotary entraining and looping discs which are coaxial with but spaced apart from each other to provide room for a thread stripping device which is secured to the frame of the sewing machine.
A thread which is stored in the form of a cone, spool or bobbin advances from the respective source through the thread tensioning device and thereupon transversely of the direction of rotation of the looping discs, through the slots in the legs of the carrier, toward the eyelet and thence to the hook or shuttle. The discs are positioned with reference to the carrier in such a way that the thread is adjacent their peripheral surfaces. When the shaft which carries the discs is set in rotary motion, flats at the peripheries of the discs engage the thread between the legs of the carrier and pull the thus engaged thread toward the stripping device which segregates the freshly looped portion of the thread from the discs and enables the hook or shuttle to advance a length of thread toward the needle. The same operation is repeated during each cycle.
If the thread happens to break, it is still likely to be engaged by the looping discs but the loop which is formed by such discs cannot be separated by the stripping device because the leader of the broken thread is no longer under tension. The broken thread is simply convoluted onto the shaft which drives the looping discs. This necessitates a lengthy interruption of operation of the sewing machine because the convolutions are not readily removable. In fact, the package of convoluted thread can cause damage to the carrier and/or to the looping discs.
OBJECTS AND SUMMARY OF THE INVENTION
An object of the invention is to provide an overlock sewing machine with novel and improved means for severing a broken thread close to the locus of the break so that the thread is severed before a considerable length of thread can be convoluted onto one or more rotary parts of the machine.
Another object of the invention is to provide a mechanism which can be installed in existing overlock sewing machines at a low cost and without necessitating any, or any appreciable, redesigning of the machine.
A further object of the invention is to provide a mechanism which does not interfere with normal operation of the machine, especially with normal progress of an unbroken thread, and which is not in the way to a person in charge of operating, repairing or inspecting the machine.
An additional object of the invention is to provide a novel and improved thread guide for use in the above outlined machine.
Still another object of the invention is to provide an overlock sewing machine which embodies the above outlined mechanism.
A further object of the invention is to provide a novel and improved method of severing broken threads in overlock sewing machines.
The invention resides in the provision of a multiple-thread overlock sewing machine with several thread sources. The machine comprises a pair of coaxial rotary thread entraining and looping members each of which can resemble a disc and each of which is preferably provided with a peripheral flat in register with the flat of the other member, and a preferably U-shaped thread guide having two portions (e.g., in the form of two substantially parallel legs made of metallic sheet material) flanking the looping members and provided with aligned thread-receiving slots. A thread which is drawn from one of the sources passes from the outside along one of the legs, through the slot of the one leg, over the looping members and into and outwardly through and beyond the slot in the other leg so that such thread is drawn off the source in response to rotation of the looping members and the thus formed loop is drawn between the two legs of the guide beyond the slots. The machine further comprises a thread stripping device which is disposed between the looping members and is positioned to separate the loop of an unbroken thread from the looping members in predetermined angular positions of such members but to permit the thread to advance with the looping members beyond the predetermined angular positions when the thread develops a break downstream of the slot in the other leg (because the broken thread is no longer under tension), and means for severing the broken thread which advances with the looping members beyond the predetermined angular positions.
The severing means can comprise a knife having a cutting edge located between the one leg of the guide and the adjacent looping member to sever the thread which is not stripped off the looping members. The slots are or can be substantially horizontal, and the cutting edge of the knife is then preferably located at a level below the slot in the one leg of the guide. The knife can be provided on the guide; in fact, the knife can constitute a projection which is an integral lug of the one leg.
The cutting edge of the knife is preferably inclined with reference to that side face of the aforementioned adjacent looping member which confronts the one leg of the guide. The looping members and the legs of the guide can be disposed in substantially parallel substantially vertical planes, and the one leg of the guide can define with the adjacent looping member a gap; the cutting edge of the knife preferably extends across such gap. The cutting edge is or can be substantially vertical.
The machine preferably further comprises means for diverting toward the cutting edge of the knife the broken thread which is advanced by the looping members beyond the predetermined angular positions. The diverting means can comprise a substantially conical protuberance on the side face of the aforementioned adjacent looping member.
The novel features which are considered as characteristic of the invention are set forth in particular in the appended claims. The improved sewing machine itself, however, both as to its construction and its mode of operation, together with additional features and advantages thereof, will be best understood upon perusal of the following detailed description of certain specific embodiments with reference to the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a front elevational view of an overlock sewing machine which embodies one form of the invention, with a portion of the housing broken away;
FIG. 2 is a side elevational view of the sewing machine as seen from the left-hand side of FIG. 1, with a portion of the housing broken away;
FIG. 3 is an enlarged view of a detail in the sewing machine of FIG. 2;
FIG. 4 is a horizontal sectional view as seen in the direction of arrows from the line IV--IV of FIG. 3; and
FIG. 5 is a vertical sectional view as seen in the direction of arrows from the line V--V of FIG. 3, with the thread omitted.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 and 2 show an overlock sewing machine 1 similar to that which is known as Bernette MO-203 (manufactured and distributed by the assignee of the present application). The sewing machine 1 comprises a housing 3 having an upper section with a built-in carrying handle and supporting a needle bar 5 for a needle 6 which can be reciprocated by a conventional driving unit, not shown. The needle bar 5 is adjacent and parallel to a reciprocable presser bar 7 (disposed at A as seen in FIG. 1) which is also mounted in and is reciprocable in the upper section of the housing 3 and has a lower end portion carrying a presser foot 9. The underside of the presser foot 9 is substantially parallel to the top surface of a work plate 11 on the lower section of the housing 3. The needle bar 5 is further adjacent a selvage or edge cutter 13 which does not form part of the invention and is mounted at a level between the work plate 11 and the upper section of the housing 3. The means for guiding the needle bar 5 and the presser bar 7 in the upper section of the housing 3 are not shown because such features are not germane to the present invention. FIG. 2 further shows a presser foot lifter lever 15 at the rear side of the upper section of the housing 3.
The machine 1 can sew with several threads which are supplied by discrete spools, bobbins or cones (one shown at 53 in FIG. 2) at the rear side of the housing 3. The yarn or thread 51 which is supplied by the illustrated source 53 passes upwardly toward and through a guide 19 on the horizontal arm of a preferably telescopic supporting rod and thereupon downwardly toward and through a second guide 19 prior to entering the lower section of the housing 3 beneath the work plate 11. The reference character 17 denotes in FIG. 2 two spindles for discrete sources 53 of thread. The lower section of the housing 3 confines the means for building a supply of thread 51 as well as the novel and improved mechanism for cutting or trimming broken threads.
The means for building a supply of thread 51 which comes from the illustrated source 53 includes a substantially U-shaped carrier c,r guide 21 which can be made of a metallic sheet material and has two spaced-apart parallel portions or legs 27, 29 flanking two parallel disc-shaped rotary thread entraining or looping members 31. (Each of the legs 27, 29 has a rearwardly open substantially horizontal slot 23. The slots 23 are aligned with one another (see FIGS. 3 and 4), and the guide 21 is fixedly secured to a frame 25 in the interior of the lower section of the housing 3. The looping members 31 are secured to a driven horizontal shaft 33 which is mounted in the frame 25 at a level below the guide 21 at such a distance from the latter that only the upper portions of the members 31 extend into the space between the legs 27 and 29. The looping members 31 resemble circular discs save for the provision of two tangentially extending flats 35 which are disposed in a common plane extending in parallelism with the axis of the shaft 33.
The outer side of the leg 27 is adjacent a substantially cup-shaped thread tensioning element 37 which is mounted on the leg 27 forwardly of the innermost or deepmost (closed) portion 24 of the respective slot 23 and whose end wall is biased toward the outer side of the leg 27 by a coil spring 40. The bias of this spring can be regulated by a screw which is shown in FIGS. 3, 4 and 5.
The space between the looping members 31 accommodates a thread stripping device 39 whose upper side is located somewhat below the lowermost parts of the slots 23 and which projects into the space between the looping members toward but short of the shaft 38 for the tensioning element 37. The right-hand end portion of the thread stripping device 39 is mounted in the frame 25 in a manner which is not specifically shown in the drawing. That side face or surface 41 of the lower entraining member 31 of FIG. 4 which confronts the adjacent leg 27 of the thread guide 21 is provided with a substantially conical thread deflecting or diverting protuberance 43 whose axis coincides with the axis of the shaft 33 and which is located at a level below the leg 27. The protuberance 43 can constitute a screw which has an externally threaded shank extending into a tapped bore of the shaft 33 to secure the looping members 31 to such shaft. The apex of the protuberance 43 has a hexagonal socket for the working end of a suitable tool which is used to secure the protuberance to or to detach it from the shaft 33. The height of the protuberance 43 is preferably such that it completely spans the clearance or gap 45 between the side face 41 of the respective entraining member 31 and the inner side of the leg 27. This can be readily seen in FIG. 4.
The sewing machine 1 further comprises a knife 47 which is mounted on the guide 21, and more specifically on the leg 27, so that it is located rearwardly of the protuberance 43 and has an elongated cutting edge 49 facing toward the web of the guide 21, i.e., toward the sources of thread at the rear side of the housing 3. The illustrated knife 47 includes a projection or lug 48 which is an integral part of and extends downwardly from the leg 27. The cutting edge 49 is inclined with reference to the side face 41 of the lower entraining member 31 of FIG. 4 and extends across the space beneath the gap 45. The cutting edge 49 is or can be substantially vertical (see FIG. 3). If desired, the knife 47 can be produced as a separate part which is separably or permanently affixed (e.g., welded) to the leg 27 of the thread guide 21. This may be desirable if the knife 47 is to be installed in an existing overlock sewing machine.
The operation is as follows:
If the thread 51 is not broken, it extends from the source 53, through the two guides 19 of FIG. 2 and along the outer side of the leg 27 prior to being trained over the shaft 38 of the tensioning device 37 and entering the deepmost portion 24 of the slot 23 in the leg 27. At such time, the flats 35 of the entraining members 31 are substantially horizontal. The thread 51 then extends (at B) in parallelism with the axis of the shaft 33 toward and outwardly through the deepmost portion of the slot 23 in the leg 29 and thence toward and through an eyelet 30 which is shown in FIG. 4. The location of the eyelet 30 is or can be such that the portion of thread 51 between the deepmost portion of the slot 23 in the leg 29 and the eyelet 30 is substantially parallel to the outer side of the leg 29 (see FIG. 4). That portion of the thread 51 which advances beyond the eyelet 30 is engaged by a hook or shuttle, not shown, of conventional design.
If the disc-shaped looping members 31 are rotated in a clockwise direction, as seen in FIG. 3, the portion of thread 51 between the deepmost portions of the slots 23 in the legs 27, 29 of the thread guide 21 is engaged by the portions 36 of peripheral surfaces of the looping members and is pulled toward the location C (FIG. 3) whereby the members 31 cause the formation of a loop within the space which is provided between the legs 27, 29 and extends from the deepmost portions of the slots 23 to the location C where the thread is separated from the members 31 by the stripping device 39. This results in separation of the freshly formed loop from the members 31, and such loop can be pulled toward the aforementioned oscillating shuttle or hook in a well known manner.
If the thread 51 happens to break downstream of the slot 23 in the leg 29 of the thread guide 21, the thread is still engaged by the portions 36 of peripheral surfaces of the disc-shaped looping members 31 and these members cause the formation of a loop substantially in the same way as in the case of an unbroken thread, i.e., the thread portion which extends between the deepmost portions of the slots 23 is pulled toward the location C in response to clockwise rotation of the shaft 33. However, and since the leader of the broken thread is not under tension, it is not stripped off the looping members 31 by the device 39. Such thread is advanced with the portions 36 to the positions D1, D2 and so on to the position Dx of FIG. 3. The thread is deflected or diverted by the conical protuberance 43 and is looped over the knife 47 in a manner as shown in FIG. 3 to be severed by the cutting edge 49 at the location E as soon as the portions 36 of the looping members 31 reach the location Dy. The thus separated length of the thread 51 cannot be convoluted onto the shaft 33 which simplifies removal of severed thread from the machine 1.
An important advantage of the improved severing mechanism is that a broken thread is severed close to the locus of the break before a considerable length of broken thread can be convoluted onto the shaft 33. This reduces the likelihood of damage to the looping members 31 during winding of broken thread onto the drive shaft 33 as well as during unwinding of accumulated thread from the shaft 33.
Another important advantage of the improved mechanism is that it can be installed in existing overlock sewing machines at a minimal cost, either by attaching a separately produced knife 47 to the leg 27 of the guide 21 or by replacing a conventional thread guide with a guide 21 which has a leg 27 with an integral projection constituting a lug 48 and serving as a knife with a cutting edge 49 oriented in a manner as described above. The knife does not interfere in any way with advancement of the thread 51 toward the shuttle when the thread is intact, i.e., when its loops can be stripped off the members 31 by the device 39 as soon as the portions 36 of members 31 reach the location C of FIG. 3. In addition, the knife 47 does not interfere with the manipulation and/or servicing of the machine 1.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic and specific aspects of our contribution to the art and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the appended claims.
|
An overlock sewing machine wherein a thread which breaks between the shuttle and the looping discs is allowed to bypass the loop stripping device and is advanced by the discs toward and against the cutting edge of a knife provided on one leg of the U-shaped thread guide which confines the looping discs. This prevents the discs from convoluting the broken thread onto the shaft which drives the discs.
| 3
|
REFERENCE TO RELATED APPLICATION
[0001] The present application relates and claims priority to U.S. Provisional Application Ser. No. 62/162,730, filed May 16, 2015, the entirety of which is hereby incorporated by reference.
BACKGROUND
[0002] 1. Field of Invention
[0003] The present invention relates to furniture, and more specifically to tables or other furniture pieces useful in areas with limited space
[0004] 2. Background of Art
[0005] Furniture that is both aesthetically pleasing while appropriately functional for a given use is desirable. A particular need exists for furniture that provides adequate functionality and aesthetics in spaces of small or limited size. For example, a studio apartment typically provides very limited living space, but the occupant may like to have adequate furniture to live not just comfortably, such as a bed, a dining table, chairs, and the like but also optimize for experience and utility of that space, such as dinner parties, office, work, etc.
[0006] One rather old but functionally useful furniture design that has addressed the need of furnishing small spaces is the Murphy bed. The Murphy bed is a sleeping bed that simply moves between a stowed position wherein it extends in a vertical plane typically against a wall and perhaps hidden behind doors that make it appear as a closet, and a deployed positioned where it simply pivots at its base to extend in the normal horizontal plane as with “fixed” beds.
[0007] Other furnishings that have been designed for smaller spaces include, for example, what are known as TV trays; small trays that are foldable between a stowed and collapsed position and a deployed, usable position. The TV trays simply include a pair of legs on each side of the tray that are pivotally movable relative to one another about their midpoints. The tray surface is also pivotally mounted to one of the legs on each side and can be releasingly and securely clipped to the other legs on each side when deployed for use.
[0008] Traditional folding tables and chairs are also functionally useful for small spaces. These tables include the table base and support legs pivotally extendible between collapsed positions and extended positions. When the table is not in use the legs are folded up against the downwardly facing surface of the table and the table stowed for later use. Similarly with the traditional folding chairs, the legs and seat portion simply pivot to permit folding of the chair's components into a single plane for storage. When use of the chair is desired, one simply unfolds the legs and seat to convert the chair into a functional piece of furniture.
[0009] Couches commonly known as futons are useful at providing a couch that can be converted into a bed by unfolding its various sections and extending the couch cushion into a mattress. Similar to couches with fold away mattresses, this type of furniture is useful for providing extra an sleeping piece in an area otherwise occupied with living room type furnishing.
[0010] While each of the examples provided above of traditional furniture used in spaces of limited size, there are drawbacks associated with each of them that make them less attractive for use by certain individuals who may otherwise have a need for such functionality. For instance, even the TV trays and folding tables and chairs require space to store them, which certain apartments or other small quarters may not provide. And while a Murphy bed is useful in saving space it is a rather heavy piece of furniture that is difficult for some individuals to manipulate. In addition, it is merely movable between a fully stowed or a fully open/deployed position; it does not have the ability to convert between say a king size bed and a twin bed, or a long bed and a short/toddler bed. Thus, it will always take up the maximum amount of space when deployed, which may not always be necessary or desired.
[0011] 3. Objects and Advantages
[0012] It is therefore an object and advantage of the present invention to provide a table that may be moved between a stowed position and a deployed position.
[0013] It is another object and advantage of the present invention to provide a table that can be deployed to various lengths to accommodate various size needs.
[0014] It is a further object and advantage of the present invention to provide a table that may be easily moved between its deployed and stowed positions with minimal strength or effort.
[0015] It is an additional object and advantage of the present invention to provide a table that can be customized in appearance
[0016] Other objects and advantages of the present invention will in part be obvious, and in part appear hereinafter.
SUMMARY OF THE INVENTION
[0017] In accordance with the foregoing objects and advantages, the present invention provides a table that is movable between stowed and deployed positions. The table essentially comprises a plurality of slats pivotally interconnected to one another and each of which extends in parallel relation to the rest. Each slat is interconnected to the adjacent slat(s) by hinge plates that are positioned along the side edges of each slat. A rail system is mounted to a wall and provides the sliding passageway for the slatted table top to move between its stowed (vertical) position and its deployed (horizontal) position. When in the vertical (retracted) orientation, the table is suspended by a gas spring loaded scissors lift (referred to herein as a “vertical assist mechanism” or “VAM”) such that the weight of the table is balanced. As the table deploys into a horizontal position, the force needed to counter balance the table mass decreases because part of it is now supported by legs that pivot outwardly from the bottom of the table onto the floor. The VAM is designed so that the user experiences a constant force when retracting or deploying the table even though the mass that is being translated is increasing or decreasing respectively. The gas spring is mostly responsible for this and the system is designed to even out any variation of the force output by the spring over its stroke.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present invention will be more fully understood and appreciated by reading the following Detailed Description in conjunction with the accompanying drawings, in which:
[0019] FIG. 1 is a perspective view of a table in its deployed position in accordance with an embodiment of the present invention.
[0020] FIG. 2 is a second perspective view thereof.
[0021] FIG. 3 is a rear elevation view thereof with the wall section partially cut away for purposes of viewing the rear of the table assembly.
[0022] FIG. 4 is a bottom plan view thereof.
[0023] FIG. 5 is a side elevation view of the table of FIG. 1 in its stowed position.
[0024] FIG. 6 is a front elevation view thereof.
[0025] FIG. 7 is a perspective view of the table of FIG. 1 in a partially/initially deployed position.
[0026] FIG. 8 is a side elevation view thereof.
[0027] FIG. 9 is a front elevation view thereof.
[0028] FIG. 10 is a perspective view of a portion of a slat assembly in accordance with an aspect of the invention.
[0029] FIG. 11 is a bottom plan view thereof.
[0030] FIGS. 12 a -12 c are side elevation views of a slate, slip surface, and slat hinge plate, respectively.
[0031] FIG. 13 is an illustrative view of the horizontal brake mechanism in accordance with an aspect of the present invention.
[0032] FIG. 14 is a schematic view of the horizontal brake mechanism in accordance with an aspect of the present invention.
[0033] FIGS. 15 a -15 j are sequential illustrative views illustrating the process associated with an aspect of the present invention.
[0034] FIG. 16 is an elevation view of the vertical assist mechanism associated with an aspect of the present invention.
DETAILED DESCRIPTION
[0035] Referring now to the drawings wherein like reference numerals refer to like parts throughout, there is seen in FIG. 1 a table designated generally by reference numeral 10 . Table 10 is manually movable between a stowed (vertically oriented position (see FIGS. 5 and 6 ) to a fully deployed (horizontally oriented) position (see FIGS. 1-4 ). If a shorter length of table is desired than is provided when fully deployed, deployment of table 10 can cease at any desired length, leaving a portion thereof in its vertically oriented position while the desired length of horizontally oriented table may be deployed and used.
[0036] Table 10 generally comprises a plurality of slats 12 that form the table top. Each slat 12 is interconnected to adjacent slat(s) 12 by hinge plates 14 that extend along the side edges of each slat 12 . A slip surface 16 is positioned between each hinge plate 14 and slat 12 to reduce friction during movement of the slats. A pin 18 passes through and interconnects two slats 12 together and the length of the pin serves as the pivot axis between the two adjacent slats 12 . As most clearly seen in FIGS. 11 and 12 c , each hinge plate 14 includes a leading edge 20 that is concave, while its trailing edge 22 is correspondingly convex in shape. This convex/concave relationship provides a smooth transition as one slat moves from its vertical to its horizontal position while the adjacent one remains in it vertical orientation.
[0037] With reference to FIGS. 13 and 14 , when a user is moving the table, a brake mechanism, designated generally by reference numeral 100 , must be disengaged. Brake mechanism 100 comprises a brake 102 attached to the underside of the leading slat, and a series of pulleys 104 around which a cable 106 travels (and cable 106 also passes through brake 102 ) and with the ends of the cable tied off to tensioning springs. Brake 102 pinches cable 106 by magnetic (or spring) biased force when in its neutral state, thereby preventing movement of cable 106 and movement of the table. To disengage brake 102 , a user would pull on the handle 108 of brake 102 , thereby freeing cable 106 from its clutch. The user's minimum push or pull force exerted on the leading slat 12 then moves the table with the assistance of the VAM to either its stowed or deployed position, respectively. Upon release of handle 108 , cable 106 once again is engaged and movement of the table is prohibited. Thus, releasing handle 108 when any desired length of table is deployed permits a table of desired size to be deployed (e.g., only one or two slats might be deployed to provide a shelf).
[0038] With reference to FIG. 16 , VAM 200 is illustrated. VAM comprises a plurality of pivotally linked legs 202 to form a scissor lift. The upper and lower extremities of legs 202 are bridged by connecting arms 204 and 206 , respectively. A gas piston 208 has its cylinder attached at one end of connecting arm 206 and its piston is carried in an arcuate slot 210 formed through a guide 212 that is attached to a leg 202 . As a user begins to move the table either towards a deployed position or towards its stowed position, gas piston 206 will provide the majority of the force and support needed to carry the weight of the table, thus minimizing the effort required of the user. The arcuate slot 210 is designed to vary the amount of force contributed by the gas piston to the movement of the table; as more of the table becomes vertically oriented towards its stowed position, the greater the amount of force contributed by the gas piston and conversely when the table nears its fully deployed position, the arcuate slot is oriented such that the gas piston again contributes a significant amount of force to hold the weight of the table as it is moved. Likewise, less force is needed when a portion of the table is deployed and a portion in the vertical plane. When the table is in its fully stowed position, gas spring 206 provides the force to prevent the table from sliding down and away from the wall.
[0039] With respect to FIGS. 15 a - 15 j, the table 10 is shown in its sequential modes of operation from shipping ( 15 a ), to installation on a wall ( 15 b ), initial deployment of a shelf ( 15 c ), with the legs locking outwardly to support the shelf/table ( 15 d ), to deployment ( 15 e ). FIG. 15 f begins the process of deployment of table 10 for table use. Retraction is started as shown in FIG. 15 g , wherein the legs will retract upwardly into their stored position on the underside of the table ( 15 h ), and finally the shelf (slat 12 ) can be pushed into the vertical plane ( 15 i ). As shown in FIG. 15 j , the table's surface can be decorated with artwork which can be interchangeable via veneers or other suitable coverings.
[0040] Also the legs will work by automatically falling down to parallel to the wall when the leading slat is lifted from the wall. These will lock in place automatically. When the table is pulled out from the wall, these will stay down and stay locked in place.
[0041] As the table is returned to retracted state, the legs can then be free to retract and will do so when the user manually pushes on them so as to fold down the leading slat to its retracted state on the wall.
|
A table provides a surface that stores flat on a wall when not in use and can be manually deployed at variable lengths, with any the remainder remaining stored on the wall. The surface easily slides down and out from its low profile retracted (vertically stored) position into a deployed (horizontal) configuration to serve as a shelf, a desk, dining/conference/work table, and the like.
| 0
|
TECHNICAL FIELD
[0001] The present invention relates to a cardan mounting for an air vent and to an air vent for guiding an air stream out of an air feed line in a heating, ventilation or air-conditioning system, particularly for passenger compartments in motor vehicles.
BACKGROUND
[0002] As is known, cardan mountings serve the purpose of mounting a first, e.g. fixed, part in relation to a second part, e.g. a part that can be moved relative to the first part, in such a way that an angular displacement between the two parts can take place virtually unhindered as long as frictional forces remain negligible. For this purpose, the two parts are each attached pivotably to at least one cardan ring, for example, wherein the two pivoting axes are arranged at right angles to one another.
[0003] Various air vents for guiding an air stream, which are used in heating, ventilation or air-conditioning systems, particularly for passenger compartments in motor vehicles, for example, are furthermore already known from the prior art. The air vents are fitted in an air duct or an air feed line and usually comprise a housing having a front air outflow opening and a rear air inflow opening and an insert, which is arranged in the housing and by means of which the direction and/or the intensity of the air stream emerging from the air vent can be modified. An air vent of this kind is disclosed in EP 2 340 178 B1, for example.
[0004] Supporting the insert of an air vent of this kind in the housing of the air vent, e.g. by means of a cardan mounting, allowing the insert to be moved into virtually any desired angular position relative to the housing in order in this way to enable the direction of the air stream emerging from the air vent to be determined, is furthermore likewise known. In addition, a further adjusting means, e.g. in the form of an adjusting wheel, by means of which the intensity of the air stream emerging from the air vent can also be controlled, is often provided on the front side of the air vent. However, this results in a relatively complex internal structure of air vents of this kind, taking up a relatively large overall volume and/or significantly restricting the options for arranging the adjusting means on the air vent.
[0005] Given this situation, it is the underlying object of the present invention to provide a cardan mounting, in particular for an air vent for use in passenger compartments of motor vehicles, which has a structure that is as simple and compact as possible and which, at the same time, requires a small number of components, thus making it possible to achieve savings both as regards the weight of the mounting and also as regards the time for assembly. The cardan mounting should furthermore have damping, such that the ventilation nozzle remains in a position set by the user. The intention is furthermore to provide an air vent that has a compact structure and furthermore facilitates arrangement of an adjusting means for controlling the intensity of the air stream emerging from the air vent.
SUMMARY
[0006] This object is achieved by a cardan mounting and an air vent having the features of the following claims. Further, particularly advantageous embodiments of the invention are disclosed by the respective dependent claims.
[0007] It should be noted that the features presented individually in the claims can be combined with one another in any technically meaningful way and give rise to further embodiments of the invention. The description additionally characterizes and specifies the invention, in particular in conjunction with the figures.
[0008] According to the invention, a cardan mounting, in particular for an air vent for guiding an air stream out of an air feed line in a heating, ventilation or air-conditioning system, particularly for passenger compartments in motor vehicles, comprises a fixed part, e.g. a housing, and a moving part, e.g. an insert, which is arranged in the housing and by means of which the direction and/or the intensity of the air stream emerging from the air vent can be modified. The fixed and the moving part are each pivotably attached to a cardan ring, wherein the two pivoting axes are arranged at right angles to one another. Moreover, the cardan ring according to the present invention is elastically deformable. In the uninstalled state, i.e. in a state in which there are no external forces acting on the cardan ring, it has an uninstalled and therefore undeformed shape.
[0009] In the uninstalled state, the cardan ring preferably has a circular ring shape. However, any other shape—square, polygonal or oval—which enables it to perform the cardan-type function is also conceivable.
[0010] In the case of the rotationally symmetrical shape of the cardan ring, it is, in contrast, extended along one pivoting axis and compressed along the other pivoting axis, as compared with the circular shape, in the installed state, i.e. when the first and second parts are attached to the cardan ring. In other words, the elastically deformable cardan ring assumes an essentially slightly elliptical shape in the installed state, in which external forces act upon it. At the bearing locations, this deformation gives rise to a preload between the cardan ring and the first and second parts, causing a certain damping of the rotary motion of the parts relative to the cardan ring, depending on the embodiment of the bearing region.
[0011] The rotationally symmetrical, circular-ring-shaped construction of the cardan ring ensures that the forces, e.g. frictional forces, which occur in the bearing locations at which the two parts are pivotably attached to the cardan ring, are balanced out after the (slight) deformation. In other words, after assembly the elastically deformable cardan ring automatically ensures uniform distribution of the forces, in particular frictional forces, acting in all the bearing locations by virtue of its symmetrical construction, and hence the cardan mounting according to the invention allows angular displacement of the two parts attached to the cardan ring relative to one another in a manner which is unhindered and smooth but nevertheless damped by the preload. It is thereby possible overall to simplify the structure of the cardan mounting since production-related component tolerances of the fixed part and/or of the moving part can be balanced out by the elastically deformable cardan ring.
[0012] As regards deformation, all other cardan rings, however configured, also behave in the manner described above for the circular-ring-shaped cardan ring.
[0013] According to an advantageous embodiment of the invention, the fixed part or the moving part causes the extension or the compression of the cardan ring in the installed state. This means that the forces required to deform the cardan ring in the installed state are applied exclusively by the fixed part or the moving part, thereby making it possible to reduce to a minimum the number of components required for the cardan mounting, namely the cardan ring, the fixed part and the moving part. Moreover, selective influencing of the extent of extension or compression of the cardan ring is possible by way of the diametric spacing of the bearing locations, provided for attachment to the cardan ring, of the fixed part or of the moving part.
[0014] Another advantageous embodiment of the invention envisages that the fixed part and the moving part both engage in the cardan ring from the inside. In this case, one of the two parts preferably causes extension of the cardan ring and thereby gives rise to a preloading force, opposed to the direction of extension, in the bearing locations provided for pivotable attachment to the cardan ring. Owing to the symmetrical construction of the cardan ring, the same preloading force is also obtained for the other part at the bearing locations thereof.
[0015] An alternative embodiment of the invention envisages that the fixed part and the moving part both engage in the cardan ring from the outside. In this case, one of the two parts preferably causes compression of the cardan ring and thereby gives rise to a preloading force, opposed to the direction of compression, in the bearing locations provided for pivotable attachment to the cardan ring. Owing to the symmetrical construction of the cardan ring, the same preloading force is also obtained for the other part at the bearing locations thereof.
[0016] According to another advantageous embodiment of the invention, the fixed part and the moving part each engage in the cardan ring by means of pivots. The pivots represent a possible embodiment of the respective bearing locations of the two parts and engage in corresponding apertures in the cardan ring. Owing to the elastic deformation of the cardan ring in the installed state and the preloading forces caused thereby at the bearing locations, no additional means of securing the pivots from sliding out of the corresponding apertures of the cardan ring is required, thereby further simplifying the construction of the cardan mounting and reducing the number of components required to implement the cardan mounting.
[0017] According to another aspect of the present invention, an air vent for guiding an air stream out of an air feed line in a heating, ventilation or air-conditioning system, particularly for passenger compartments in motor vehicles, is provided, comprising a housing having a front air outflow opening and a rear air inflow opening and an insert, which is arranged in the housing and by means of which the direction and/or the intensity of the air stream emerging from the air vent can be modified. According to the invention, the insert is supported in the housing by means of a cardan mounting in accordance with one of the embodiments according to the invention which have been described above.
[0018] Another advantageous embodiment of the air vent according to the invention envisages that, in a front central region, the insert has an adjusting means for controlling the intensity of the air stream emerging from the air vent.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0019] Further features and advantages of the invention will become apparent from the following description of an illustrative embodiment of the invention, not to be taken as restrictive, which is explained in greater detail below with reference to the drawing. In said drawing, which is schematic:
[0020] FIG. 1 shows an isometric view of a first illustrative embodiment of a cardan mounting according to the invention before assembly.
[0021] FIG. 2 shows an isometric exploded view of the cardan mounting shown in FIG. 1 after assembly.
[0022] FIG. 3 shows a distribution of preloading forces on the cardan ring in accordance with the first illustrative embodiment, shown in FIG. 2 , of the cardan mounting according to the invention.
[0023] FIG. 4 shows a distribution of preloading forces on a cardan ring according to a second embodiment of a cardan mounting according to the invention.
[0024] FIG. 5 shows a front view of an illustrative embodiment of an air vent according to the invention.
[0025] FIG. 6 shows a sectional view of the air vent from FIG. 5 along section line A-A.
[0026] FIG. 7 shows a sectional view of the air vent from FIG. 6 along section line C-C.
[0027] FIG. 8 shows a sectional view of the air vent from FIG. 5 along section line B-B.
DETAILED DESCRIPTION
[0028] In the various figures, identical parts are always provided with the same reference signs, and they are therefore generally also described only once.
[0029] FIG. 1 represents schematically an isometric view of a first illustrative embodiment of a cardan mounting 1 according to the invention before assembly. The cardan mounting 1 shown comprises a fixed part 2 , e.g. a fixed part connected to a housing (not shown) of an air vent (likewise not shown), and a moving part 3 , e.g. an insert, which is arranged in the housing and is used to modify the direction and/or the intensity of the air stream emerging from the air vent. Parts 2 and 3 are each attached pivotably to a cardan ring 4 . As is apparent, the two pivoting axes of parts 2 and 3 are arranged at right angles to one another. It can furthermore be seen in FIG. 1 that the cardan ring 4 has a circular ring shape, i.e. a substantially rotationally symmetrical configuration, in the unloaded state before assembly.
[0030] In the first illustrative embodiment of the cardan mounting 1 , which is shown in FIG. 1 , both the fixed part 2 and the moving part 3 engage in the cardan ring 4 from the inside. For this purpose, both parts 2 and 3 have pivots 5 at the bearing locations thereof, which are provided for pivotable attachment to the cardan ring 4 , said pivots each engaging in corresponding apertures 6 in the cardan ring 4 after assembly of the cardan mounting 1 .
[0031] FIG. 2 represents an isometric exploded view of the cardan mounting 1 shown in FIG. 1 , after assembly. It is apparent that, after assembly, i.e. after the two parts 2 and 3 have been mounted on the cardan ring 4 , the cardan ring 4 is extended along the pivoting axis of the fixed part 2 and compressed along the pivoting axis, at right angles thereto, of the moving part 3 , as compared with the circular shape, illustrated in FIG. 1 , of the cardan ring 4 . As a particularly preferred option, the fixed part 2 in the illustrative embodiment of the cardan mounting 1 which is shown in FIG. 2 causes the extension of the cardan ring 4 in the direction of the pivoting axis of the fixed part 2 . It is thereby advantageously achieved that the deformation of the cardan ring 4 gives rise to preloading forces at the bearing locations of both parts 2 and 3 , said forces being the same for both parts 2 and 3 .
[0032] FIG. 3 shows a distribution of the preloading forces 7 , indicated by corresponding arrows, on the cardan ring 4 in accordance with the first illustrative embodiment, shown in FIG. 2 , of the cardan mounting 1 according to the invention. Owing to the symmetry of the cardan ring 4 , the preloading force 7 caused by the fixed part 2 on the cardan ring 4 deformed thereby (vertical direction in FIG. 3 ) gives rise to a preloading force 7 of the same magnitude for the moving part 3 (horizontal direction in FIG. 3 ). As a result, substantially the same forces, in particular frictional forces, act on the cardan ring 4 at all the bearing locations of parts 2 and 3 . Moreover, both the fixed part 2 and the moving part 3 are clamped by the preloading forces 7 acting on the cardan ring 4 , with the result that an additional means of securing parts 2 and 3 for the purpose of pivotable fixing on the cardan ring 4 can be omitted, reducing the components required to implement the cardan mounting 1 and significantly simplifying the construction thereof.
[0033] FIG. 4 shows a distribution of preloading forces 7 on a cardan ring 4 in accordance with an alternative embodiment of a cardan mounting 8 according to the invention. Cardan mounting 8 differs from cardan mounting 1 essentially only in that both the fixed part 2 and the moving part 3 engage in the cardan ring 4 from the outside. The fixed part 2 (vertical direction in FIG. 4 ) thus now preferably causes compression of the cardan ring 4 , as a result of which said ring is deformed in accordance with the illustration in FIG. 4 . As has already been described above in connection with the explanation of FIG. 3 , the preloading force 7 on the cardan ring 4 caused by the fixed part 2 gives rise to a preloading force 7 of the same magnitude for the moving part 3 (horizontal direction in FIG. 4 ) owing to the symmetry of the cardan ring 4 . In this embodiment of the cardan mounting 8 too, it is the case that substantially the same forces, in particular frictional forces, act on the cardan ring 4 at all the bearing locations of parts 2 and 3 . Moreover, both the fixed part 2 and the moving part 3 are clamped by the preloading forces 7 acting on the cardan ring 4 , with the result that an additional means of securing parts 2 and 3 for the purpose of pivotable fixing on the cardan ring 4 can be omitted, likewise reducing the components required to implement the cardan mounting 8 and simplifying the construction thereof.
[0034] FIG. 5 represents a front view of an illustrative embodiment of an air vent 9 according to the invention for guiding an air stream out of an air feed line (not shown) in a heating, ventilation or air-conditioning system, particularly for passenger compartments in motor vehicles. The air vent 9 illustrated essentially comprises a housing 10 having a front air outflow opening 11 and a rear air inflow opening 12 (visible in FIG. 6 ) and an insert 13 , which is arranged in the housing 10 and by means of which the direction and/or the intensity of the air stream emerging from the air vent 9 can be modified. In the air vent 9 illustrated in FIG. 5 , the insert 13 is supported in the housing 10 by means of the cardan mounting 1 (not shown). The insert 13 of the air vent 9 illustrated in FIG. 5 furthermore has, in the front central region thereof, an adjusting means 14 for controlling the intensity of the air stream emerging from the air vent 9 . The adjusting means 14 can advantageously be arranged unhindered in the central region of the insert 13 since the cardan mounting 1 (and also 8 ) according to the invention leaves sufficient free space, especially in the central region, as is clearly apparent in FIGS. 1 and 2 . The transmission means 16 (visible in FIG. 6 ) which are required to control the intensity of the air stream by means of a control flap 15 (likewise visible in FIG. 6 ) and which are driven by the adjusting means 14 can then be arranged in said free space.
[0035] FIGS. 6 , 7 and 8 represent different sectional views of the air vent 9 shown in FIG. 5 , wherein a sectional view of the air vent 9 from FIG. 5 along section line A-A is shown in FIG. 6 , a sectional view of the air vent 9 from FIG. 6 along section line C-C is shown in FIG. 7 , and a sectional view of the air vent 9 from FIG. 5 along section line B-B is shown in FIG. 8 .
[0036] The cardan mounting according to the invention and the air vent according to the invention have been explained in detail by means of illustrative embodiments shown in the figures. However, the cardan mounting and the air vent are not restricted to the embodiments described herein but also include further embodiments with the same action.
[0037] In a preferred embodiment, the cardan mounting according to the invention is used in an air vent for guiding an air stream from an air feed line in a heating, ventilation or air-conditioning system, particularly for passenger compartments in motor vehicles.
[0038] The foregoing has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the embodiments to the precise form disclosed. Obvious modifications and variations are possible in light of the above teachings. All such modifications and variations are within the scope of the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.
|
The invention relates to a cardan mounting for an air vent, comprising a fixed part and a moving part, which are each pivotably attached to a cardan ring, wherein the two pivoting axes are arranged at right angles to one another. The cardan ring is elastically deformable, circular-ring-shaped in the uninstalled state and extended along one pivoting axis and compressed along the other pivoting axis, as compared with the circular shape, in the installed state. The invention furthermore relates to an air vent having a cardan mounting of this kind.
| 1
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to lighting fixtures and more specifically to lighting fixtures including a reflector having sharp cutoff characteristics.
2. Description of the Prior Art
Lighting fixtures housing a high intensity gaseous discharge (HID) lamp of appreciable wattage (e.g., 1000 watts) are used in a wide variety of applications. Many of these applications are situations where the light from the fixture spreads and provides general illumination over a wide area.
For example, a fixture in the middle of a parking lot may conveniently project light downwardly equally over a 360-degree area. By contrast, however, it readily may be recognized that it is desirable to provide light from a fixture near the edge of the lot adjoining a building having windows downwardly and outwardly over only a 180-degree area. It is desirable that light from a corner-located fixture be directed downwardly over only a 90-degree area. And, in all of the applications referred to above, it is undesirable to project light vertically above an angle that would be a nuisance from a location across the street.
Therefore, it is common to design light fixtures or luminaires of various configurations to cut off light from projecting or emanating from such fixtures beyond a certain angle or angles. But, it may be recognized that beyond the designed cutoff angle, not all of the light is cut off, only a high percentage of such light. A luminaire light distribution is designated as being cut off in accordance with IES standards when the candlepower per 1000 lamp lumens does not numerically exceed 25 (2.5%) at an angle of 90 degrees above nadir (horizontal) or 100 (10%) at a vertical angle of 80 degrees above nadir.
One popular design of luminaire used to achieve a high degree of lateral and a certain degree of vertical cutoff is an asymmetrical fixture. In such a fixture the lamp reflector usually includes side reflectors substantially parallel to the aiming axis for cutting off lateral reflections. The curvature of the remaining reflector (i.e., rearward to the lamp bulb) is then at a large arcuate angle with respect to the aiming axis on one side when compared to the arcuate angle on the other side, providing a wider opening on the first side than on the second side. Whether a light fixture which is asymmetrical can be characterized by a discussion to the standard cutoff terminology mentioned above, or with respect to aiming angles, the terminology that is common in a discussion of floodlight characteristics, it is recognized that the sharpness of cutoff on an asymmetrical fixture can be very important.
One of the reflector shapes most favored for a sharp cutoff reflector is the parabolic shape. This is because the light from the focal point of such a reflector is reflected outwardly from the reflector surface parallel to the aiming axis, which is also the long axis of the reflector parabola. A wider than parabolic arcuate spread would project a wider light dispersion and a narrower than parabolic arcuate reflector spread would cause cross light reflections, also resulting in a wider light dispersion. Most prior art asymmetrical fixtures generally have one side which is parabolic but one side which is not, the rear reflectors blending into a continuous curve. Hence, light from at least one portion of the rearward reflector is not parallel to the elongate fixture axis.
Louvers and other light restrictions have also been employed in the prior art to provide means for limiting the amount of light in one or more directions while permitting light to emanate in one or more other directions. Such louvers, however, also sharply decrease the overall efficiency of light production. Another technique for similarly restricting light is the darkening of certain reflective surfaces when compared to the specular treatment of other surfaces. Obviously, such treatment also decreases light efficiency.
It is therefore a feature of the present invention to provide an improved, highly efficient asymmetrical lamp fixture including a parabolic reflector segment that has an extremely sharp light cutoff in one direction.
It is another feature of the present invention to provide an improved, highly efficient asymmetrical lamp fixture having a shield located to enhance cutoff without impairing efficiency, as in the case with prior art louvers.
It is yet another feature of the present invention to provide an improved, highly efficient asymmetrical lamp fixture including a window opening at an angle to the elongate axis of the fixture to improve the direction of reflector light but at a sufficiently large angle with respect to the elongate axis so as not to appreciably degrade or impair the light emanating from the fixture.
SUMMARY OF THE INVENTION
A preferred embodiment of the invention includes, in a reflector system included in an asymmetrical light fixture, a top and rearward parabolic reflector segment for providing a narrow beam above the elongate axis of the reflector and a bottom and rearward parabolic reflector segment for providing a wider beam below the elongate axis of the reflector. The lamp of the fixture is located at the concentric focal points of these parabolic reflector segments. A shield parallel to the elongate axis is located above such axis and is positioned so that its window-terminating end is only slightly above such axis, preferably at a location point just 10 degrees thereabove. The rearward end of the shield blocks the lamp bulb from emanating from the fixture without reflection, but does not block the rear part of the lamp from primary reflection from the top and rearward segment. The underneath side of the shield is made reflective to enhance the overall light from the lower part of the fixture. The window is angled preferably 60 degrees to the elongate axis to further restrict light from the top portion of the reflector more than from the bottom portion, while still not appreciably impairing, by internal reflection, light that emanates through the window.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above-recited features, advantages and objects of the invention, as well as others which will become apparent, are attained and can be understood in detail, more particular description of the invention briefly summarized above may be had by reference to the embodiments thereof which are illustrated in the appended drawings, which drawings form a part of this specification. It is to be noted, however, that the appended drawings illustrate only typical embodiments of the invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
In the drawings:
FIG. 1 is an oblique pictorial of a preferred embodiment of a light fixture in accordance with the present invention.
FIG. 2 is a cross sectional view of the reflector system included in the light fixture shown in FIG. 1, the section being taken at line 2--2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Now referring to the drawings, and first to FIG. 1, a preferred embodiment of a lighting fixture shown in its housing, in accordance with the present invention, is illustrated in an oblique pictorial. Housing 10 is shown conveniently mounted to a supporting structure in the form of a post. Window opening 14 is angled downwardly in a manner more fully described hereinafter so as to provide illumination from the fixture in a downwardly and outwardly direction. The window can be glass or a plastic film having good transmittance properties.
FIG. 2 is a cross sectional view of the lighting fixture, showing the relationships of the internal light fixture system. Also shown is the structure for mounting housing 10 to post 12. The upper end of the post is conveniently bifurcated for receiving a mounting flange 16 therein, flange 16 being fixedly secured to housing 10. A bolt-and-nut arrangement 18 through appropriate receiving holes in the flange and the bifurcated end of the post provides means for securing housing 10 in its desired attitude or position.
Now referring to the reflector system shown in FIG. 2, a preferred embodiment of such arrangement in accordance with the present invention is illustrated. The elongate axis 20, although not positioned horizontally since the housing is angled forward as hereinafter described, is sometimes referred to in describing the geometric relationships of the fixture as "horizontal". Likewise, axis 22, the complementary Cartesian axis coordinated with axis 20, is sometimes referred to in the geometric discussion which follows as the "vertical" axis, although, in truth, it is not vertical, as hereinafter explained.
Lamp 24 is located within the fixture with its center at focal point of the reflector segments hereinafter described, which focal point coincides with the crossing intersection of axes 20 and 22. Lamp 26 is typically an elongated gaseous-filled lamp held in position by its socket or sockets (not shown) so that its elongate axis is at right angles to the plane of the drawing at point 26. A suitable holding arrangement for a lamp is illustrated in patent application Ser. No. 021,269, filed Mar. 15, 1979, by the same inventor and commonly assigned, which disclosure is fully incorporated herein by reference for all purposes. The particular bulbous configuration of lamp 24 is not important to the invention; however, a lamp having a relatively constant diameter for a significant dimensional length is illustrated for ease of understanding in the discussion that follows. Therefore, for such purpose, lamp 24 can be assumed to have a substantially uniform diameter, as shown.
In order to cope with the problem of achieving a sharp cut-off from a substantially tubular source, a family of curves having the reflecting properties shown in FIG. 2 have been developed. The ray from the surface of the tube nearest the reflector results in a reflected ray from the surface of the reflector which is parallel to the axis. The parametric equation for defining such a family of curves are:
y=1/2[x(p-1/p)-a(p+1/p)],
x=p(c-2aφ)-a,
where a is the radius of the tube; p=dy/dx=tanφ; and c=-2y, when x=-a. In the formula y is the elongate axis and x is the orthogonal axis therewith. The center of the tube is located at the x,y crossing, which is also the focal point for the curves.
The shape of the reflector defined by such equations is approximately parabolic. Note that a true parabolic fixture would reflect parallal rays from a point source of light, whereas the fixture above corrects for this bulb dimension insofar as it reflects parallel rays from the most rearward bulb surface. For purposes herein, however, the term parabolic will be used to include not only truly parabolic or substantially parabolic shaped curves, but also curves defined by the above equations.
Hence, as discussed above, top reflector segment 28 of the reflector system is parabolically shaped with its focal point at point 26 and has a rather narrow opening. That is, the end of reflector segment 28 at window 14 has already asymptotically reached a position approaching a parallel line to elongate axis 20. With respect to the equations set out above for the preferred shape of the reflector segments, a preferred embodiment of the present invention includes a top reflector segment 28 having a value c equal to 2.9. The rearward end of segment 28 terminates slightly behind the front part of lamp 24 with respect to a line drawn therethrough parallel with window 14.
The slope of segment 28 is so shallow that if it were extended to its vertex, the segment would interfere with the envelope of lamp 24. Therefore, at a position 30, where the vertical axis intersects the arc of reflector 28, a short reflector segment 32 parallel to the horizontal axis, is connected. Such connection assures that parabolic rearward reflector segment 34, connected to the other end of reflector segment 32, is spaced apart from the surface of lamp 24. A preferred value a for parabolic reflector sgement 34 is 4.
Bottom reflector segment 36 is also parabolically shaped, having a preferred value c of 4.6. Hence, it may be seen that the slope of this segment is not nearly as steep as for the top segment. Moreover, the vertex position is even further removed from lamp 24 than reflector 34 is from lamp 24, thereby necessitating a connecting piece 38 between segments 34 and 36 along axis 20.
Window 14 is located along axis 20 at a distance to provide the beam width desired from the reflector. However, the window is not at right angles with axis 20, as with most luminaires, even asymmetrical ones, but instead is at an angle of about 60 degrees to axis 20. Such a window location has several beneficial advantages.
First, it shortens the length of bottom reflector segment 36 with respect to top reflector segment 28. This means that cutoff in the downward direction is approximately back toward pole 12 with the reflector angled as shown. This may be seen by considering the direction of the light ray emanating from the front surface of lamp 24 as it passes by the front corner or exit pupil of the fixture at the window edge of reflector segment 36.
Primary reflected light from center 26 of lamp 24 is reflected forward from reflector segment 36 parallel to axis 20, an important characteristic of a parabolic reflector. However, the light "cone" from the surfaces of lamp 24 results in a primary reflected light spread. Direct light just past the exit pupil edge of the fixture is almost straight down from the fixture as shown in the drawing, with all other direct and primary reflective light emanations being in front of such downward emanation.
The second advantage of window 14 being angled the way it is is that the length of reflector segment 28 is longer than the length of reflector segment 36, thereby advantageously reducing the cutoff angle of segment 28 even beyond that caused by the difference in the respective parabolic arc slopes of the reflector segments.
The third advantage of window 14 being at only about 60 degrees to axis 20 is that the light transmittance through the lens is not greatly impaired compared with a lens positioned at a right angle to axis 20. That is, the light reflected back into the fixture from the 60-degree lens is not very great, as it would be with a more sharply angled lens.
The position and length of shield 40 is determined as follows. A line 42 is drawn from focal point 26 at an angle approximately 10 degrees above horizontal axis 20. The front end of shield 40 is placed at the point that line 42 intersects the plane of window 14. Shield 40 is parallel to axis 20. Another line 44 is drawn from focal point 26 to the window end of reflector segment 28. The rear end of shield 40 is determined by the intersection of shield 40 with line 44.
Such a location of the shield blocks all direct light from lamp 24 above line 42. All primary reflected light from the rearward portion of lamp 24 is permitted to be reflected from reflector segment 28. Hence, the spill light is greatly reduced, thereby sharpening the cutoff characteristics.
The top surface of the shield is darkened by any convenient means, such as by painting with black paint. The underneath side is made specular, as with the other reflective surfaces, so that secondary reflections from the top shield surface are greatly reduced and primary reflections from the bottom surface increase the efficiency of the downwardly directed light. Hence, the shield blocks non-useful light rays and redirects other rays more usefully.
Obviously, shield 40 can be located at a different angle than 10 degrees, in the 5-40 degree range, but a 10-degree angle has proven extremely satisfactory in actual practical designs of the invention. Of course, a differently located shield would have a different length than a 10-degree located shield.
The above design permits sharp cutoff from a fixture of relatively limited dimension never before achieved and can be thought of as an extremely useful technique of "miniaturizing" so as to attain equal results otherwise achievable only with fixtures of much larger dimension (e.g., having shallow parabolic reflectors of great length). Not only is there a material savings, but the efficiency of such a fixture is extremely high.
While a particular embodiment of the invention has been shown and described, it will be understood that the invention is not limited thereto since many modifications may be made and will become apparent to those skilled in the art. For example, three parabolic segments are shown. The number can be reduced to two or even one and still be within the scope of the broad concept of the invention.
|
A light fixture comprising parabolic reflector segments therein, the lamp being located at the focal point of the segments. One segment has an arc preferably more shallow than the other segment. The window opening is angled preferably at an angle of 60 degrees to the elongate axis of the parabolic segments to provide sharper light cutoff or less spill light from one reflector segment than from the other. A shield positioned parallel to the elongate axis and on the side of the axis within the reflector segment where the cutoff characteristics are the greatest, permits primary reflected light from the lamp, while preventing direct light from the lamp to pass above the shield. The specular underside of the shield enhances light reflection therefrom while the darkened top shield surface blocks secondary reflection above the cutoff angle.
| 5
|
RELATED APPLICATIONS
[0001] This application is a continuation application under 35 U.S.C. §120 of the prior application Ser. No. 11/051,764 filed on Feb. 7, 2005, attorney docket 47004.000122, entitled “System and Method for Card Processing With Automated Payment of Club, Merchant, and Service Provider Fees,” which was a continuation of prior application Ser. No. 09/325,536, attorney docket 47004.000040, which was filed Jun. 4, 1999, entitled “Credit Instrument and System with Automated Payment of Club, Merchant and Service Provider Fees,” which issued as U.S. Pat. No. 6,882,984 on Apr. 19, 2005, both of the aforementioned applications being incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The present invention relates generally to a system and method for providing credit instruments whereby the credit processing system is preconfigured with a series of participating clubs, merchants, or service providers such that an applicant can provide for automated payment of dues and fees without having to engage in a separate transaction with each club, merchant or service provider.
BACKGROUND OF THE INVENTION
[0003] It is increasingly common that consumers pay for many of their expenses using credit cards, bankcards or like instruments rather than using cash or checks. Consumers do this because they find it more convenient that sending cash or checks. Using credit cards in this fashion is also desirable because the consumer can borrow using his/her credit card when personal funds are low, and also because an itemized list of payments is generated each month.
[0004] Some clubs, merchants or service providers may require fixed payments on a periodic basis, such as weekly, monthly, semi-annually, and so forth. In the case of a club, such as a health club, a consumer may be required to send dues each month. Using a credit card, the consumer may send in a payment slip each month with the credit card number, expiration date and a signature authorizing the charge to the consumer's credit card. Or the consumer may call the club's place of business to give like information verbally over the phone. Or the consumer may contact the club to give like information using a home computer accessing the Internet.
[0005] In each case the consumer is relieved of the inconvenience of sending cash, checks or the equivalent. Yet in each case the consumer still must initiate the transaction each month by mail, telephone or computer. For the customer associated with a number of clubs requiring periodic payments, this may involve a significant number of transactions for the consumer to initiate each week or month. Moreover, since payment due dates may differ for each club, the consumer cannot make the overall task more efficient by doing all the payments at once unless he/she is willing to pay some bills early or some bills late. Thus, this approach to paying bills using a credit instrument has significant shortcomings for the consumer.
[0006] From the perspective of the club, processing credit card information is advantageous since processing tends to be easier than for checks. However, there are still significant shortfalls. The club must await the submission of payment from the consumer for each cycle. Sometimes consumers will be late in contacting the club to submit their credit card information. Sometimes communication lapses will result in incorrect information being submitted to the club, such as when the consumer fills in the wrong credit card information or a customer service representative misunderstands information given over the telephone.
[0007] And even when no such difficulties arise, the club still must initiate the transaction with the card provider by submitting a separate charge for each consumer on each payment cycle. For a club having hundreds or thousands of members, this may entail the initiation of hundreds or thousands of charges at different times. This is a significant disadvantage because of the time and costs imposed on the club. Additionally, charges may be imposed on the club and/or the card provider when an interchange processor is contacted for each transaction initiated by the club. Additionally, there may be communications difficulties in contacting a card provider bank or interchange to submit the charge, such as when a direct-dial connection fails or an Internet or like computer network connection fails.
[0008] Sometimes a consumer will give a club permission to bill his/her credit card on an ongoing basis so that the consumer does not have to initiate payment each cycle. While this may lighten the burden on the consumer somewhat, it does not eliminate the burden on the club, which still must submit a charge to the consumer's credit card each cycle. Moreover, the consumer must still engage in an initial transaction with each club, merchant or service provider, to grant this authorization to bill the consumer's credit card on a periodic basis. For the consumer wishing to give such authorization to multiple clubs, merchants or service providers, a series of separate transactions must be undertaken. This is a significant shortcoming.
[0009] Other problems and drawbacks also exist.
SUMMARY OF THE INVENTION
[0010] For these and like reasons, what is desired is a system and method of providing a credit card system that is associated with a series of clubs, merchants, service providers or the like so that a fully automated payment of dues or fees can be effectuated with minimal transactions.
[0011] Accordingly, it is one object of the present invention to overcome one or more of the aforementioned and other limitations of existing systems and methods for payment of fees or dues using a credit instrument.
[0012] It is another object of the invention to provide a credit instrument that is pre-associated with a series of clubs, merchants or service providers so that a cardholder can authorize automated payment for multiple business concerns in a single transaction with the card provider.
[0013] It is another object of the invention to provide such a credit instrument where the information for multiple business concerns is stored at a credit system processor so that the creation of automated payment agreements for a consumer for a plurality of such business concerns is easily effectuated.
[0014] It is another object of the invention to provide a credit instrument application system where an applicant is solicited to join clubs and set up automated payment agreements at the same time the application is being processed so that a competitive marketing advantage is conferred on the associated business concerns.
[0015] It is another object of the invention to provide such a credit instrument associated with a series of business concerns such that a competitive advantage is conferred on the associated business concerns because the cardholder is encouraged to maintain the accounts therewith.
[0016] It is another object of the invention to provide such a credit instrument associated with a series of business concerns that provides a competitive advantage for the card provider by maximizing revenue and creating barriers to exit for both the associated business concerns and the cardholders.
[0017] To achieve these and other objects of the present invention, and in accordance with the purpose of the invention, as embodied and broadly described, an embodiment of the present invention comprises an apparatus and method for a card that allows a cardholder to set up auto-charge payment of dues and fees to a series of clubs, merchants or service providers. The card also may be used for other transactions that accept credit cards. The system includes a database containing information of the associated clubs, merchants and service providers, so that applicants and cardholders can easily configure auto-charging for multiple business concerns in one sitting. The system may then process auto-charge transactions in an automated fashion without requiring a cardholder to submit payment authorization or the business concern to submit a charge for each periodic payment. Inconvenience and administrative costs to the cardholder and the business concerns are greatly reduced. The system and method provide a competitive advantage to the associated business concerns to secure the initial account and then to retain it. The system and method encourages card loyalty of both the card members and the business concerns to the card provider.
[0018] The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute part of this specification, illustrate several embodiments of the invention and, together with the description, serve to explain the principles of the invention. It will become apparent from the drawings and detailed description that other objects, advantages and benefits of the invention also exist.
[0019] Additional features and advantages of the invention will be set forth in the description that follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the system and methods, particularly pointed out in the written description and claims hereof as well as the appended drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The purpose and advantages of the present invention will be apparent to those of skill in the art from the following detailed description in conjunction with the appended drawings in which like reference characters are used to indicate like elements, and in which:
[0021] FIG. 1 is a block diagram of the credit card processing system according to an embodiment of the invention, including the network, central server system, user systems, credit card database and various processor systems.
[0022] FIG. 2 is a block diagram according to an embodiment of the invention illustrating an exemplary partner and associated clubs, merchants or service providers.
[0023] FIG. 3 is a block diagram according to an embodiment of the invention illustrating data that may be stored by the system for various partners.
[0024] FIG. 4 is a block diagram according to an embodiment of the invention illustrating data that may be stored in the system for installations corresponding to an associated partner.
[0025] FIG. 5 is a block diagram according to an embodiment of the invention illustrating data that may be stored in the system for a club, merchant or service provider.
[0026] FIG. 6 is a block diagram according to an embodiment of the invention illustrating data that may be stored in the system for auto-charging dues or fees for a club, merchant or service provider.
[0027] FIG. 7 is a block diagram according to an embodiment of the invention illustrating data that may be stored in the system for a member or cardholder.
[0028] FIG. 8 is a flowchart illustrating a method, according to an embodiment of the invention, for a card provider to provide an auto-charge feature to cardholders for associated clubs, merchants and service providers.
[0029] FIG. 9 is a flowchart illustrating a method, according to an embodiment of the invention, for a user of the system to process an application on behalf of an applicant, including the selection of auto-charge options for associated clubs, merchants and service providers.
[0030] FIG. 10 is a flowchart illustrating a method, according to an embodiment of the invention, for the system to execute batch processing of auto-charge fees or dues for cardholders who have selected the auto-charge option for clubs, merchants or service providers.
DETAILED DESCRIPTION OF THE INVENTION
[0031] As discussed in the Summary of the Invention, the present invention is directed to a method and apparatus for a credit instrument that supports auto-charging to clubs, merchants and service providers.
[0032] The auto-charge feature of the card can be used to automatically charge dues and fees to a cardholder's account for clubs, merchants, service providers and other business concerns. As can be appreciated by those skill in the art, the inventive concept is well-adapted to setting up auto-charging when there is an ongoing relationship between the cardholder and the business concern, such as a health club, where payments are to be made each month. For the sake of clarity and brevity of this detailed description, the explanation of the invention shall be discussed in terms of associated “clubs,” although it is to be understood that this also embraces merchants, service providers and other business concerns.
[0033] Additionally, the description will refer to “partners.” Partners may be entities that are associated with a number of clubs, such as a university or military branch. A partner may provide data to a card provider of a number of clubs so that applicants (e.g., students or alumni or service members) can easily join up and set up auto-charge arrangements therewith. By “partnering” with the card provider, both the partner and the card provider derive benefits of bringing the plurality of clubs into the system. Of course, those of skill in the art will recognize that the benefits of the system can be derived where there are no partners, i.e., where clubs become participants in the system without an intermediate partner.
Overview of the System
[0034] FIG. 1 depicts an overview of the system, according to an embodiment of the present invention, including central server system 100 ; network 150 ; user systems 105 ; credit card database module 110 ; non-monetary business processor system 115 ; report processor system 120 ; application processor system 125 ; credit bureau data module 130 ; monetary processor system 135 ; dues processor system 140 ; and transaction processor system 145 .
[0035] Central server system 100 may comprise a server system for receiving applications, maintaining a database, processing transactions and interfacing with user systems over network 150 . Generally, central server system 100 includes hardware and software for supporting system administration, database management, application and transaction processing, report generation, and network-related operations. In one embodiment, control server system 100 may interface with user systems 105 over the Internet or like packet-switched networks. In such an embodiment, central server system 100 may have software to support graphical user interface (GUI) with user systems 105 through browser pages or the like (e.g., incorporating HTML or XML mark-up language) so that users need little or no specialized hardware or software.
[0036] Central server system 100 may use server hardware running Microsoft NT™ and using Oracle v. 7.3.4 for database operations. Central server system 100 may support network related operations using software such as Weblogic™ v.3.1 for Unix. Software for processing transactions and applications is well known in the art and, for example, may be programmed in high level languages such as C++. Central server system 100 may be a secure system employing encryption technology, such as 128 bit SSL (secure sockets layer) encryption, to protect data transmitted over the network. Central server system 100 may also require a user name and password for a party to access the system over network 150 . Central server system 100 may support interface with user systems 105 through the application of servlets and/or applets, know to those of skill in the art, for supporting a substantially platform independent interface with users who have “standard” computer hardware and software.
[0037] User systems 105 may comprise any system capable of interfacing with server system 100 over network 150 . User systems 105 may comprise “standard” computer systems that do not require specialized hardware or software to interface with central server system 100 . User systems 105 may comprise personal computers, microcomputers, minicomputers, portable electronic devices, a computer network or other system operable to send and receive data through network 150 . In one embodiment, user systems 105 may comprise a personal computer running Windows NTT™ and Microsoft Internet Explorer™ 4.0.
[0038] Network 150 may comprise any network that allows communications amongst the components, and may encompass existing or future network technologies, such as the existing “Internet,” “World Wide Web,” Wide Area Network, “Internet Protocol-Next Generation” (Ipng) and like technologies. In one embodiment, network 150 comprises the Internet so that user systems 105 can access central server system 100 as a web site and interface therewith using standard browser pages.
[0039] Credit card database module 110 represents the storage media employed to store data for the system. Credit card database module 110 may be one or more physically distinct media, such as hard drives, floppy drives, CD-ROM and other existing or future storage technologies supporting ready access. Credit card database module 110 may store the account data for the system, such as transactions data, partner data (to be discussed further below), installation data (to be discussed further below), club data, auto-charge data, member data and so forth. Generally, this module stores records of member accounts (e.g., for posting charges and payments), records of associated partners and clubs, and records of auto-charge data.
[0040] Application processor system 125 is for processing credit card applications for the cards. Application processor 125 may communicate with credit bureau data module 130 for retrieving and evaluating information of an applicant's credit-worthiness in order to accept or deny an application. Application processor 125 may process applicant information submitted by an applicant through user system 105 and report results back to central server system 100 , which may add the applicant to credit card database module 110 if an applicant is approved.
[0041] Report processor system 120 may extract data from the database (e.g., credit card database module 110 ) for reports to be generated periodically or by request. Report processor system 120 may present such reports as browser or like pages to user systems 105 . In one embodiment, report processor 120 comprises Crystal Info™ software as the reporting engine. In one embodiment, report processor system 120 can be accessed over the Internet by users such as partners and/or clubs to retrieve information regarding partner club affiliation, club membership, account status and the like.
[0042] Non-monetary business processor system 115 may be a processing module supporting central server system 100 so that users can change certain information stored in credit card database module 110 . A “user” generally refers to a party that is authorized to access central server system 100 . In one embodiment, where a military branch is a partner, each base or installation may have a user authorized to accept applications and modify system data, such as changing the address of a cardholder stored in credit card database module 110 . Generally, the card provider may have a plurality of persons authorized as users. In one embodiment, there is a plurality of levels of authorization for users, such that a card provider user may have access to all data, a partner user may have access only to that data pertaining to that partner, and a cardholder user may have access only to that data pertaining to the cardholder's account.
[0043] Monetary processor system 135 may comprise a module for submitting charges to a cardholder's account, such as charges, payments and adjustments. Monetary processor system 135 may submit a charge request, such as a merchant number, terminal ID, account number, charge amount and current date, to transaction processor system 145 . Monetary processor system 135 is generally capable of operating in nominal real time so that charge requests are submitted for processing as they are received. In one embodiment, monetary processor system 135 is capable of processing so-called “on-us” charges submitted directly to the system (e.g., submitted directly to the card provider or bank) and so-called “not-on-us” charges submitted through an interchange (e.g., a Visa™ or MasterCard™ interchange, well known to those of skill in the art). Generally, monetary processor system 135 processes charges other than the auto-charges, such as merchant charges, adjustments, cardholder payments, and the like.
[0044] Dues processor system 140 prepares charge requests associated with auto-charge fees or dues. Dues processor system 140 generally processes “on-us” charges so that contacting an interchange is not required. Dues processor 140 will periodically (e.g., daily) determine the auto-charge payments required for cardholders. A set of transactions is prepared for “batch processing” and the transactions may be sent to transaction processor 145 as a group. In one embodiment, dues processor system 140 is also capable of preparing transactions from external files received, for example, from a utility on a daily basis. This function is similar to the auto-charge feature for clubs and the like, except the amount of each transaction may vary based on the data received from the external file. In another embodiment, dues processor system 140 is capable of preparing “special club” transactions, such as processing charges submitted based on a merchant code set up in the system for the “general's party” or like special occasion amenable to having charges submitted and processed in a group fashion.
[0045] Transaction processor system 145 processes the transactions for the system. Generally, transaction processor receives transaction requests, accesses an account database (see, e.g., credit card database module 110 ) and determines if the transaction is authorized or declined. Based on the result, the pertinent card member account and merchant account is updated as appropriate. In one embodiment, a transaction request may comprise a merchant number, terminal ID (identifying the terminal submitting the request), account number, charge amount, and current date. Several categories of merchant numbers may be available to identify the merchant and the nature of the transaction request. These categories may include dues billing, dues adjustment, special event, recurring charge (e.g., external file from a utility submitted on a daily basis), payment or other. A transaction request, as described above, may be submitted to transaction processor system 145 , which may return a six-digit authorization code, a decline code, a decline and confiscate message or a call bank message. The transaction processor 145 or central server system 100 may post the result to the card member's account and transfer any payment to a club account (such as a direct deposit transaction).
Partners
[0046] FIG. 2 illustrates the concept of partners for the system. Partner 200 may be a military branch that is associated with a series of clubs such as garden club 205 , officer's club 210 , health club 215 and other clubs, merchants or service providers 220 . More generally, a partner may comprise a business concern, group or association that itself is associated with a series of clubs or the like. For example, a partner may be a university or military branch that wishes to have data of its various clubs and the like entered onto the system so that students, alumni, or military personnel can readily join clubs and set up auto-charge payment arrangements. The benefits from such an arrangement to the card provider, partner and clubs are substantial.
[0047] As previously noted, the system can operate and provide substantial benefits without intermediate partners. Yet, it can be appreciated that the benefits and efficiencies may be maximized when the card provider has an arrangement with an intermediate partner associated with a number of constituent clubs.
Data in Credit Card Database 110
[0048] FIGS. 3-7 illustrate the types of data that may be stored in credit card database module 110 . As those of skill in the art can appreciate, the allocation of the data types is functional and descriptive. Credit card database module 110 may be a fully relational database so that each data type can be associated with other data types as appropriate.
[0049] FIG. 3 illustrates the partner data that may be stored. In this exemplary embodiment, partner data includes Air Force 300 , Army 305 , Navy 310 , State University 315 and other partners 320 . Each represents a partner with whom the card provider is associated.
[0050] FIG. 4 illustrates the various “installations” in the system. An installation refers to a physical location of a partner that has a plurality of locations. In the military paradigm, an installation may correspond to a base. For example, for a Navy partner, the installations may include Navy Base Norfolk 400 , Navy Base Washington D.C. 405 , Navy Base Cecil Field 410 , and other partner bases 415 . By including installation data, the system can provide the appropriate club data for each base. For example, when a new recruit applies for a card at Navy Base Norfolk 400 , the system may provide the appropriate list of clubs. When the new recruit is transferred to Navy Base Washington D.C. 405 , the new recruit member data is easily “transferred” or reassigned to the new base without re-entering all of his/her data. Such installation data is also useful to the partner for evaluating billings per installation or club membership per installation.
[0051] FIG. 5 illustrates the club (or merchant or service provider, etc.) data that may be stored in credit card database module 110 . In this exemplary embodiment, for a club there may be partner 500 (identifying the partner the club is associated with), merchant code(s) 505 , name 510 (name of the club), type 515 (e.g., identifying whether the entity is a club, merchant, service provider, utility, etc.), address/phone 520 , manager name 525 and installation ID 530 (identifying the installation). Regarding merchant code(s) 505 , a club may be assigned several merchant codes to cover different types of transactions, such as dues and dues adjustment.
[0052] FIG. 6 illustrates the auto-charge data that may be stored in credit card database module 110 . This data may be stored for a club to provide the various options for the auto-charge feature of the system. This way when a card member decides that he/she would like to automatically pay the officer's club, the appropriate data for that club is present in the system. In the exemplary embodiment of FIG. 6 , the auto-charge data comprises description 605 (describing the club and/or nature of the auto-charge), frequency 610 (describing the frequency of payment such as daily, monthly, quarterly, etc.), ID 615 (identifying the club), installation/lump fee 620 (whether the club will accept installations or requires lump fees), cancellation policy 625 (explaining cancellation policy of the club), refund policy 630 (explaining the refund policy of the club), promotional rates 635 (providing promotional rates for, e.g., new members, or differential rate structures depending on rank or other personal characteristics), and price/fee 640 (price or fee for the club).
[0053] FIG. 7 illustrates an exemplary embodiment of the data that may be stored in credit card database module 110 for the cardholders. Cardholder data may comprise auto-charge data 700 , which may further comprise frequency 705 , number of payments 710 , amount 715 , and date 717 (provides date of the auto-charge payment, e.g., the 19th of each month). Auto-charge data 700 may have an entry for each club the cardholder is paying using the auto-charge feature. Military 720 lists data for a card member in the military, such as name/address 725 , phone 730 , status 735 (e.g., retired, active duty or reserve), rank 740 , and agent code 745 (identifies the installation to which the cardholder belongs). The cardholder data may further comprise card number 750 , member ID 755 (e.g., may be social security number), merchant codes 760 (identifies clubs/merchants/service providers that the cardholder is associated with), and other account data 770 . In one embodiment, merchant codes 760 is also stored on the card so that the card not only supports normal credit card applications and the auto-charge capability, but can also function as a “door pass” that members may use to gain entry or authorization for clubs.
Graphical User Interfaces for the System
[0054] In one embodiment, central server system 100 interfaces with user systems 105 over the Internet or like packet-switched network using a standard GUI interface, such as browser pages accessed over the World Wide Web.
[0055] In this embodiment, there is a log in page for an authorized user, who must provide a user name and password. In this embodiment, there is a so-called “home page” which includes options for member lookup (for locating members), application processing (for processing applications), member maintenance (for changing member data, such as an address or installation), batch processing (for batch financial transactions), reports (for preparing reports) and administration (for profiles, maintenance of installations, clubs, and merchants). In this embodiment, there may be an application browser page for submitting an application over the Internet.
Methods of Using the System
[0056] According to an embodiment of the present invention, a method is provided for a credit card system that is associated with a series of clubs, merchants, service providers or the like so that a fully automated payment of dues or fees can be effectuated. Referring to FIG. 8 , a card provider reaches an agreement with a partner associated with a plurality of clubs, according to step 1200 . The card provider then updates a database to include the partner and plurality of clubs, as in step 1205 (e.g., see FIGS. 2 , 3 , 4 , 5 and 6 ). In one embodiment, a card provider reaches such an agreement with a military branch which then provides data describing installations and clubs that could be stored in a database such as credit card database module 110 . The card provider and/or partner solicits applications for the credit instrument and invites the applicant to join various clubs and/or set up auto-charge arrangements, according to step 1210 . For example, the new recruit is invited to apply for a card and also to join various clubs such as the Officer's Club and golf club, for which the auto-charge feature may be set up. According to step 1215 , auto-charge data is entered into the processing system (e.g., see FIG. 7 ) for each member selecting the auto-charge feature for a club. Based on the auto-charge data entered for the members, the system processes charges automatically, according to step 1220 . Charges are posted to the members' accounts, according to step 1225 . In one embodiment, steps 1220 and 1225 may be processed as batch transactions, as previously discussed. In one embodiment, steps 1220 and 1225 are performed as “on-us” transactions so that interchange fees are avoided, providing savings to the card provider and/or partner and/or clubs. In step 1230 , payment is issued to the partner or clubs. In one embodiment, payment is issued to the partner, such as to a military base, by automated direct deposit. In another embodiment, it may be provided that payment is issued directly to clubs.
[0057] According to an embodiment of the present invention, FIG. 9 depicts a method for processing an application for a credit card system that is associated with a plurality of clubs and that supports auto-charging. The user logs on to the system, as in step 1305 , and the system authenticates the user, as in step 1310 . In one embodiment, where the partner is a military branch, each installation or base may have an authorized user for accepting applications on behalf of service personnel. The user submits the applicant's name, address and other general data on behalf of the applicant, as in step 1315 . The user requests whether the applicant wants to auto-charge certain clubs, as in step 1320 . The user submits the applicant's auto-charge data, as in step 1325 . The application is submitted to the application processor, as in step 1330 (e.g., see FIG. 1 , application processor system 125 ). The application decision is returned to the user, as in step 1335 . The credit card database is updated to include the applicant if the application is approved, as in step 1340 (e.g., see FIG. 1 , credit card database module 110 ; FIG. 7 ).
[0058] According to an embodiment of the invention, FIG. 10 depicts a method of batch processing auto-charge dues or fees for the system. Referring to FIG. 10 , the system (e.g., see FIG. 1 , central server system 100 ) invokes the batch processing logic (e.g., see FIG. 1 , dues processor system 140 ), according to step 1400 . The server system builds a list of members at each installation or base, according to step 1405 . The server system builds a list of clubs (for which the auto-charge option is enabled) for each member, according to step 1410 . Central server system 100 obtains the dues or fees amount for each member, according to step 1415 . The server system sends dues files (e.g., a batch of transaction requests) to transaction processor system 145 for authorization (e.g., see FIG. 1 , transaction processor system 145 ), according to step 1420 . The server system receives the results of the transaction requests, i.e., an authorization number or rejection for the transaction requests, as in step 1425 . The server system posts the transactions to the members' accounts, as in step 1430 . The server system transfers funds to club accounts, as in step 1435 . The server system may then issue reports to partners on authorization failure/success and gross/net charges, as in step 1440 .
[0059] Other embodiments and uses of this invention will be apparent to those having ordinary skill in the art upon consideration of the specification and practice of the invention disclosed herein. The specification and examples given should be considered exemplary only, and it is contemplated that the appended claims will cover any other such embodiments or modifications as fall within the true scope of the invention.
|
An apparatus and methods for a card that allows a cardholder to set up auto-charge payment of dues and fees to a series of clubs, merchants or service providers. The card also may be used for other transactions that accept credit cards. The apparatus includes a database containing information of the associated clubs, merchants and service providers, so that applicants and cardholders can easily configure auto-charging for multiple business concerns in one sitting. The apparatus may process auto-charge transactions in an automated fashion without requiring a cardholder to submit payment authorization or the business concern to submit a charge for each payment. Inconvenience and administrative costs to the cardholder and the business concern are reduced. The system and method provide a competitive advantage to the associated business concerns to secure the initial account and then to maintain it. The system and method encourages card loyalty of both the card members and the business concerns to the card provider.
| 6
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Patent Application No. PCT/IB2013/052077, filed Mar. 15, 2013, which claims priority to foreign South African Patent Application No. 2012/01951, filed Mar. 15, 2012, the contents of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
This invention relates to the production of 2,2,3-trifluoro-3-(trifluoromethyl)oxirane, commonly known as hexafluoropropylene oxide (HFPO), in particular the gas phase production of HFPO from hexafluoropropylene (HFP) and molecular oxygen.
BACKGROUND OF THE INVENTION
HFPO, the epoxide product of the partial oxidation of HFP, is a highly reactive and versatile intermediate that can be converted to perfluoroalkylvinylethers. It is used in the production of proton-exchange members for fuel cells and to make heat-resistant fluids, high-temperature lubricants, high-performance elastomers and surfactants. Known non-catalytic epoxidation processes for the production of HFPO suffer from various problems such as the production of large quantities of environmentally unfavourable waste and/or high reagent costs due to the use of solvents and/or chemical oxidising agents such as hypohalites, hydrogen peroxide and organic peroxides, which can also be hazardous to operators. Moreover, with known non-catalytic batch processes which employ oxygen as the oxidising agent for the epoxidation of HFP, it is difficult to achieve adequate rates of production of HFPO. This invention seeks to ameliorate the abovementioned problems, at least to some extent, while achieving an adequate rate of production of HFPO i.e. a good selectivity towards HFPO at an acceptable yield.
SUMMARY OF THE INVENTION
According to a first aspect of the invention, there is provided a process for the production of HFPO, which process includes:
introducing a feedstock comprising HFP and molecular oxygen into a heated reaction zone of a reactor, with the reaction zone being at a reaction temperature T r , where 180° C.≦T r ≦230° C.; allowing the feedstock to react, by epoxidation of the HFP, to produce HFPO; and withdrawing the HFPO from the reaction zone,
with the introduction of the feedstock into the reaction zone and the withdrawal of the product from the reaction zone being continuous.
The process may include pretreating the reactor by heating the reaction zone of the reactor to a pretreatment temperature T p , where 180° C.≦T p ≦230° C., and thereafter passing gaseous HFP and oxygen through the reaction zone at a first HFP:O 2 molar ratio, x, for a period of time, while maintaining the pretreatment temperature T p in the reaction zone; and thereafter adjusting the HFP:O 2 molar ratio to a second value, y, where y≠x, to achieve the HFPO production.
The pretreatment temperature, T p , is preferably approximately 200° C.
The process thus includes maintaining the reaction zone, during the conversion of HFP to HFPO after the pretreatment of the reactor, i.e. during a HFPO production phase, at the reaction temperature (T r ) of 180° C. to 230° C. More preferably, Tr is 200° C.-215° C., still more preferably 205° C.-210° C., most preferably about 207° C.
The molar ratio, x, of HFP:O 2 may be about 1:1, while the molar ratio, y, of HFP:O 2 may be in the range of 0.25:1 to 1.81:1, provided that y is not the same as x. More preferably, the molar ratio, y, of HFP/O 2 is in the range of 1:1-1.4:1, still more preferably 1.1:1-1.35:1, most preferably about 1.2:1. It will be appreciated that y will be selected to enhance the conversion of HFP and the yield of HFPO, with the selection of y taking into account the reaction temperature, T r , and the residence time (space time) of the feed (HFP and O 2 ) in the reaction zone.
The period of time that the reactor is pretreated may be at least 60 hours, and may be up to 80 hours.
The pressure in the reactor, during the pretreatment as well as subsequently, may be 3 to 6.5 bar, preferably about 4.5 bar. Such a moderate operating pressure is advantageous in that industrial experience has shown that the operational risk associated with processes using high pressures, even in the liquid phase, is generally greater. This may be explained in terms of the reaction mechanism. The oxidation of HFP is a complex free-radical chain process involving initiation, branching and termination steps. In a radical chain reaction scheme there exists competition for radicals or chain carriers between the branching and termination steps. If the propagation steps produce more chain carriers than the termination steps consume, the reaction can become self-accelerating. The population of the chain carriers grows exponentially and detonation occurs. For the HFP-O 2 system, this sequence of events is more likely to occur at higher pressures.
The gaseous residence or space time of the feedstock in the reaction zone during the pretreatment as well as subsequently, during the HFP conversion to HFPO, i.e. during the HFPO production phase, may be in the range of 80 to 160 seconds, e.g. about 120 seconds.
In the process, the HFP/O 2 feedstock is thus fed continuously into the reaction zone, while the HFPO product is withdrawn continuously from the reaction zone. The process is thus a continuous process.
The HFP/O 2 feed rate may be such that flow through the reaction zone is laminar.
The reactor may be in the form of a cylindrical tube of constant cross-sectional area and fabricated from metal. The metal preferably is, or includes, copper. The reactor tube is accordingly copper-based, and may thus be of copper. The reactor tube may have a surface-to-volume ratio of at least 2000 m −1 , preferably about 2670 m −1 . The reactor tube may be helically coiled. The reactor tube may be located in a jacket containing a heat transfer fluid, for example oil, the reactor tube being immersed in the heat transfer fluid. The interior of the jacket may be in flow communication with a heating apparatus for heating the oil to the pretreatment temperature (T p ) and to the reaction temperature (T r ) and maintaining it, so that the inside of the reactor tube, i.e. the reaction zone, will be maintained at the pretreatment temperature (T p ) or the reaction temperature (T r ).
Use of small diameter tubing and copper as material of construction results in efficient removal of reaction heat, e.g. since copper has both a relatively good thermal conductivity and a relatively high thermal mass. To a lesser extent, increased rates of heat transfer are obtained in the coiled tubes due to secondary flow (in the direction perpendicular to the axial flow) through the action of centrifugal force on fluid elements.
The pretreatment of the reactor may include a preparatory drying step for removing any moisture from the reactor prior to commencing passage of the HFP and the oxygen through the reactor. The preparatory drying step may include heating the reactor and/or passing a chemically inert gas, e.g. helium, through the reactor.
It is believed that the pretreatment step results in higher subsequent values of HFP conversion and of HFPO yield due to a gradual build-up of a film of high-molecular weight, oligomeric oxidation products on the inner surface of the reactor tube, which as indicated above may be of metal, and it is postulated that this results in passivation of the surface, which results in the higher conversion and yield values.
According to a second aspect of the invention, there is provided a process for the production of HFPO, which process includes:
introducing a feedstock comprising HFP and molecular oxygen into a heated reaction zone of a reactor comprising a copper-based cylindrical tube of constant cross-sectional area, with the tube being helically coiled and having a surface-to-volume ratio>2000 m −1 , with the reaction zone being at a reaction temperature T r , where 180° C.≦T r ≦230° C.; allowing the HFP and the molecular oxygen to react, by epoxidation of HFP, to produce HFPO; and withdrawing the HFPO from the reaction zone,
such that there is laminar flow of the feedstock and the HFPO through the reaction zone.
According to a third aspect of the invention, there is provided a process for the production of HFPO, which includes
pretreating a reactor by heating a reaction zone of the reactor to a pretreatment temperature T p , where 180° C.≦T p ≦230° C., and thereafter passing gaseous HFP and oxygen through the reaction zone at a first HFP:O 2 molar ratio, x, for a period of time, while maintaining the pretreatment temperature T p in the reaction zone; and thereafter adjusting the HFP:O 2 molar ratio to a second value, y, where y≠x, with the HFP being converted by means of epoxidation to HFPO.
As indicated in the introductory portion above, it is difficult to achieve adequate rates of production of HFPO with known batch processes. It has, however, unexpectedly been found that if there is careful temperature regulation, adequate yield of, and selectivity for, HFPO can in fact be achieved. It is believed that there is a propensity for the oxirane structure of HFPO to decompose at the elevated temperatures that are needed for initiation of the epoxidation reaction and that the problem is exacerbated because of high temperatures being obtained due to localised exothermic heat effects. It is believed that inefficient removal of reaction heat from conventional batch reactors has been a reason why they have been unable to achieve adequate rates of production of HFPO. It is further believed that a high reactor surface-to-volume ratio as well as heat transfer enhancement through the action of secondary flow in a coiled reactor tube also promotes HFPO yield by allowing for efficient removal of reaction heat.
Moreover, as hereinbefore set out, the reactor may be a cylindrical tube of constant cross-sectional area fabricated from metal, preferably copper. The use of copper is advantageous since it has both a relatively good thermal conductivity and a relatively high thermal mass, the combination of which is conducive to good temperature control. The reactor tube may have a surface-to-volume ratio of at least 2000 m −1 , preferably about 2670 m −1 . The continuous feedstock (HFP/O 2 ) flow rate into the reactor tube may be 100-200 ml/min, which provides laminar flow through the reactor tube. The reactor tube may be helically coiled.
The invention will now be described in more detail by way of non-limiting example and with reference to the accompanying schematic drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a longitudinal partial sectional view of a reactor in which a process according to the invention may be carried out;
FIG. 2 shows, in simplified block diagram form, a process, according to the invention, for producing HFPO implemented by a pilot plant;
FIG. 3 is a plot showing the effect of reaction temperature on the conversion of HFP, selectivity towards HFPO and yield of HFPO, at a fixed HFP/O 2 molar feed ratio (1 mol/mol) and space time (120 seconds);
FIG. 4 is a plot showing the effect of HFP/O 2 molar feed ratio on the conversion of HFP, selectivity towards HFPO and yield of HFPO, at a fixed reaction temperature (205° C.) and space time (120 seconds);
FIG. 5 is a plot showing the effect of space time on the conversion of HFP, selectivity towards HFPO and yield of HFPO, at a fixed reaction temperature (205° C.) and HFP/O 2 molar feed ratio (1 mol/mol);
FIG. 6 is a plot showing the effect of reactor temperature on the concentration of HFPO, COF 2 and CH 3 COF in the product which exits the reactor, at a fixed HFP/O 2 molar feed ratio (1 mol/mol) and space time (120 seconds);
FIG. 7 is a plot showing the effect of HFP/O 2 molar feed ratio on the concentration of HFPO, COF 2 and CH 3 COF in the product which exits the reactor, at a fixed reaction temperature (205° C.) and space time (120 seconds);
FIG. 8 is a plot showing the effect of space time on the concentration of HFPO, COF 2 and CH 3 COF in the product which exits the reactor, at a fixed reaction temperature (205° C.) and HFP/O 2 molar feed ratio (1 mol/mol);
FIG. 9 is a parity plot showing the observed HFPO yield and the HFPO yield predicted by a quadratic response surface model; and
FIG. 10 is a parity plot showing the observed HFPO selectivity and the HFPO selectivity predicted by a quadratic response surface model.
DETAILED DESCRIPTION
Referring to FIGS. 1 and 2 , reference numeral 10 indicates a reactor in which a process for producing HFPO in accordance with the invention can be carried out. FIG. 2 shows a pilot plant 11 for implementing the process. The reactor 10 comprises a bank of four helical reactor coils 12 a , 12 b , 12 c , 12 d and a jacket 14 , the reactor coils 12 a , 12 b , 12 c , 12 d being located within the jacket 14 . The jacket 14 includes a cylindrical wall 16 with a radially outwardly projecting flange 17 at an upper end thereof. The jacket 14 includes a lower dished end 18 which is welded to the wall 16 and a circular top 20 which is secured to the flange 17 by means of six circumferentially spaced M 22 bolts 22 . FIG. 1 shows the reactor 10 in an open condition, with the top 20 spaced above the flange 17 . However, in use, the reactor 10 is closed, with the top 20 adjacent the flange 17 , the jacket 14 being sealed. Each reactor coil 12 a , 12 b , 12 c , 12 d has a surface-to-volume ratio of 2670 m −1 . The reactor coils 12 are immersed in a heat transfer fluid, in this example oil, contained within the jacket 14 .
The reactor coils 12 a , 12 b , 12 c , 12 d were fabricated from ⅛ inch nominal size, copper refrigeration tubing and were formed from straight lengths of the tubing, which were bent into a coil shape and joined end-to-end to form the helical coils. Standard compression unions were used to join the individual lengths of tubing. The jacket 14 was fabricated from a length of 6-inch, schedule 40 304L stainless steel pipe 16 . The flange 17 was drilled and tapped for receipt of the bolts 22 .
The reactor has an inlet 24 and four outlets 26 , 28 , 30 , 32 . The inlet 24 and the outlets 26 , 28 , 30 , 32 extend through the top 20 . A flow line 34 leads into the reactor coil 12 a and a flow line 36 leads from the reactor coil 12 a . A connector 38 is located on flow line 36 and connects the flow line 36 to the outlet 26 and to a flow line 42 . Flow line 42 leads to the reactor coil 12 b , and a flow line 44 leads from the reactor coil 12 b . A connector 46 is located on flow line 44 and connects the flow line 44 to the outlet 28 and to a flow line 50 . Flow line 50 leads to the reactor coil 12 c, and a flow line 52 leads from the reactor coil 12 c . A connector 54 is located on the flow line 52 and connects the flow line 52 to the outlet 30 and to a flow line 58 . Flow line 58 leads to the reactor coil 12 d , and a flow line 60 leads from the reactor coil 12 d to the outlet 32 . The aggregate volume of the reactor coils 12 a , 12 b , 12 c, 12 d is 2.65×10 −4 m 3 , and the aggregate length of the reactor coils 12 a , 12 b , 12 c, 12 d is 150 m.
An external oil-bath heating and circulating apparatus 64 ( FIG. 2 ) is used to raise and maintain the temperature of the reactor coils 12 a , 12 b , 12 c , 12 d , line 66 leading from an oil reservoir 67 to the reactor 10 and line 68 leading from the reactor 10 to the reservoir 67 . To monitor the reaction temperature, type K thermocouples (not shown) were inserted into the reactor tube at a position 200 mm from the inlet 24 and 200 mm from each of the outlets 26 , 28 , 30 , 32 , as well as midway along the length of each reactor coil 12 a , 12 b , 12 c , 12 d.
The pilot plant 11 includes a flow line 70 which leads from a gaseous HFP source 72 and includes a flow line 74 which leads from an oxygen source 76 . The flow lines 70 , 74 lead to a very short common flow line 78 (essentially an asymmetric T connector). The flow line 78 leads to the inlet 24 of the reactor 10 . To control the flow rate of HFP, forward pressure regulator 80 and thermal mass flow controller 84 are provided on the flow line 70 . To control the flow rate of oxygen, forward pressure regulator 82 and thermal mass flow controller 86 are provided on the flow line 74 .
Flow lines 88 , 90 , 92 , 94 respectively lead from the reactor outlets 26 , 28 , 30 , 32 to a common flow line 96 via a 5-port, 4-way switching valve 98 . By means of the switching valve 98 , one or more of the flow lines 88 , 90 , 92 , 94 can selectively be closed off. In this way, the length of the reaction zone in the reactor 10 can be varied. The flow line 96 leads to a catch pot 100 . A flow line 102 leads from the catch pot 100 to an off-gas KOH scrubber 104 , which has an outlet 106 at a top thereof for venting off the scrubbed gaseous product. The scrubber 104 is equipped with 20 mm nylon Pall rings and is charged with a 20wt % aqueous solution of potassium hydroxide. A sample line 108 leads off from the line 102 to an automated, pneumatically-driven 6-port sample valve 110 equipped with a 300 μl sample loop. The valve 110 is connected to two gas chromatographs (not shown) and to a wet test meter (not shown). The flow lines 78 , 88 , 90 , 92 , 94 , 96 and the portions of the flow lines 70 and 74 that respectively lead from the mass flow controllers 84 , 86 to the flow line 78 are heat traced lines, the temperature of these lines being maintained between 60° C. and 100° C., preferably 80° C.
Various trials of the process for producing HFPO were conducted, the reactor 10 being operated, after pretreatment of the reactor coils, at various reaction temperatures, gaseous residence times (space times) and HFP/O 2 molar feed ratios. In particular, various reaction temperatures selected within a range of 180 to 230° C., various space times in the reaction zones were selected within a range of 80 to 160 seconds and various HFP/O 2 molar feed ratios were selected within a range of 0.25:1 and 1.81:1. Only a single factor (i.e. reaction temperature, space time or HFP/O 2 molar feed ratios) was varied at a time, whilst maintaining the other two factors at fixed values.
To pretreat the reactor 10 , the reactor coils are heated to a selected pretreatment temperature (T p ) for the epoxidation process, and thereafter gaseous HFP and oxygen is passed through the reactor 10 while maintaining the pretreatment temperature, the molar feed ratio of the HFP and the oxygen being approximately 1:1, the flow rate of the HFP/O 2 fed to the reactor 10 being 100-200 ml/min and the average total pressure in the reactor 10 being 4.5 bar. The conversion of HFP and yield of HFPO was found to stabilize after approximately 80 hours, at higher yield values than those obtained for the original newly installed reactor tube before the pretreatment. The operating temperature is maintained by means of the oil-bath heating and circulating apparatus 64 . It has been found that pretreatment need only be performed once for newly installed reactor coils. After the pretreatment, if subsequent conversion of HFP by means of epoxidation to HFPO is stopped at some time and then restarted, then another pretreatment is not necessary.
To conduct each trial after the pretreatment of the reactor coils, the HFP:O 2 molar feed ratio was adjusted to the HFP:O 2 molar feed ratio selected for the trial, while still maintaining the reaction temperature (T r ), the HFP and oxygen being continuously fed into one end of the reactor 10 via the inlet 24 and the reaction products being withdrawn continuously from the exit end via the outlet 26 or 28 or 30 or 32 . In particular, the length of the reaction zone and thus the gaseous residence time (space time) in the reactor 10 was selected by using the switching valve 98 to selectively close off one or more of the flow lines 88 , 90 , 92 , 94 (thereby adjusting the effective length of the reaction zone) and making an appropriate adjustment of the total inlet flow rate of the reactants. In this way, various space times in the reaction zones were selected within a range of 80 to 160 seconds.
The flow rates of the HFP and the oxygen were controlled using the mass-flow controllers 84 , 86 . The HFP feed gas was found to be 99.8% pure via gas-chromatography, with HFPO and trace amounts of hexafluorocyclopropane as impurities. Oxidation in the reaction zone was implemented under isothermal conditions, the temperature being maintained by means of the oil-bath heating and circulating apparatus 64 at a temperature selected by a thermostat (not shown), and at an average total pressure of 4.5 bar. The pressure drop over the reactor zone was less than 10% of the total operating pressure. The product from the reactor 10 was scrubbed through the off-gas scrubber 104 to remove noxious gases prior to venting via the outlet 106 , the product being contacted with the KOH solution in a counter-current fashion. It will be appreciated that in a commercial implementation to the process (not shown), a portion of the product from the reactor may be recycled through the reactor, and the portion of the product that is not recycled may be sent to a separation stage to separate out the HFPO from remainder of the reactor effluent.
During the production process, samples of the product gas were withdrawn via flow line 108 for composition analysis. Samples were withdrawn from the reactor exit stream via the valve 110 . The analyses of gaseous products were performed using two gas chromatographs (not shown) which were operated with an injection split ratio of 175:1. The mole fractions of HFPO, HFP, hexafluorocyclopropane (cyclo-C 3 F 6 ) and tetrafluoroethylene (C 2 F 4 ) were established using a Shimadzu G.C. 2010 gas chromatograph equipped with an Agilent GS-GasPro PLOT column (30 m×0.32 mm ID) as well as both a thermal conductivity detector and a flame ionization detector. The column oven was operated isothermally at 30° C. for 25 minutes. Unreacted oxygen and the acid fluoride byproducts, i.e. carbonyl fluoride (COF 2 ) and trifluoroacetyl fluoride (CF 3 COF), were separated on a Shimadzu G.C. 2014 gas chromatograph equipped with a Hayesep D packed column and a thermal conductivity detector. This analysis was carried out isothermally at 95° C.
The performance of the coiled laminar-flow reactor 10 (with a very high length-to-diameter ratio of 76200) was well approximated by a simply plug flow reactor model, as a result of the flattening of the radial concentration profiles through extensive radial diffusion and secondary flow through the action of centrifugal force on fluid elements.
FIGS. 2 to 4 show the effect of three operating variables (reaction temperature, molar feed ratio and space time) on the conversion of HFP, selectivity towards HFPO and yield of HFPO. For the purposes of this specification, conversion of HFP, selectivity towards HFPO and yield of HFPO, are defined by the following equations respectively:
X
HFP
=
F
HFP
0
-
F
HFP
F
HFP
0
×
100
%
(
1
)
S
HFPO
=
F
HFPO
F
HFP
0
-
F
HFP
×
100
%
(
2
)
Y
HFPO
=
F
HFPO
F
HFP
0
×
100
%
(
3
)
where:
F i =outlet molar flow rate of component i, mol s −1
F i 0 =inlet molar flow rate of component i, mol s −1
X HFP =conversion of HFP, %
S HFPO =selectivity towards HFPO, %
Y HFPO =yield of HFPO, %
FIGS. 6 to 8 respectively show the effect of reaction temperature, HFP/O 2 molar feed ratio and space time on the concentration HFPO, COF 2 and CF 3 COF in the product which exits the reactor 10 .
In order to further assess the effect of operating conditions on the product distribution obtained from the gas-phase oxidation of HFP and to probe for optimal reaction conditions, a central composite experimental design was used, reaction temperature (X 1 ), HFP/O 2 molar feed ratio (X 2 ) and space time (X 3 ) being chosen as the variables to be considered. The central composite design consisted of 20 experiments composed of a two-level, full-factorial design, 4 axial design points and 6 centre points.
The selected test limits for each variable are presented in Table 1, along with the observed responses.
The relationship between the independent variables and the response function (either HFPO selectivity or HFPO yield) was approximated by a quadratic response surface model, which in general form is given by Equation 4,
Y
=
β
0
+
∑
i
=
1
3
β
i
X
i
+
∑
i
=
1
3
β
ii
X
i
2
+
∑
i
<
j
∑
j
β
ij
X
i
X
j
(
4
)
where Y is the predicted response, β 0 is the intercept coefficient, β i are the coefficients of the linear terms, β ii are the coefficients of the squared terms, β ij are the coefficients of the interaction terms and X i and X j are the independent variables. The coefficients of the full quadratic polynomial expression were established using the method of least squares to obtain Equations 5 and 6 below.
Y HFPO =−2169.0252+17.9302 X 1 +28.6987 X 2 +5.1114 X 3 +1.006×10 −1 X 1 X 2 −1.2640×10 −2 X 1 X 3 −9.9461×10 −2 X 2 X 3 −3.9314×10 −2 X 1 2 −16.3222 X 2 2 −9.6724×10 −3 X 3 2 (5)
S HFPO =−2486.2318+22.0926 X 1 +18.3312 X 2 +4.6853 X 3 +2.3359×10 −1 X 1 X 2 −9.2480×10 −3 X 1 X 3 −3.1757×10 −1 X 2 X 3 −5.2091×10 −2 X 1 2 −11.3147 X 2 2 −1.0443×10 −2 X 3 2 (6)
The adequacy of each model was checked and confirmed with an analysis of variance (ANOVA) test. The results are presented in Table 2. Parity plots of the observed and predicted responses, i.e. HFPO yield and HFPO selectivity, are presented in FIGS. 9 and 10 , respectively. The coefficients of multiple determination for each model were found to be satisfactory. The computed value of the Fischer test statistic was greater than the tabulated value F (p−1, N−p,α) (p is the number of parameters in the model, N is the number of experiments and α in this case represents the significance level) of 4.94 at the 99% level of significance, for both models, indicating a statistically significant regression. The least squares regression results and significance effects of the regression coefficients for the HFPO yield and HFPO selectivity models are presented in Tables 3 and 4, respectively.
TABLE 1
Central composite design and experimental
X 1
X 2
X 3
Temper-
HFP/O z
Space
HFPO
HFPO
ature
Feed ratio
time
Conversion
selectivity
Yield
Run a
[° C.]
Level b
[mol/mol]
Level b
[seconds]
Level b
of HFP [%]
[%]
[%]
F1
190
−1
0.5
−1
100
−1
25.22
28.55
7.20
F2
220
+1
0.5
−1
100
−1
99.51
28.30
28.17
F3
190
−1
1.5
+1
100
−1
27.36
44.47
12.16
F4
220
+1
1.5
+1
100
−1
80.33
41.75
33.54
F5
190
−1
0.5
−1
140
+1
45.33
43.96
19.93
F6
220
+1
0.5
−1
140
+1
99.90
23.14
23.11
F7
220
+1
1.5
+1
140
+1
81.30
33.36
27.12
F8
190
−1
1.5
+1
140
+1
48.55
37.70
18.30
S1
205
0
1
0
86
−α
71.63
53.43
38.28
S2
205
0
1
0
154
+α
49.86
45.33
22.60
S3
205
0
0.25
−α
120
0
80.59
42.63
34.36
S4
205
0
1.841
+α
120
0
49.99
49.86
24.93
S5
180
−α
1
0
120
0
68.45
49.57
33.93
S6
230
+α
1
0
120
0
30.92
23.69
7.33
C1
205
0
1
0
120
0
97.98
23.40
22.93
C2
205
0
1
0
120
0
70.94
52.24
37.06
C3
205
0
1
0
120
0
74.52
55.38
41.27
C4
205
0
1
0
120
0
70.47
54.45
38.37
C5
205
0
1
0
120
0
70.67
55.51
39.23
C6
205
0
1
0
120
0
67.31
56.17
37.81
a F = orthogonal factorial design points, S = axial design points, C = centre points
b −1 = low value, 0 = centre point value, +1 = high value, −α = low axial value, +α = high axial value
TABLE 2
ANOVA results and regression statistics for the HFPO yield and
selectivity response models
Statistics
HFPO yield model
HFPO selectivity model
R 2
0.966
0.9389
Adjusted R 2
0.936
0.884
Standard error
2.680
3.980
F-statistic
32.144
17.073
p-value
3.223 × 10 −6
6.064 × 10 −5
Regression Mean Square
231.016
270.336
Residual Mean Square
7.186
15.834
TABLE 3
Least squares regression results and significance effects of the regression
coefficients for the HFPO yield model.
Parameter
Term
Coefficient
t-value
p-value
β 0
intercept
−2169.0252
−13.4617
9.8432 × 10 −8
β 1
X 1
17.9302
13.1465
1.2330 × 10 −7
β 2
X 2
28.6987
0.9890
3.4599 × 10 −1
β 3
X 3
5.1114
6.5857
6.1877 × 10 −5
β 12
X 1 X 2
1.006 × 10 −1
0.7960
4.4451 × 10 −1
β 13
X 1 X 3
−1.2640 × 10 −2
−4.0009
2.5146 × 10 −3
β 23
X 2 X 3
−9.9461 × 10 −2
−1.0493
3.1870 × 10 −1
β 11
X 1 2
−3.9314 × 10 −2
−12.3696
2.1953 × 10 −7
β 22
X 2 2
−16.3222
−5.3302
3.3284 × 10 −4
β 33
X 3 2
−9.6724 × 10 −2
−5.5872
2.3176 × 10 −4
TABLE 4
Least squares regression results and significance effects of the regression
coefficients for the HFPO selectivity model.
Parameter
Term
Coefficient
t-value
p-value
β 0
intercept
−2486.2318
−10.3955
1.1127 × 10 −6
β 1
X 1
22.0926
10.9129
7.0974 × 10 −7
β 2
X 2
18.3312
0.4255
6.7942 × 10 −1
β 3
X 3
4.6853
4.0669
2.2612 × 10 −3
β 12
X 1 X 2
2.3359 × 10 −1
1.2452
2.4142 × 10 −1
β 13
X 1 X 3
−9.2480 × 10 −3
−1.9720
7.6882 × 10 −2
β 23
X 2 X 3
−3.1757 × 10 −1
−2.2572
4.7587 × 10 −2
β 11
X 1 2
−5.2091 × 10 −2
−11.0417
6.3645 × 10 −7
β 22
X 2 2
−11.3147
−2.4891
3.2035 × 10 −2
β 33
X 3 2
−1.0443 × 10 −2
−4.0641
2.2713 × 10 −3
Interaction surface and contour plots for each combination of operating variables were generated using the two quadratic response models (Equations 5 and 6 above) and, with the use of a Nelder-Mead simplex optimization algorithm, optimum operating points for HFPO yield and HFPO selectivity were obtained. In particular, an optimum HFPO yield of 40% was obtained at 210° C., using a HFP/O 2 molar feed ratio of 1.158 and a space time of 120 seconds. An optimum HFPO selectivity of 56% was obtained at 205° C., using a HFP/O 2 molar feed ratio of 1.337 and a space time of 113 seconds. A combined optimum HFPO yield of 39.5% and HFPO selectivity of 55.2% (i.e. best trade-off between HFPO selectivity and HFPO yield) was obtained at 207° C., with a HFP/O 2 molar feed ratio of 1.210 and a space time of 118 seconds.
By means of the invention, a process is provided which can achieve a relatively high rate of production of HFPO, without the use of a catalyst and which avoids the use of large quantities of solvents and/or chemical oxidising agents such as hypohalites, hydrogen peroxide and organic peroxides. The process, as illustrated and described above, is relatively simple and is conducted at a relatively low pressure 4.5 bar as compared with some conventional processes, thus reducing the possibility of detonation.
|
A process for the production of HFPO includes introducing a feedstock comprising HFP and molecular oxygen into a heated reaction zone of a reactor. The reaction zone is at a reaction temperature T r , where 180° C.≦T r ≦230° C. The feedstock is allowed to react, by epoxidation of the HFP, to produce HFPO. The HFPO is withdrawn from the reaction zone. The introduction of the feedstock into the reaction zone and the withdrawal of the product from the reaction zone is continuous.
| 2
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a boundary scan circuit and to a testing method performed thereby, more particularly to a built-in self-testing method for an IEEE Std. 1149.1 boundary scan circuit and to an IEEE Std. 1149.1 boundary scan circuit with a built-in self-testing capability.
2. Description of the Related Art
Built-in self-test (BIST), which is defined as the testing of an integrated circuit through built-in hardware features, is a testing method which can overcome testing problems usually encountered when conducting tests for complex VLSI circuits. Chip level BIST architecture involves: a test pattern generator, such as a linear feedback shift register (LFSR), connected to input nodes of an application logic; an output response analyzer, such as a multiple input signature register (MISR), connected to output nodes of the application logic; and a test controller for controlling operation of the test pattern generator and the output response analyzer.
LFSRs are well studied and widely used in VLSI circuitry because they are simple and fairly regular in structure, which are important for VLSI implementation. They are also used extensively in design for testability (DFT) techniques because their shift property integrates easily with serial scan. Their good performance in pseudo-exhaustive and pseudo-random pattern generation, and their ability to compress the circuit output response also make them popular in BIST environments. FIGS. 1 and 2 respectively show the circuit designs of an LFSR and an MISR having the characteristic polynomial p(x)=1+c 1 x+c 2 x 2 +. . . +c n x n .
Since BIST permits execution of the testing operation at the speed of the system clock, testing can be performed at a much shorter time than other known testing techniques. In addition, BIST does not require the use of an Automatic Test Equipment (ATE). However, the silicon area must be increased to accommodate the test pattern generator, the output response analyzer and the test controller. This results in a lower chip yield and in higher manufacturing costs.
Recent advancements in the field of electronics manufacturing, such as surface mount technology (SMT) and multi-chip module (MCM), have caused numerous testing problems at the board level. The IEEE has issued a boundary scan standard (IEEE Std. 1149.1) to help alleviate the problem of testing connections at this level.
IEEE Std. 1149.1 provides a framework for reducing the test costs at board level by reusing pre-existing test patterns to a component on a board regardless of how pins of the component are interconnected. FIG. 3 illustrates a boundary scannable board design. A boundary-scan cell is provided adjacent to each component pin so that signals at component boundaries can be controlled and observed to determine whether a short circuit or open circuit condition has occurred on the board, and to detect the presence of a fault in an integrated circuit on a circuit board. Also, in-circuit testing is achieved by mere use of a special instruction to shift the pre-existing test patterns to the chip boundary, thereby simplifying testing at the board level. Moreover, the input and output boundary-scan cells, which cooperate to form input and output boundary-scan registers, can facilitate design debugging and fault diagnosis since the boundary-scan registers can be used to sample data flowing through the component without interfering with normal operation of the latter.
Referring to FIG. 4, a conventional boundary-scan cell of an IEEE Std. 1149.1 boundary scan circuit is shown to comprise a two-channel first multiplexer 11, a D-type first flip-flop 12, a D-type second flip-flop 13, and a two-channel second multiplexer 14. The first multiplexer 11 has a first data input which serves as a signal input, a second data input which serves as a scan input, a channel select input which receives a first control signal ShiftDR, and an output. The first flip-flop 12 has a data input connected to the output of the first multiplexer 11, a clock input for receiving a first clock signal ClockDR, and an output which serves as a scan output. The second flip-flop 13 has a data input connected to the output of the first flip-flop 12, a clock input for receiving a second clock signal UpdateDR, and an output. The second multiplexer 14 has a first data input which serves as a signal input, a second data input which is connected to the output of the second flip-flop 13, a channel select input which receives a second control signal Mode, and an output which serves as a signal output.
Referring to FIG. 5, the boundary scan test circuitry includes a test access port (TAP) system. Testing is performed by shifting test instructions and test data into the boundary-scan component via the TAP system. The TAP system is a 16-state system and has several input ports and one output port. These ports include: Test Data In (TDI) which provides serial inputs for test instructions shifted into the instruction register and for data shifted through the boundary-scan register or other test data registers; Test Data Out (TDO) which is the serial output for test instructions and data from the test data registers; Test Clock (TCK) which provides the clock for the test logic and which is a dedicated input that allows the serial test data path to be used independent of component-specific system clocks and that permits shifting of test data concurrently with normal component operation; Test Mode Select (TMS) which cooperates with TCK to cause operation of the TAP system from one state to another; and Test Reset (TRST*) which is an active-low input signal that provides asynchronous initialization of the TAP system.
Boundary scan test functions are accomplished via various test instructions which are defined by IEEE Std. 1149.1. Three of these test instructions, EXTEST, SAMPLE/PRELOAD and BYPASS, are mandatory for every boundary-scan device.
The EXTEST instruction is concerned primarily with testing of circuitry external to the device using the boundary-scan register of the device. A test vector is pre-loaded into the boundary-scan register, and the EXTEST instruction is used to drive the test vector to the external circuitry. When the EXTEST instruction is used to test the interconnection line, a test pattern is pre-loaded into the output boundary-scan register of one device and is then propagated to the next device. The response is latched on the input cells and is shifted to the TDO for examination. The EXTEST instruction also permits cluster testing, wherein components that do not incorporate boundary scan technology are tested. In cluster testing, data is shifted to the cluster/device input cells. Outputs from the cluster are captured by the input cells of a second boundary-scan device. The captured data is then shifted out of the second boundary-scan device for examination.
The BYPASS instruction allows the TDO buffer to generate the same bit stream as TDI. This is done by placing a single shift-register, called the bypass register, between TDI and TDO. When one does not wish to test a particular component, but the test data sequence must shift through that component to test another device, the BYPASS instruction is issued to that particular component to bypass the test data sequence.
The SAMPLE/PRELOAD instruction permits the execution of two functions: it allows sampling of normal operation data at the periphery of a component, and placing of an initial data pattern at latched parallel outputs of the boundary-scan cells. This instruction is used to load data onto the latched outputs prior to selection of another test instruction, such as the EXTEST instruction.
As with BIST, boundary scan technology requires an increase in the silicon area to accommodate the TAP system and the input and output boundary-scan registers.
The general acceptance of boundary scan by the designer and the Automatic Test Equipment (ATE) community makes boundary scan an effective test strategy. The incorporation of BIST with the boundary scan registers and the TAP controller provides a flexible framework at all levels of testing--chip level, board level and system level.
Although the use of BIST in a boundary scan environment has been proposed beforehand, the traditional approach is to provide separate hardware for performing BIST and boundary scan test. This increases the hardware overhead incurred.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a built-in self-testing method for an IEEE Std. 1149.1 boundary scan circuit which involves sharing of flip-flops and controllers between BIST and boundary scan testing so that no substantial increase in the hardware overhead is incurred.
A second object of the present invention is to provide an IEEE Std. 1149.1 boundary scan circuit with a built-in self-testing capability which incorporates boundary-scan cells that are operable so as to perform both BIST and boundary scan test.
A third object of the present invention is to provide a test pattern generator, such as a linear feedback shift register, which utilizes input boundary-output boundary-scan cells when executing built-in self-testing;
reconfiguring the input boundary-scan register to operate as a test pattern generator that provides test patterns to the logic circuit for a predetermined number of clock cycles upon receipt of the built-in self-test control signal;
reconfiguring the output boundary-scan register to operate as an output response analyzer that is driven by the logic circuit for the predetermined number of clock cycles upon receipt of the built-in self-test control signal; and
scanning contents of the output boundary-scan register and comparing the contents of the output boundary-scan register with a predetermined signature to detect presence of a fault after the predetermined number of clock cycles.
According to another aspect of the present invention, an IEEE Std. 1149.1 boundary scan circuit capable of performing built-in self-testing includes a logic circuit, cascaded input boundary-scan cells that form an input boundary-scan register connected to input nodes of the logic circuit, cascaded output boundary-scan cells that form an output boundary-scan register connected to output nodes of the logic circuit, and a test access port system for controlling operation of the input and output boundary-scan cells. The test scan cells of an IEEE Std. 1149.1 boundary scan circuit to provide test patterns to a logic circuit when executing BIST.
A fourth object of the present invention is to provide an output response analyzer, such as a multiple-input shift register, which utilizes output boundary-scan cells of an IEEE Std. 1149.1 boundary scan circuit that are driven by a logic circuit when executing BIST.
A fifth object of the present invention is to provide a family of input and output boundary-scan cells for an IEEE Std. 1149.1 boundary scan circuit that can be reconfigured to operate as a test pattern generator or as an output response analyzer when executing BIST.
According to one aspect of the present invention, a built-in self-testing method for an IEEE Std. 1149.1 boundary scan circuit which includes a logic circuit, cascaded input boundary-scan cells that form an input boundary-scan register connected to input nodes of the logic circuit, cascaded output boundary-scan cells that form an output boundary-scan register connected to output nodes of the logic circuit, and a test access port system for controlling operation of the input and output boundary-scan cells, comprises the steps of:
controlling the test access port system to provide a built-in self-test control signal to the input and access port system includes controllable means for providing a built-in self-test control signal to the input and output boundary-scan cells when executing built-in self-testing, in addition to the original test access port defined by IEEE Std. 1149.1--1990. The input boundary-scan register is reconfigurable to operate as a test pattern generator that provides test patterns to the logic circuit for a predetermined number of clock cycles upon receipt of the built-in self-test control signal, and the output boundary-scan register is reconfigurable to operate as an output response analyzer that is driven by the logic circuit for the predetermined number of clock cycles upon receipt of the built-in self-test control signal. Contents of the output boundary-scan register are scannable for comparison with a predetermined signature to detect presence of a fault after the predetermined number of clock cycles.
The test access port system operates in a Run-Test/Idle mode when built-in self-testing is executed. The boundary scan circuit further comprises means for providing a system clock to the input and output boundary-scan cells when built-in self-testing is executed.
According to still another aspect of the present invention, a linear feedback shift register, which acts as a test pattern generator, comprises cascaded input boundary-scan cells of an IEEE Std. 1149.1 boundary scan circuit. The input boundary-scan cells form an input boundary-scan register that is adapted to be connected to input nodes of a logic circuit of the boundary scan circuit. The input boundary-scan register is reconfigurable to operate as a test pattern generator that is adapted to provide test patterns to the logic circuit for a predetermined number of clock cycles upon receipt of a built-in self-test control signal from a test access port system of the boundary scan circuit.
According to a further aspect of the present invention, a multiple-input shift register, which acts as an output response analyzer, comprises cascaded output boundary-scan cells of an IEEE Std. 1149.1 boundary scan circuit. The output boundary-scan cells form an output boundary-scan register that is adapted to be connected to output nodes of a logic circuit of the boundary scan circuit. The output boundary-scan register is reconfigurable to operate as an output response analyzer driven by the logic circuit for a predetermined number of clock cycles upon receipt of a built-in self-test control signal from a test access port system of the boundary scan circuit. Contents of the output boundary-scan register are scannable for comparison with a predetermined signature to detect presence of a fault after the predetermined number of clock cycles.
Since no separate test pattern generator, output response analyzer and BIST controller is required in the BIST boundary scan circuitry of this invention, no substantial increase in the overall hardware overhead is incurred.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become apparent in the following detailed description of the preferred embodiment with reference to the accompanying drawings, of which:
FIG. 1 is a block diagram of a conventional linear feedback shift register (LFSR);
FIG. 2 is a block diagram of a conventional multiple-input shift register (MISR);
FIG. 3 illustrates a conventional boundary scannable board design;
FIG. 4 is a schematic circuit diagram of a conventional boundary-scan cell;
FIG. 5 is a circuit block diagram of a conventional boundary-scan device;
FIG. 6 is a schematic circuit diagram of a first input boundary-scan cell according to the present invention;
FIG. 7 is a schematic circuit diagram of a second input boundary-scan cell according to the present invention;
FIG. 8 is a schematic circuit diagram of a third input boundary-scan cell according to the present invention;
FIG. 9 illustrates how the family of input boundary-scan cells shown in FIGS. 6 to 8 are combined to form an LFSR with a characteristic polynomial p(x)=x 4 +x 3 +1;
FIG. 10 is a schematic circuit diagram of a first output boundary-scan cell according to the present invention;
FIG. 11 is a schematic circuit diagram of a second output boundary-scan cell according to the present invention;
FIG. 12 is a schematic circuit diagram of a third output boundary-scan cell according to the present invention;
FIG. 13 illustrates how the family of output boundary-scan cells shown in FIGS. 10 to 12 are combined to form an MISR with a characteristic polynomial p(x)=x 4 +x 3 +1;
FIG. 14 illustrates the architecture of an instruction register and decoder for generating the various control signals for the boundary-scan cells of this invention;
FIG. 15 is a table which shows the codes assigned to the different test instructions to be loaded into the instruction register, and the logic values of the different control signals in accordance with the test instructions;
FIG. 16 is a schematic circuit diagram of an instruction decoder which complies with the table shown in FIG. 15;
FIG. 17 is a schematic circuit diagram of a logic circuit for providing a system clock to the boundary-scan cells during a Run-Test/Idle controller state of the test access port (TAP) system; and
FIG. 18 is a sample logic circuit which incorporates the BIST boundary scan circuit of this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the boundary scan circuit of the present invention, the input boundary-scan register should be reconfigurable as a pseudo-random pattern generator (PRPG), while the output boundary-scan register should be reconfigurable as a signature analyzer (SA) to incorporate the BIST capability in the boundary scan environment. To achieve this purpose, a family of boundary-scan cells which can be reconfigured as a linear feedback shift register (LFSR) or as a multiple-input shift register (MISR) is disclosed.
FIGS. 6 to 8 illustrate three input boundary-scan cells 20, 30, 40 which can be combined to form an LFSR.
Referring to FIG. 6, the input boundary-scan cell 20 comprises a four-channel first multiplexer 21, a D-type flip-flop 22, and a two-channel second multiplexer 23. The first multiplexer 21 has a first data input which serves as a signal input, a second data input which serves as a feedback input fb, third and fourth data inputs which are connected to one another and which serve as a scan input, a pair of channel select inputs which receive a first control signal BIST* and a second control signal ShiftDR respectively, and an output. The flip-flop 22 has a data input connected to the output of the first multiplexer 21, a clock input for receiving a clock signal mClockDR, and an output which serves as a scan output. The second multiplexer 23 has a first data input which is connected to the first data input of the first multiplexer 21, a second data input which is connected to the output of the flip-flop 22, a channel select input which receives a third control signal Mode, and an output which serves as a signal output.
Referring to FIG. 7, the input boundary-scan cell 30 comprises a four-channel first multiplexer 31, a D-type flip-flop 32, and a two-channel second multiplexer 33. The first multiplexer 31 has a first data input which serves as a signal input, second, third and fourth data inputs which are connected to one another and which serve as a scan input, a pair of channel select inputs which receive the first control signal BIST* and the second control signal ShiftDR respectively, and an output. The flip-flop 32 has a data input connected to the output of the first multiplexer 31, a clock input for receiving the clock signal mClockDR, and an output which serves as a scan output. The second multiplexer 33 has a first data input which is connected to the first data input of the first multiplexer 31, a second data input which is connected to the output of the flip-flop 32, a channel select input which receives the third control signal Mode, and an output which serves as a signal output.
Referring to FIG. 8, the input boundary-scan cell 40 comprises a four-channel first multiplexer 41, a D-type flip-flop 42, a two-channel second multiplexer 43 and a two-input exclusive-OR (XOR) gate 44. The XOR gate 44 has a first input which serves as a feedback input fb, a second input which serves as a scan input, and an output. The first multiplexer 41 has a first data input which serves as a signal input, a second data input which is connected to the output of the XOR gate 44, third and fourth data inputs which are connected to one another and which are further connected to the second input of the XOR gate 44, a pair of channel select inputs which receive the first control signal BIST* and the second control signal ShiftDR respectively, and an output. The flip-flop 42 has a data input connected to the output of the first multiplexer 41, a clock input for receiving a clock signal mClockDR, and an output which serves as a scan output. The second multiplexer 43 has a first data input which is connected to the first data input of the first multiplexer 41, a second data input which is connected to the output of the flip-flop 42, a channel select input which receives the third control signal Mode, and an output which serves as a signal output.
FIG. 9 illustrates how the input boundary-scan cells 20, 30, 40 are combined to form an LFSR with a characteristic polynomial p(x)=1+x 3 +x 4 . The LFSR has four cascaded stages that are arranged, from left to right, in the following manner: The first stage consists of the boundary-scan cell 20 and corresponds to a coefficient c 0 of the characteristic polynomial. The succeeding stages consist of the boundary-scan cell 30 if a coefficient c i of the characteristic polynomial is zero for 1≦i≦n-1, and consist of the boundary-scan cell 40 if the coefficient c i of the characteristic polynomial is one for 1≦i≦n-1. A previous stage corresponding to the coefficient c i-1 of the characteristic polynomial is connected to a succeeding stage corresponding to the coefficient c i of the characteristic polynomial by connecting the scan output of the previous stage to the scan input of the succeeding stage. Feedback inputs of the different stages are connected to the scan output of a final stage corresponding to the coefficient c n-1 of the characteristic polynomial.
FIGS. 10 to 12 illustrate three output boundary-scan cells 50, 60, 70 which can be combined to form an MISR.
Referring to FIG. 10, the output boundary-scan cell 50 comprises a four-channel first multiplexer 51, a D-type first flip-flop 52, a D-type second flip-flop 53, a two-channel second multiplexer 54, and a two-input XOR gate 55. The XOR gate 55 has a first input which serves as a signal input, a second input which serves as a feedback input fb, and an output. The first multiplexer 51 has a first data input which is connected to the first input of the XOR gate 55, a second data input which is connected to the output of the XOR gate 55, third and fourth data inputs which are connected to one another and which serve as scan inputs, a pair of channel select inputs which receive the first control signal BIST* and the second control signal ShiftDR respectively, and an output. The first flip-flop 52 has a data input connected to the output of the first multiplexer 51, a clock input for receiving a first clock signal mClockDR, and an output which serves as a scan output. The second flip-flop 53 has a data input connected to the output of the first flip-flop 52, a clock input for receiving a second clock signal UpdateDR, and an output. The second multiplexer 54 has a first data input which is connected to the first input of the XOR gate 55, a second data input which is connected to the output of the second flip-flop 53, a channel select input which receives the third control signal Mode, and an output which serves as a signal output.
Referring to FIG. 11, the output boundary-scan cell 60 comprises a four-channel first multiplexer 61, a D-type first flip-flop 62, a D-type second flip-flop 63, a two-channel second multiplexer 64, and a two-input XOR gate 65. The XOR gate 65 has a first input which serves as a signal input, a second input which serves as a scan input, and an output. The first multiplexer 61 has a first data input which is connected to the first input of the XOR gate 65, a second data input which is connected to the output of the XOR gate 65, third and fourth data inputs which are connected to one another and which are further connected to the second input of the XOR gate 65, a pair of channel select inputs which receive the first control signal BIST* and the second control signal ShiftDR respectively, and an output. The first flip-flop 62 has a data input connected to the output of the first multiplexer 61, a clock input for receiving the first clock signal mClockDR, and an output which serves as a scan output. The second flip-flop 63 has a data input connected to the output of the first flip-flop 62, a clock input for receiving the second clock signal UpdateDR, and an output. The second multiplexer 64 has a first data input which is connected to the first input of the XOR gate 65, a second data input which is connected to the output of the second flip-flop 63, a channel select input which receives the third control signal Mode, and an output which serves as a signal output.
Referring to FIG. 12, the output boundary-scan cell 70 comprises a four-channel first multiplexer 71, a D-type first flip-flop 72, a D-type second flip-flop 73, a two-channel second multiplexer 74, and first and second two-input XOR gates 75, 76. The first XOR gate 75 has a first input which serves as a signal input, a second input which serves as a scan input, and an output. The second XOR gate 76 has a first input which is connected to the output of the first XOR gate 75, a second input which serves as a feedback input fb, and an output. The first multiplexer 71 has a first data input which is connected to the first input of the first XOR gate 75, a second data input which is connected to the output of the second XOR gate 76, third and fourth data inputs which are connected to one another and which are further connected to the second input of the first XOR gate 75, a pair of channel select inputs which receive the first control signal BIST* and the second control signal ShiftDR respectively, and an output. The first flip-flop 72 has a data input connected to the output of the first multiplexer 71, a clock input for receiving the first clock signal mClockDR, and an output which serves as a scan output. The second flip-flop 73 has a data input connected to the output of the first flip-flop 72, a clock input for receiving the second clock signal UpdateDR, and an output. The second multiplexer 74 has a first data input which is connected to the first input of the first XOR gate 75, a second data input which is connected to the output of the second flip-flop 73, a channel select input which receives the third control signal Mode, and an output which serves as a signal output.
FIG. 13 illustrates how the output boundary-scan cells 50, 60, 70 are combined to form an MISR with a characteristic polynomial p(x)=1+x 3 +x 4 . The MISR has four cascaded stages that are arranged, from right to left, in the following manner: The first stage consists of the boundary-scan cell 50 and corresponds to a coefficient c 0 of the characteristic polynomial. The succeeding stages consist of the boundary-scan cell 60 if a coefficient c i of the characteristic polynomial is zero for 1≦i≦n-1, and consist of the boundary-scan cell 70 if the coefficient c i of the characteristic polynomial is one for 1≦i≦n-1. A previous stage corresponding to the coefficient c i-1 of the characteristic polynomial is connected to a succeeding stage corresponding to the coefficient c i of the characteristic polynomial by connecting the scan output of the previous stage to the scan input of the succeeding stage. Feedback inputs of the different stages are connected to the scan output of a final stage corresponding to the coefficient c n-1 of the characteristic polynomial.
As shown in FIG. 4, the conventional boundary-scan cell has the following I/O ports: Signal input, Signal output, Scan input, Scan output, Mode, ShiftDR, ClockDR and UpdateDR. Aside from possessing the ports of the conventional boundary-scan cell, the input and output boundary-scan cells 20, 30, 40, 50, 60, 70 of this invention further include additional I/O ports and XOR gates to reconfigure the same for use in an LFSR or MISR. The additional I/O ports receive the control signal BIST*, which is a low-active signal that should be logic 0 when BIST is to be performed and that should be logic 1 when otherwise, and the feedback input fb, which is the global feedback of LFSR or MISR. The XOR gates help the boundary-scan cells 20, 30, 40, 50, 60, 70 to behave as an LFSR or as an MISR.
In order to incorporate the BIST capability in the IEEE Std. 1149.1 boundary scan environment, an additional RUNBIST test instruction is added to initiate BIST. In this embodiment, a two-bit instruction register is used to implement four test instructions: EXTEST, BYPASS, SAMPLE/PRELOAD and RUNBIST. The architecture of the instruction register and decoder is shown in FIG. 14. The control signal BIST* is a low-active signal that comes from the instruction decoder. The control signal BIST* should be logic 0 when the RUNBIST instruction is loaded into the instruction register and should be logic 1 when other instructions are loaded into the instruction register. The control signals Mode, BIST* control the behavior of the boundary-scan cells 20, 30, 40, 50, 60, 70. The control signal DR -- select is used to select which data register output is to be provided to the TDO. Preferably, the control signal DR -- select is generated to select the bypass register when the BYPASS test instruction is loaded into the instruction register.
FIG. 15 is a table which shows the codes assigned to the different test instructions, and the logic values of the different control signals in accordance with the test instructions.
To implement the instruction decoder shown in FIG. 14, the table shown in FIG. 15 is converted into truth tables for the control signals Mode, BIST*, DR -- select. The instruction decoder is then implemented according to the resulting truth tables. The schematic circuit diagram of an instruction decoder for the present invention is shown in FIG. 16.
According to IEEE Std. 1149.1, BIST should be performed when the test access port (TAP) system of the boundary scan circuit is in the Run-Test/Idle state. In order to generate test patterns and compact circuit output responses in the Run-Test/Idle state, the original clock signal ClockDR used by the conventional boundary-scan cells and provided by the TAP system should be modified so that it can clock the test pattern generator and the output response analyzer in the Run-Test/Idle state.
FIG. 17 is a schematic circuit diagram of a logic circuit for modifying the original clock signal ClockDR so as to generate the modified clock signal mClockDR. The 4-bit binary word ABCD represents the encoded state of the TAP system. After the RUNBIST test instruction is loaded into the instruction register and the TAP system is in the Run-Test/Idle state (ABCD=0011), the clock signal mClockDR will behave as the system clock. Thus, the logic circuit of FIG. 17 serves primarily to provide the system clock to the input and output boundary-scan cells 20, 30, 40, 50, 60, 70 when BIST is performed.
FIG. 18 illustrates a sample logic circuit which incorporates the BIST boundary scan circuit of this invention. As shown, a 12-pin (excluding the Vdd and GND pins) integrated circuit chip has four buffer circuits B that serve as its logic circuit, and a boundary scan standard circuit which includes a TAP system with an instruction register IR, a bypass register BYPASS, an input boundary-scan register IBS having four input boundary-scan cells, and an output boundary-scan register OBS having four output boundary-scan cells. In this example, the conventional TAP system is modified in accordance with FIGS. 14, 16 and 17 so as to enable a TAP controller of the same to generate the control signal BIST* and the clock signal mClockDR, the input boundary-scan register IBS is configurable to correspond with the LFSR shown in FIG. 9, while the output boundary-scan register is configurable to correspond with the MISR shown in FIG. 13. Thus, aside from its ability to perform BIST, the boundary scan circuit of this invention still complies with IEEE Std. 1149.1.
When the RUNBIST instruction is loaded into the instruction register IR and is decoded, the control signal BIST* is at logic 0, and the control signal ShiftDR is similarly at logic 0. For the input boundary-scan register IBS, the multiplexers 21, 41 of the boundary-scan cells 20, 40 select the feedback input fb, while the multiplexer 31 of the boundary-scan cell 30 selects the scan input. The input boundary-scan register IBS acts as a test pattern generator for providing test patterns to the buffer circuits B at this time. On the other hand, for the output boundary-scan register OBS, the multiplexers 51, 61, 71 of the boundary-scan cells 50, 60, 70 select the output of the XOR gates 55, 75, 76 respectively. The output boundary-scan register OBS acts as an output response analyzer driven by the buffer circuits B at this time.
BIST of the sample logic circuit is performed as follows:
1. With the use of the SAMPLE/PRELOAD instruction, a seed value of the LFSR, such as 1111, and a seed value of the MISR, such as 0000, is loaded.
2. When the RUNBIST instruction is loaded and decoded, the control signal BIST* is generated, thereby configuring the input boundary-scan register IBS to operate as an LFSR and the output boundary-scan register IBS to operate as an MISR.
3. The TAP system is operated in the Run-Test/Idle state for a specified number of TCK cycles, such as 15 clock cycles, to complete BIST.
4. The result at the end of BIST is scanned out from the output boundary-scan register OBS (BIST,=0, ShiftDR=1) and is compared with a predetermined signature, such as 1001, to detect the presence of a fault.
It has thus been shown that no separate test pattern generator, output response analyzer and BIST controller is required in the BIST boundary scan circuitry of this invention. Thus, no substantial increase in the overall hardware overhead is incurred.
While the present invention has been described in connection with what is considered the most practical and preferred embodiment, it is understood that this invention is not limited to the disclosed embodiment, but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation so as to encompass all such modifications and equivalent arrangements.
|
An IEEE Std. 1149.1 boundary scan circuit which is capable of performing built-in self-testing includes a logic circuit, cascaded input boundary-scan cells that form an input boundary-scan register connected to input nodes of the logic circuit, cascaded output boundary-scan cells that form an output boundary-scan register connected to output nodes of the logic circuit, and a test access port system for controlling operation of the input and output boundary-scan cells. The test access port system provides a built-in self-test control signal to the input and output boundary-scan cells when executing built-in self-testing. The input boundary-scan register is reconfigurable to operate as a test pattern generator that provides test patterns to the logic circuit for a predetermined number of clock cycles upon receipt of the built-in self-test control signal. The output boundary-scan register is reconfigurable to operate as an output response analyzer that is driven by the logic circuit for the predetermined number of clock cycles upon receipt of the built-in self-test control signal. A family of input and output boundary-scan cells that can be reconfigured as a linear feedback shift register and as a multiple-input shift register is also disclosed.
| 6
|
CROSS-REFERENCE TO RELATED APPLICATIONS
Claiming Benefit of 35 U.S.C. §19(e)
This patent application is related to U.S. provisional patent application, serial No. 60/306,751, filed on Jul. 20, 2001 by Derek J. Layfield.
TECHNICAL FIELD OF THE INVENTION
The present invention relates generally to a connector and connection system, particularly to a connector and connection system useful in the building and construction industries. More particularly, the present invention relates to a connecting device and a method of using the connecting device for joining two substantially planar substrates together in which at least a part of the connecting device also acts as a guiding means allowing the two substrates to be joined together in substantial alignment with one another.
FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT STATEMENT
This invention was not developed in conjunction with any Federally sponsored contract.
MICROFICHE APPENDIX
Not applicable.
INCORPORATION BY REFERENCE
The related U.S. provisional patent application, serial No. 60/306,751 filed on Jul. 20, 2001, is hereby incorporated by reference in its entirety including figures.
BACKGROUND OF THE INVENTION
Modular building panels have been used to lessen the cost of constructing buildings such as houses, office partitions, walls and the like by minimizing the number of components required. Modular panels can be made in the factory and assembled on site, thus panels can be made more uniform in the factory which lessens the labor required for building the walls of a building or similar. However, when two or more building panels need to be joined together to form a wall the panels need to be more or less accurately aligned with each other in order to produce a smooth wall having a pleasing appearance.
In the past, compressed straw panels have required the use of external metal connectors to join two adjacent panels together. The metal connectors can take a variety of different forms. One particular form is a double saddle or double yoke arrangement interconnected through a web portion in opposed facing relationship. Each yoke or saddle straddles the end of one of the panels so that when the two panels are adjacent each other one yoke or saddle engages one panel and the other yoke or saddle engages the other panel to join the panels together when the connector is fastened to both of the panels. The use of previously available connectors, including the metal connector, have suffered from one or more problems or shortcomings. One of the major disadvantages of using metal connectors is alignment of two adjacent panels when joining them together. As the metal connectors need to be reasonably flexible to accommodate adjustment of the panels the clips are made from relatively light weight metal with the effect that the clips can be easily bent nut of shape when joining two panels together which causes misalignment of the panels when forming the wall or partition. Additionally, the metal clips require fastening to the outside surfaces of the panels by suitable fasteners such as nails, screws and the like, which results in part of the clips being exposed on the external surfaces of the wall panels. The exposure of the metal clips is unsightly and detracts from the appearance of the walls as well as having the potential to inflict damage and injury. Extra operations to finish the wall are tea tilted in order to mask or cover the clips such as, for example, by plastering over the clips. This extra finishing operation is time consuming and expensive in materials and labor costs. Additionally, because of the light weight nature of the clips the wall panels can flex or move slightly with respect to each other which in turn has a tendency to crack the plaster covering the clip which ultimately exposes the clip and leads to increased misalignment of the panels. Another problem of using existing clips is that they do not provide any means for aligning the two panels with respect to each other when joining the panels together. As the clips can move or distort when the panels are being positioned in abutting relationship, it is difficult to accurately align the panels and maintain the panels in this aligned position while fixing the panels into place. Even if the panels were originally aligned, the use of the clips does not necessarily maintain the panels in alignment.
One example of the modular building panels used to make walls, partitions or the like is straw-based panels made of compressed straw sandwiched between layers of paper or paperboard. Wheat, rice or other types of straw are typically used therein. An example where modular compressed straw panels are used is in the construction of exterior walls wherein said modular panels are used as both structural and insulting members, thus eliminating the need for spaced studs, interior sheet rock and insulation placed there between. In interior partition applications, for example, modular building panels might be used in lieu of hollow panels comprised of a framework supporting planar surface members on each side thus providing improved structural and acoustic properties. The use of previously available connectors, including the metal connector discussed supra, has consistently suffered from one or more problems or shortcomings. One of the major disadvantages of using metal connectors is alignment of two adjacent panels when joining them together. The metal connectors need to be reasonably flexible to accommodate adjustment of the panels, so the clips are made from relatively light weight metal with the effect that the clips can be easily bent out of shape when joining two panels together which causes misalignment of the panels when forming the wall or partition. Additionally, the metal clips require fastening to the outside surfaces of the panels by suitable fasteners such as nails, screws and the like, which results in part of the clips being exposed on the external surfaces of the wall panels. The exposure of the metal clips is unsightly and detracts from the appearance of the walls as well as having the potential to inflict damage and injury. Extra operations to finish the wall are then required in order to mask or cover the clips such as, for example, plastering over the clips followed by taping and bedding the joints. This extra finishing operation is time consuming and expensive in materials and labor costs. Additionally, because of the light weight nature of the clips the wall panels can flex or move slightly with respect to each other which in turn has a tendency to crack the plaster covering the clip which ultimately exposes the clip and leads to increased misalignment of the panels.
Another, and perhaps more significant problem of using existing connecting means, is that they do not provide any means for aligning the two panels with respect to each other when joining the panels together. As existing connecting means can move or distort when the panels are being positioned in abutting relationship, it is difficult to accurately align the panels and maintain the panels in this aligned position while fixing the panels into place. Even if the panels are initially aligned, the use of the existing connecting apparatuses does not necessarily maintain the panels in alignment over the long term.
Therefore, there is a need for a connecting system for modular panels that overcomes the shortcomings of currently available connecting means by not only connecting modular panels together, but also aligning said panels prior to and during connection. Further, there is a need for a connecting system for modular panels that is not exposed to the exterior wall surface, thus not requiring additional finishing.
SUMMARY OF THE INVENTION
The present invention relates generally to a connector and connection system, particularly to a connector and connection system useful in the building and construction industries. More particularly, the present invention relates to a connecting device and a method of using the connecting device for joining two substantially planar substrates together in which at least a part of the connecting device also acts as a guiding means allowing the two substrates to be joined together in substantial alignment with one another. Further, the present invention relates to a connection system for joining a plurality of building panels together, particularly panels composed of compressed straw, to form a straight wall, partition or similar structure in substantially the same plane. Said structure being constructed without having any external fittings or without having to mask or otherwise hide any fasteners, fittings or the like across the joint between the panels.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described by way of example with reference to the accompanying drawings in which:
FIG. 1 is a perspective view of two panels being joined by the connection system of the present invention in which one panel is shown provided with four connectors and the other panel with four recesses in a position where the two panels are not in alignment with each other.
FIG. 2 is a close-up perspective view of one form of the connection system of the present invention showing one form of the connector in the receiving means and one form of fastening means lined up accordingly.
FIG. 3 is a partial cross-section view of the connection system of the present invention showing the two panels separated from each other in which each panel is provided with a recess and one panel is provided with a connector.
FIG. 4 is a partial cross-section view of one form of the connection system of the present invention showing the two panels in abutting relationship with the connector received in two opposed recesses.
FIG. 5 is a partial cross-section view showing the connector fixed in place between two panels when in abutting relationship with each other.
FIG. 6 is a partial cross-section view showing three embodiments of connectors each disposed within a like shaped receiving means (recess.
DETAILED DESCRIPTION OF THE INVENTION
The invention discussed herein describes a system that provides for the easy alignment and connection of modular panels. Said invention is comprised of at least two panels, a connector and at least one receiving means in each panel. Said connector may take the form of a disc or any substantially flat and substantially bilaterally symmetric shape. Said receiving means may commonly take the form of a recess in said panel. Said recess generally having the form of a slot and having a shape that substantially matches one half of said symmetric connector.
Although the present invention will be described with particular reference to one form of the connector and connecting system in the form of a substantially circular disc, it is to be noted that the scope of the present invention is not limited to the described embodiment but rather the scope of the invention is more extensive so as to include other forms and arrangements of the connector and the connecting system and to the use of the various forms of the connectors in joining substrates together in more or less accurate alignment with each other.
Typically, the connector is a substantially flat or planar member that can adopt any suitable or convenient shape. Connector shapes include, but are not limited to, circular discs, elliptical discs, discs of any polygonal shape including square plates, rectangular plates, or any other shape. Said connector having a first and second part. The first part of said connector is that part which is received in the receiving means of a first substrate that is in position and securely located in place during construction of a wall. The second part of said connector is the part of the connector opposite the first part and is the part received in the receiving means of a second substrate as the second substrate is in abutting relationship with the first substrate. The second part of the connector is the guide means which extends outwardly from a one edge of the fixed substrate, typically a vertical side edge.
Typically, the first and second parts of the connector are the two halves of one disc with the first half and second half being essentially identical to each other and being different parts of the same disc, essentially mirror images of one another. As discussed supra, however, this connector may take a variety of generally flat shapes.
The external surface or surfaces of the connector may either be smooth or rough. When an adhesive is used to secure said connector to said first and second substrate, a roughened external surface may be required to enable a better bond with the adhesive. Further, the surface may be imparted a variety of textures with the texture pattern taking any suitable form or arrangement and having any suitable depth. One preferred surface treatment is the roughened side of masonite or similar hardboard, compressed board, manufactured board or the like.
Typically, said substrate is a building panel. In this disclosure, the building panel is a modular panel comprised of a compressed straw core lined on all sides by paper or paperboard. The compressed straw is arranged in layers with the straw fibers in substantially parallel orientation extending transversely across the panel from side to side when the panel is in a normal in-use orientation.
For better illustration, subject panels are typically rectangular in shape. In a typical application, said panels will be oriented such that the longer edges are substantially vertical and the shorter edges are substantially horizontal. In this orientation, said straw fibers will be assume a generally horizontal orientation.
In a typical configuration, said compressed straw panels have vertical edges (side faces) that are in opposed face to face relationship with each other when two adjacent panels are in abutting relationship with each other. Typically, the side faces are substantially squared, thus enabling a flat face to face contact between abutted panels. The front and rear faces of said panels may be tapered near the vertical side edges. Said taper provides a slight depression when panels are properly installed and are abutted edge to edge. Typically, the depression is covered with a suitable strip or similar, such as tape in order to provide a smooth finish to the joint or to completely mask the joint.
Compressed straw panels tend to exhibit greater integrity along their vertical edges or sides rather than along their horizontal edges when in the normal in-use orientation, described supra. Therefore, receiving means for accepting subject connectors are located in the vertical edges of the panel. Typically, the receiving means is a trench, groove, slot, cut out or similar recess for receiving part of said connector, and extends through a plurality of fiber/straw layers. The receiving means are provided in one or both side edges of the panels and each edge may be provided with a plurality of receiving means. Said receiving means will be shaped to substantially match the outer shape of one half of said connector. As disclosed in the drawings herein, when in place, outer surface of said connector will the contact the inner surface of said receiving means at all places except the top and bottom edges of said receiving means near the panel edge. A gap between said connector and said receiving means at the top and bottom edges provides for panels to be more easily guided into alignment during installation.
The shape of the receiving means or recess typically corresponds to the shape of the connector and the size of the recess is sufficient to accommodate receiving said connector. In a typical example, the recess is circular, part circular, curved, elliptical or similar. Correspondingly, the connector is like shaped, ie., circular, curved, elliptical or similar. The radius of curvature of the recess is slightly greater than the curvature of the connector and is of a slightly larger size to permit adjustable movement of the second panel with respect to the fixed panel during alignment and connection. The recess will typically be sized to allow only vertical adjustment between abutted panels, and not horizontal movement. The depth of the recess will be sized to accept approximately half of the connector therein.
The length of the opening of the recess is typically longer than the length of the connector so that there is clearance between the edges of the recess and the connector to allow the second panel to be brought into contact with the fixed panel at an angle or while being slightly inclined to the fixed panel.
Accordingly, the width of the recess will about the same dimension as the thickness of the connector providing a snug fit and preventing the panels from moving with respect to each other in any direction substantially perpendicular to the panel faces.
Each building panel is provided with one or more recesses. Importantly, the recesses of different panels are in alignment with each other when the panels are in their normal in-use positions. Typically, each panel is provided with spaced apart recesses along one side edge and with combinations of recesses and connectors along the opposite side edge. This configuration acts to further enhance the ease with which said panels are installed as pluralities of panels are easily aligned and connected in a systematic manner. For example, a group of panels will each be provided with four receiving means on each left and right edge. Accordingly, receiving means on left edges will be each provided with a connector fixably attached therein.
The connector is typically fixed into the recess by a suitable chemical or mechanical fastening means. Typical chemical fastening means include adhesives, glues, bonding agents or the like. Typical mechanical fastening means include nails, screws, dowels, pins or similar. Typically, the recess is provided with an internal fixing arrangement in which the connector and recess are each provided with complementary parts of the internal fixing arrangement.
Referring now to FIGS. 1 and 2, wherein one form of the connection system of the present invention is detailed. Fixed panel ( 2 ) is provided in place forming part of the wall to be formed using the compressed straw panels. Panel ( 2 ) is made from compressed straw in which the individual fibres of straw are oriented to lie substantially horizontally in parallel relationship with the upper and lower ends ( 4 , 6 ) of panel 2 . Four separate semicircular recesses ( 8 ) are formed at regular spaced apart intervals over the length of side edge ( 10 ) of panel ( 2 ). Recess ( 8 ) is substantially semi-circular as shown more particularly in FIGS. 2, 3 and 4 .
A connector disc ( 12 ) is located within each recess ( 8 ). Connector ( 12 ) can take any suitable shape or form. One particularly preferred shape is a circular disc. Disc ( 12 ) may be made from any suitable material and be made in any suitable size and in any suitable shape. Importantly, to insure a quasi-rigid fit, the shape of the connector will be substantially the same as the shape of the recess. One particularly preferred material of disc ( 12 ) is hardboard such as, for example, masonite or similar compressed board. The width of recess ( 8 ) corresponds to the thickness of disc ( 12 ) so that disc ( 12 ) is snugly received in recess ( 8 ) without any appreciable sideways movement, play or clearance. This assists in alignment of the two panels.
In a preferred embodiment, the radius of curvature of recess ( 8 ) is slightly larger than the radius of connector ( 12 ) to permit substantially vertical adjustment of the panels with respect to each other when joining the panels together. However, it is to be noted that connector ( 12 ) is centrally located within recess ( 8 ) so that there is a gap ( 14 ) between the circumference of the connector ( 12 ) and the edge of recess ( 8 ) along edge ( 10 ) of panel ( 2 ).
Disc ( 12 ) is securely fastened within recess ( 8 ) by a chemical or mechanical fastening means such as adhesive, glue or similar, or a nail, or screw ( 16 ) or similar. If a mechanical fastener is used the head of the fastener is recessed within the side face of panel ( 2 ) to provide for a smooth finished surface.
Either one or both outer surfaces of disc ( 12 ) are roughened or have a similar surface treatment so as to enhance the fixing of the disc within the recess, particularly if adhesive, glue or similar chemical bonding is used by partially filling recess ( 8 ) or coating the surfaces of disc ( 12 ).
Although four spaced apart recesses ( 8 ) are shown in FIG. 1, panel ( 2 ) can have any number of recesses and connectors located therein.
Continuing to refer to FIGS. 1 and 2, a second panel ( 20 ) is provided with four spaced apart semi-circular recesses ( 8 ) along the side edge ( 10 ). The spacing of recesses ( 8 ) of panel ( 2 ) is the same as the spacing of recesses ( 8 ) of panel ( 20 ) that when panel ( 20 ) is brought into abutting relationship with panel ( 2 ) the exposed parts of discs ( 12 ) can be received in recesses ( 8 ) of panel ( 20 ). It is to be noted that in FIG. 1, second panel ( 20 ) is shown oriented at about 90 degrees to the final aligned abutting position of the finished wall merely to more clearly show the arrangement of recesses ( 8 ), and not to show the abutting relationship which is shown in FIG. 2 .
Operationally, panel ( 2 ) is manufactured and shipped from the factory in a configuration such that side edge ( 10 ) is provided with recesses ( 8 ) and discs ( 12 ) rigidly fixed therein and extending therefrom. The other edge of panel ( 2 ) is provided with recesses ( 8 ) only. All finished panels, for example, will be provided with a plurality of matching, like spaced, recesses along both side edges, while the recesses along the left side edge will be provided with connectors rigidly attached therein.
During installation, panel ( 2 ) is securely fixed in position as the first panel of an internal wall, partition or similar. After panel ( 2 ) is firmly fixed in position, a second panel ( 20 ) is taken and oriented so that side edge ( 10 ) of panel ( 20 ) having recesses ( 8 ) is facing toward side edge ( 10 ) of panel ( 2 ). Panel ( 20 ) is placed near panel ( 2 ) so that one of the connectors ( 12 ), preferably the lower most connector, is placed adjacent the lower most recess ( 8 ) of panel ( 20 ). In this orientation panel ( 20 ) is not vertical but rather is inclined to the vertical with the space between the respective tops of panels ( 2 ) and ( 20 ) greater than the distance between the respective bottoms of panels ( 2 ) and ( 20 ). Panel ( 20 ) in this inclined position is brought into alignment by discs ( 12 ) being received in each of the recesses ( 8 ) of panel ( 20 ) in turn. This manoeuvre is possible because of clearance gap ( 14 ) provided at either side of disc ( 12 ) by recess ( 8 ) in edges ( 10 ). Panel ( 20 ) can then be easily moved from being inclined to panel ( 2 ) to being directly vertically aligned along the edge ( 10 ) of panel ( 2 ). Panel ( 20 ) is then moved closer to panel ( 2 ) into aligned abutting relationship with all four discs ( 12 ) received in both sets of recesses ( 8 ) of the panels. The exposed part of connectors ( 12 ) when received in recesses ( 8 ) of panel ( 20 ) guide the position of panel ( 20 ) into alignment with panel ( 2 ) since there is no sideways clearance or play between the exposed part of connector ( 12 ) and recess ( 8 ) of panel ( 20 ).
Prior to inserting disc ( 12 ) into recess ( 8 ) the exposed surfaces of disc ( 12 ) can be coated with a suitable adhesive so that when panel ( 20 ) is in alignment with panel ( 2 ) disc ( 12 ) is adhered internally to the walls of recess ( 8 ) and fixed thereto. Alternatively, when disc ( 12 ) is received in recess ( 8 ) of panel ( 20 ) an external fastener in the form of a screw ( 22 ) can be used to retain the connector in the recess. Many alternative forms of external fasteners may be used in lieu of screw ( 22 ) such as a nail or a dowel pin in a suitably sized hole drilled through panel ( 2 ) and disc ( 12 ).
FIGS. 3 and 4 further show the preferred relationship between connector ( 2 ) and recess ( 8 ) and further illustrates gap ( 14 ) that provides for the adjustment of panels ( 20 ) and ( 2 ) from a non-vertically parallel orientation to an abutted relationship with one another. FIG. 3 showing panels ( 2 ) and ( 20 ) spaced apart and FIG. 4 showing panels ( 2 ) and ( 20 ) in a final abutted configuration. FIGS. 4 and 5 show external fasteners ( 22 ) and ( 16 ) placed through panels ( 20 ) and ( 2 ) respectively, and furthers shows both external fasteners ( 22 ) and ( 16 ) each placed through disc ( 12 ).
FIG. 6 illustrates three alternate embodiments of disc ( 12 ) in the form of a substantially elliptical plate ( 27 ), a substantially square or diamond shaped plate ( 28 ) and a hexagonal plate ( 29 ). FIG. 6 in no way illustrates every alternate embodiment possible, nor every alternate embodiment covered by the claims contained herein.
Advantages of the present invention include that the connector not only acts as a connector for joining the two building panels together in abutting relationship but also acts as a guide during assembly of the wall to ensure that the panels making the wall are aligned with each other.
If an adhesive is used between the parts of the connector and the recess no external fitting or fastener need be used to fix the connector in place in the two recesses.
By having a suitably sized gap between the connector and the ends of the recess, vertical adjustment of the panels with respect to each other is possible to assist in assembling or constructing the wall. Having the width of the recess about the same as the width of the connector obviates the need to have sideways or lateral adjustment since the two panels are horizontally aligned with each other because of this close fit.
The described arrangement has been advanced by explanation and many modifications may be made without departing from the spirit and scope of the invention that includes every novel feature and novel combination of features herein disclosed.
Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is understood that the invention includes all such variations and modifications that fall within the spirit and scope.
|
A connector and connection system useful in the building and construction industries for joining two substantially planar composite fiber panels together in which at least a part of the connecting device also acts as a guiding means allowing the two panels to be joined together in alignment with one another. The connector and connection system is especially useful for joining a plurality of compressed straw building panels to form a straight wall, partition or similar structure in substantially the same plane, said structure being constructed without having any external fittings or without having to mask or otherwise hide any fasteners, fittings or the like across the joint between the panels.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of Invention
The instant invention relates to a drawing frame to draw fiber slivers with drawing rollers constituting pre-drawing and main drawing roller pairs and power transmission means to drive said drawing rollers as well as a sliver discharge mechanism.
2. Background of Art
The utilization of drawing rollers with two or more pairs of rollers to draw fiber slivers is known. The circumferential speed of the pairs of rollers increases from the inlet of the drawing frame to the outlet of the drawing frame. The lower roller of the roller pairs is driven by toothed wheels or toothed belts so to produce the slippage-free operation which is absolutely necessary for orderly drawing of the fiber slivers. The upper rollers are pressed against the lower rollers and the rollers thus clamp the fiber material running through between them.
It has been shown that toothed-wheel drives as well as toothed-belt drives of the drawing frame rollers have a detrimental effect upon the uniformity of fiber sliver drawing.
With toothed-wheel drives the clearance which exists between the individual teeth of the toothed wheels causes the roller pairs not to be driven simultaneously but one after the other, especially during run-up of the drawing-frame. This produces irregularities in the drawing of the fiber sliver.
DE-OS 20 44 996 proposes driving the drawing rollers via toothed belts. When such drives are used it was found that the accumulation of dirt between the teeth of the drive and deflection wheels over which the toothed belts are guided, as well as between the teeth of the toothed belt, cause irregular rotational movements of the drawing frame rollers to be produced. These irregularities lead to interference in the drawing of the fiber sliver as well as to increased wear of the drive elements. Especially where small toothed wheels are used and with toothed belts with small tooth divisions, such as are required for predrawing rollers because of the limited space available, soiling of the tooth clearances has a very detrimental effect. Manual cleaning of drive and deflection wheels as well as of the toothed belts is time consuming.
In addition to dirt, the oscillating characteristics of the drive means at the constantly increasing drawing speeds seriously impair the uniformity of fiber sliver drawing. Toothed-belt drives have unfavorable oscillating characteristics at high predrawing speeds.
SUMMARY OF THE INVENTION
It is the object of the instant invention to create a substantially maintenance-free drawing-frame roller drive without slippage between the drive element and the drawing-frame roller, making it possible to drive the drawing-frame rollers in an orderly, uniform and rapid manner.
This object is attained through the instant invention in that power transmission means are used to drive the drawing-frame rollers, whereby at least one of these power-transmission means is a flat belt wrapping around the driving wheels, with the loop of the flat belt wrapping around at least one of the driving wheels being increased by the installation of deflection pulleys. Flat belts surprisingly make it eminently possible to achieve high speeds of the drawing-frame rollers at delivery speeds of over 500m/min. Their utilization as power-transmission means to drive drawing-frame rollers has apparently failed until now because it did not appear possible to ensure slippage-free transmission of the drive forces in this manner. By installing deflection wheels to increase the angle of wrap of the flat belt around the driving wheels of the drawing-frame rollers it has been possible for the first time to achieve slippage-free and thereby precisely adjustable rotational speeds of drawing-frame rollers in the field of roller drawing frames. By providing deflection wheels, the wrap of the flat belt around the driving wheels is increased to such an extent that the power transmission makes it possible to achieve slippage-free and therefore precisely adjustable rotational speeds of drawing-frame rollers. By providing deflection wheels, the wrap of the flat belts around the driving wheels is increased to such an extent that the power transmission from drive motor to the drawing-frame rollers is slippage-free. A further advantage is achieved by applying deflection or driving wheels to the flat belts on both sides, one after the other. In this manner the flat belt is bent from the left side as well as from the right side per revolution. This varied bending of the flat belt ensures cleaning and thereby constant transmissible power.
The pre-drawing rollers are advantageously connected to each other by means of a flat belt for driving. This results in precise assignment of the speed conditions of the pre-drawing roller pair. If at least one deflection pulley is installed in the direction of belt movement between the driving wheels of the pre-drawing rollers, the flat belt extending around the deflection pulley and the driving wheels is bent alternately as it revolves and the wrap is thus increased.
An angle of wrap of at least 180° between flat belt and driving wheel of the lower drawing-frame roller has proven to be advantageous. With this wrap an essentially slippage-free drive of the pre-drawing rollers was obtained. If the flat belt is led over a deflection pulley installed on a tensioning lever provided with a spring element to produce the required belt tension, uniform running of the drawing-frame rollers is advantageously ensured.
Where flat belts are used in a very dusty environment, it is advantageous to install cleaning devices. These cleaning devices act upon the contact surfaces of the driving wheels, the deflection pulleys and of the running surfaces of the flat belts. This prevents impurities from being ground into the flat belt, the disks and the rollers, leading to unfavorable changes of the friction parameters that would cause slippage. This would lead to unwanted changes in the multiplication conditions of the drawing-frame rollers.
In order to change the draft of the fiber sliver it is advantageous for at least one of the driving wheels installed on the drawing-free rollers to be capable of being replaced. By using driving wheels with different diameters, changes in gear multiplication conditions are easily achieved.
In an advantageous further development of the device the flat belt is taken over a deflection pulley rotatably mounted on a free end of a tensioning lever capable of being swiveled around an axis. The tensioning lever is connected by means of a spring to a stationary housing part in such manner that the tensioning roller exerts a tensioning force upon the flat belt. The path of the spring is advantageously sufficiently great so that when different driving wheel diameters are used, the flat belt can still be brought to its desired tension. This desired tension can be set by means of a clamp screw provided on the tensioning lever.
Rubber has proven to be an advantageous material for the flat belts. Flat belts made of rubber achieve good results from the point of view of stretchability, slippage in combination with steel driving wheels and oscillation behavior. If the flat belts are provided with traction elements made of polyamide, good results are achieved in the draft uniformity of the fiber sliver.
If the flat belts are provided with aramide traction elements, the results can be further improved with respect to the oscillating behavior of the flat belt.
When flat belts are used where at least the surfaces coming into contact with the driving wheels are structured, high frictional values are obtained, contributing to slippage-free drive of the drawing-frame rollers.
BRIEF DESCRIPTION OF THE DRAWINGS
An embodiment of the invention is explained through the figures in which
FIG. 1 shows a section of the gear plan of a drawing frame
FIG. 2 shows a pre-drawing drive and
FIG. 3 shows a main drawing drive.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The section of a gear plan of a drawing frame shown in FIG. 1 shows the connections between motor 1 and drawing-frame rollers 30, 31, 32. The lower drawing-frame rollers in particular are driven by means of flat belts. The rotation of the upper drawing-frame rollers is obtained by pressing the upper rollers against the lower rollers.
The driving wheels 2 driven by motor 1 are connected by means of a flat belt 20 and driving wheels 3 to a main drive shaft 40. The driving wheels 2 and 3 are made in the form of step rollers so that different gear multiplications can be achieved by wrapping the flat belt 20 therearound.
The rotations of the drawing-frame rollers 30, 31, 32 are adjusted from the main drive shaft 40 via driving wheels 4 and 10. The driving wheel 4 is connected for driving by means of a belt 22 and a driving wheel 5 to an intermediate drive shaft 41. The drawing-frame roller 30 is driven by the intermediate drive shaft 41 via driving wheels 6 and 7 which are connected to each other by a belt 23. Thanks to the arrangement of the driving wheels 4, 5, 6 and 7 which have different diameters, a suitable rotational movement can be transmitted to the drawing-frame roller 30 at a function of the fiber sliver to be drawn as well as of the draft to be imparted to the fiber sliver. By exchanging the wheels 4, 5, 6 or 7, changes in the rotational speed of the drawing-frame roller 30 can be achieved. Toothed belts 22 and 23 are preferably used for this drive in the draft modification gear system that includes the wheels 4, 5, 6 and 7. The degree of draft can be varied by changing the arrangement of the different diameter wheels 4, 5, 6 and 7.
The drawing-frame rollers 30, 31 effecting a pre-drawing of the fiber sliver are connected for drive by means of a flat belt 24. Through an appropriate selection of the diameter of the driving wheels 8 and 9 it is possible to achieve a rotational speed ratio between the drawing-frame rollers 30 and 31 that determines the extent of pre-drawing of the fiber sliver. Driving wheels 8 and 9 with a diameter essentially between 20 and 40 mm have been shown to be advantageous. For an adaptation to different fiber material to be drawn, the distance between drawing-frame rollers, in particular between the pre-drawing roller 30 and 31, can be changed.
A rotational movement serving to drive the calendar rollers 422 via a driving wheel 11 on an intermediary drive shaft 42 to drive the rotational tray 437 and the can tray 46 is selected from the main drive shaft 40 by means of the driving wheel 10 and a flat belt 21. The flat belt 21 furthermore selects the rotational movement of the drawing-frame roller 32 by means of a driving wheel 12. The drawing-frame roller 32 effects the main draft of the fiber sliver.
The fiber sliver delivered by the drawing-frame roller 32 and going into a running direction A is brought by the calendar rollers 442 into the discharge pipe 438 of the discharge wheel 437 and is discharged from this rotating discharge pipe 438 into a rotatable can 47. The calendar rollers 442 are driven via intermediary drive shaft 42 and a driving wheel 44 is driven via a flat belt 441. The rotating tray 437 is driven via a driving wheel 43 mounted on the intermediary drive shaft 42 by means of a flat belt 431 which drives the driving wheel 434 via deflection pulleys 432 in form of an V-drive, said driving wheel 434, being fixedly connected to driving wheel 43, driving the rotating tray 437 via flat belt 436. The utilization of a flat belt installed in form of a V-drive is much less expensive and more reliable in operation then a bevel-gear drive which can also be used. The can tray 46 is driven by means of drive 45 via driving wheel 434 to impart a rotational movement to the can 47 selectively during the filling process. This advantageous arrangement makes it possible to carry out an absolutely jolt-free depositing of the fiber sliver into the can and thereby also to ensure problem-free presentation at further processing machines.
FIG. 2 shows the drive of the pre-drawing rollers. The driving wheels 8 and 9 are connected to each other for drive by means of the flat belt 24. A deflection pulley 13 is installed between the driving wheel 8 and the driving wheel 9. The deflection pulley 13 advantageously causes the driving wheels 8 and 9 to be contacted by the flat belt 24 over a large area of their circumferential surface. The driving disk 8 is surrounded by the flat belt 24 with an angle of wrap of over 180°. This also applies to the driving wheel 9. This driving wheel 9 is also surrounded by the flat belt 24 with an angle of wrap that is also greater than 180° . As a result the frictional force between the flat belt 24 and the driving wheels 8 or 9 is sufficiently great so that slippage-free driving of the drawing-frame rollers 30 and 31 connected to the driving disks 8 and 9 can be achieved. Rubber has proven to be an advantageous frictional partner for the flat belt 24 and steel for the driving wheels 8 or 9. Especially synthetic rubber, e.g. acrylonitrile butadien rubber with a structured surface yields good frictional values of
0.7. If the flat belts are provided with polyamide traction elements, the flat belts can be stretched to such an extent that the belt tension capable of being produced yields very quiet running and thus good drawing results.
The deflection pulley 13 is advantageously stationary and placed in such a manner between the driving wheels 8 and 9 that an angle of wrap of over 180° is ensured independently of the size of the driving wheels 8 and 9. In order to process different fiber materials, the distances between drawing-frame rollers are modified. In order to avoid a decrease of the angle of wrap to less than 180° for instance, at least two attachment points are provided for the deflection pulley 13 at which said deflection pulley 13 is held between the driving wheels 8 and 9 in a stationary manner.
To equal advantage, the deflection pulley 13 is installed in such manner that the tensioning roller and the deflection pulley are on the same side of the plane in which the axes of the predrawing drawing rollers lie. This plane divides the space into two areas, with the tensioning roller and the deflection pulley being both in one of these areas.
If flat polyamide belts are used the advantage is gained that this type of belt cannot be over-stretched in practice. Easy assembly of the flat belts is thereby possible. In case of highly precise drawing of the fiber sliver, or when extremely high drawing speeds are used, the utilization of flat belts provided with aramide traction bodies has proven advantageous. Such flat belts have an even better oscillating and stretching behavior than the polyamide belt, so that oscillations and rotational speeds of the drawing-frame rollers can be further reduced.
The tensioning of the flat belt 24 is effected by means of a deflection pulley 14 mounted on a tensioning lever 50. The tensioning lever 50 is mounted rotatably over a rotational axis 51. A spring 53 produces pre-tensioning of the flat belt 24 to a predetermined bearing tension. The deflection pulley 14 is fixed in its position by means of an adjusting screw 52. The path of the spring 53 is sufficiently long so as to compensate for the utilization of driving wheels 8 and 9 with different diameters producing a change in position of the deflection pulley 14 while the length of the flat belt 24 is maintained. A handle 54 is provided on the tensioning lever 50 in order to release the tension of the flat belt 24. The pre-tension of the belt 24 is reduced by loosening the adjusting screw 52 and by turning the handle 54 against the spring force in order to replace the flat belt 24 or to change the size or position of the driving wheels 8, 9. By fixing the tensioning lever 50 in this position by means of the adjusting screw 52, rapid and easy replacement of the flat belt 24 is made possible.
If different flat belts 24 are used, springs with different spring forces are used in function of the desired belt tension, these spring forces being adapted to these belt tensions. It may also be advantageous to provide several points of attachment of the spring 52 on the tensioning lever 50 so that the spring force may be varied by using different lever arms.
Wheel cleaners 60 are provided on the driving wheels 8 and 9 as well as on the deflection pulley 13 and on the tensioning roller 14. These disk cleaners 60 cause stripping of the contact surfaces between the disks and the flat belt 24. Accumulation of dirt on the disks, leading to faulty drawing of the fiber sliver is thus avoided. Such drawing faults are due on the one hand to the fact that dirt causes accelerations and decelerations of the driving wheels and on the other hand to the fact that changes in the friction coefficient provoke slippage between flat belt 24 and driving wheels 8 and 9. In a particularly dusty environment it is advantageous to bring such cleaning elements also into engagement with the contact surfaces on the flat belt 24. Band strippers 61 should be placed so that they strip off the flat belt 24 before contact with the driving disks 8 and 9. Cleaning devices of this type can of course also be used with the other flat-belt drives of the drawing frame.
Stripping brushes which are in contact with the disks, rolls and flat belt are most suitable cleaning devices.
FIG. 3 shows the drive of drawing-frame roller 32 which serves to effect the main drawing action. The rotational movement is transmitted from the drive shaft 40 via a driving wheel 10 to the flat belt 21. In the embodiment of FIG. 3 the driving wheel 12 of the drive of the drawing-frame roller 32 on the one hand, and the driving wheel 11 of the drive of the intermediate driving shaft 42 on the other hand is moved by means of the flat belt 21. Two deflection pulleys 15 and 16 are provided after the driving wheel 11, in direction P of belt movement. These deflection pulleys 15, 16 cause the driving wheel 10 to be surrounded by flat belt 21 at a large angle of wrap. This ensures that the rotational movement of the main drive shaft 40 is transmitted without slippage to the flat belt 21. In the embodiment of FIG. 3 the driving wheel 11 of the intermediate drive shaft 42 serves as a deflection pulley to increase the angle of wrap of the flat belt 21 around the driving wheel 12, thus ensuring slippage-free driving of the drawing-frame roller 32.
By using high-faced driving wheels disks and deflection pulleys, good lateral guidance of the belts is ensured.
The instant invention is not limited to the embodiment shown here. Drawing frames according to the instant invention can be used wherever fiber slivers or roves are to be drawn at particularly high speeds. This not only applies to the drawing frames described here, but also to drawing frames of spinning machines, for example.
|
Drawing frame for drawing fiber sliver with draw frame rollers comprising a pair of pre-drawing rollers and a main drawing roller pair. Power transmission members in the form of flat belts are used for driving the draw frame rollers. A deflection pulley engages the flat belts between respective pairs of wheels deflecting the belts for increasing the angle that the flat belt extends around the respective wheels to provide a non-slip engagement between the flat belts and the respective wheels.
| 3
|
FIELD OF THE INVENTION
[0001] The present invention relates generally to components, systems, and methods for stabilizing a medical device in a proper position. More particularly, the present invention relates to such components, systems, methods that may be used to maintain a medical device in a level position.
BACKGROUND OF THE INVENTION
[0002] Some medical devices will only operate properly if they are maintained in a substantially level position. In addition, it is generally undesirable for a medical device to tip over, as such tipping could break or otherwise adversely affect the device.
[0003] In view of the above, currently available medical devices are sometimes stabilized and/or maintained in a level position through the use of floor stands. For example, some currently available medical devices have a flat, substantially rectangular section attached at the bottom thereof. When the device is being carried or otherwise moved, the substantially rectangular section is positioned so as to be completely within the edges of the bottom of the device. In other words, the substantially rectangular section does not protrude beyond the edges of the bottom of the device and therefore is unlikely to contact anything as the device is being moved.
[0004] Either shortly before or shortly after the medical device is set down on the floor pursuant to being moved, the substantially rectangular section is pivoted relative to the bottom of the medical device so as to protrude beyond an edge thereof. As a result, the substantially rectangular section increases the overall footprint of the medical device on the floor and thereby stabilizes the medical device.
[0005] As medical devices become smaller, the bottoms of the medical devices also become smaller. At a certain point, the bottom of a medical device becomes too small to allow one of the currently available substantially rectangular sections to be positioned completely within the edges thereof. Therefore, some of the currently available smaller medical devices include substantially rectangular sections that protrude beyond the edges of the bottom of the device. These sections may therefore come into contact with, for example, patients, medical personnel, or medical equipment, and may causing injury and/or damage. Other currently available smaller medical devices do not include a substantially rectangular section at all. These devices are therefore relatively unstable when set down on the floor.
[0006] At least in view of the above, it would be desirable to provide mechanisms and/or systems that stabilize and/or level a small medical device without increasing the risk of physical injury or damage when moving the device. It would also be desirable to provide methods for stabilizing and/or leveling a small medical device using such mechanisms and/or systems.
SUMMARY OF THE INVENTION
[0007] The foregoing needs are met, to a great extent, by the present invention wherein, in a first embodiment thereof, a floor stand for a medical device is provided. The floor stand includes a connection component configured to be connected to a medical device. The floor stand also includes a telescoping component connected to the connection component and moveable relative to the telescoping component, wherein the telescoping component is configured to stabilize the medical device in a vertical position when the telescoping component is in an extended position relative to the connection component, and wherein the connection component and telescoping component are configured to engage a portion of the medical device and to attach to the medical device.
[0008] In accordance with a second embodiment of the present invention, a method of retractably supporting a medical device is provided. The method includes engaging a portion of a medical device with a connection component and a telescoping component, wherein the connection component and the telescoping component are configured to attach to the medical device. The method also includes moving the telescoping component connected to the connection component to an extended position relative to the connection component to stabilize the medical device in a vertical position.
[0009] In accordance with a third embodiment of the present invention, another floor stand for a medical device is provided. The floor stand includes connecting means for connecting to a medical device. The floor stand also includes stabilizing means for stabilizing the medical device in a vertical position when the stabilizing means is in an extended position relative to the connecting means, wherein the stabilizing means is connected to the connecting means and moveable relative thereto and wherein the connecting means and stabilizing means are configured to engage a portion of the medical device and to attach to the medical device.
[0010] There has thus been outlined, rather broadly, certain embodiments of the invention in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
[0011] In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
[0012] As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 illustrates a perspective view of a floor stand according to a first embodiment of the present invention, wherein the floor stand is connected to a medical device.
[0014] FIG. 2 illustrates a perspective view of the floor stand and a portion of the medical device illustrated in FIG. 1 , wherein the floor stand is in a retracted position.
[0015] FIG. 3 illustrates a perspective view of the floor stand and a portion of the medical device illustrated in FIGS. 1 and 2 , wherein the floor stand is in an extended position.
[0016] FIG. 4 illustrates an exploded perspective view of the floor stand illustrated in FIGS. 1-3 .
DETAILED DESCRIPTION
[0017] The invention will now be described with reference to the drawing figures, in which like reference numerals refer to like parts throughout. FIG. 1 illustrates a perspective view of a floor stand 10 according to a first embodiment of the present invention, wherein the floor stand 10 is connected to a medical device 12 . FIG. 2 illustrates a perspective view of the floor stand 10 and a portion of the medical device 12 illustrated in FIG. 1 , wherein the floor stand 10 is in a retracted position. FIG. 3 illustrates a perspective view of the floor stand 10 and a portion of the medical device illustrated in FIGS. 1 and 2 , wherein the floor stand 10 is in an extended position.
[0018] As illustrated in FIGS. 1-3 , the floor stand 10 includes a connection component 14 that is configured to be connected to the medical device 12 . According to certain embodiments of the present invention, the medical device 12 is a chest drainage unit that, for example, may be used to evacuate air and/or fluid from a patient's chest cavity. Such evacuation helps to re-establish normal intrathoracic pressure in the patient's chest cavity and also facilitates the re-expansion of the patent's lungs to restore normal breathing dynamics. However, upon practicing one or more embodiments of the present invention, one of skill in the art will appreciate that, according to certain embodiments of the present invention, the chest drainage unit illustrated in FIG. 1 may be replaced with another medical or non-medical device.
[0019] FIG. 4 illustrates an exploded perspective view of the floor stand 10 illustrated in FIGS. 1-3 . As illustrated in FIG. 4 , the connection component 14 includes a receiving portion 16 . Typically, the receiving portion 16 is configured to allow a protrusion 18 (illustrated in FIGS. 1-3 ) extending from a bottom surface 19 of the medical device 12 to extend through the connection component 14 . In the embodiment of the present invention illustrated in FIGS. 1-4 , the receiving portion 16 takes the form of a cut-out that the protrusions 18 may slide with respect to.
[0020] According to certain embodiments of the present invention, the protrusion 18 includes a substantially cylindrical portion configured to extend through the receiving portion 16 of the connection component 14 . Also, according to certain embodiments of the present invention, the receiving portion 16 is configured to accommodate the rotation of the protrusion 18 therewithin, regardless of whether the protrusion 18 includes a substantially cylindrical portion or not.
[0021] The floor stand 10 illustrated in FIGS. 1-4 also includes a telescoping component 20 that is connected to the connection component 14 . As illustrated in FIG. 4 , the telescoping component 20 includes a receiving portion 22 that is configured to accommodate insertion of the above-discussed protrusion 18 therein.
[0022] Typically, the above-discussed cylindrical portion of the protrusion 18 is inserted into the receiving portion 22 . Also, according to certain embodiments of the present invention, the receiving portion 22 is configured to allow for the protrusion 18 to be rotated therewithin. As such, according to certain embodiments of the present invention, the entire floor stand 10 is rotatable relative to the medical device 12 to which it is connected.
[0023] FIGS. 2 and 3 illustrate how the above-discussed connection component 14 and telescoping component 20 are connected to each other according to one embodiment of the present invention. More specifically, FIGS. 2 and 3 illustrate that the connection component 14 and the telescoping component 20 are placed adjacent to each other and that the connection component 14 is surrounded on three side thereof by a lip 24 on the exterior of the connection component 14 .
[0024] When the floor stand 10 is positioned on a floor below the medical device 12 , the lip 24 prevents the telescoping component 20 from moving horizontally relative to the connection component 14 in all but one direction. Also, the floor and the medical device 12 prevent the connection component 14 and the telescoping component 20 from moving vertically relative to each other. As such, the telescoping component 20 illustrated in FIGS. 1-4 is substantially limited to moving in only one horizontal direction relative to the connection component 14 . According to certain embodiments of the present invention, the floor stand 10 is configures such that the telescoping component 20 is slidable relative to the connection component 14 in the single remaining horizontal direction of movement.
[0025] FIG. 1 illustrates the floor stand 10 as being positioned substantially parallel to the two side surfaces 21 , 23 of the medical device 12 illustrated therein. However, because, as discussed above, both the connection component 14 and the telescoping component 20 are rotatable relative to the medical device 12 , the floor stand 10 can be rotated so as to be substantially perpendicular to the two side surfaces of the medical device 12 .
[0026] According to certain embodiments of the present invention, when the floor stand 10 is positioned substantially perpendicular to the side surfaces 21 , 23 of the medical device 12 , no portion of the floor stand 10 protrudes beyond the exterior edges 25 , 27 , 29 , 31 of the bottom surface 19 of the medical device 12 . As such, the floor stand 10 is unlikely to come into contact with any persons or objects as the medical device 12 is being carried or moved (e.g., when the floor stand 10 is being lifted and/or transported by a patient or member of themedical staff using the handle 26 illustrated at the top of the medical device 12 in FIG. 1 ).
[0027] When the floor stand 10 is positioned substantially parallel to the side surfaces 21 , 23 of the medical device 12 (i.e., when the floor stand 10 is positioned as illustrated in FIG. 1 ), the telescoping component 20 may be in the retracted position relative to the connection component 14 illustrated in FIG. 2 , in the extended position illustrated in FIG. 3 , or in an intermediate position between the two. According to certain embodiments of the present invention, the floor stand 10 (particularly the telescoping component 20 thereof) is configured to stabilize the medical device 12 in a vertical or substantially vertical position relative to the floor upon which the floor stand 10 is sitting. According to some embodiments of the present invention, the floor stand 10 is configured to maintain the medical device 12 in a level or substantially level position.
[0028] Both the above-mentioned stabilization and leveling typically occur when the telescoping component 20 is in the extended position illustrated in FIG. 3 relative to the connection component 14 . In other words, when the floor stand 10 is positioned substantially parallel to the side surfaces 21 , 23 of the medical device 12 and when the telescoping component 20 extends further away from the edges of the medical device 12 , the effective footprint of the medical device 12 is increased. Thus, additional stability is provided, which prevents the medical device 12 from being tipped over. The increased effective footprint also typically aids in leveling the device. However, according to certain embodiments of the present invention, adjustable extensions may protrude, for example, from surfaces of the floor stand 10 adjacent to the floor to further promote the leveling of the medical device 12 .
[0029] FIGS. 2 and 3 also illustrate a plurality of tabs 28 (on the telescoping component 20 ) and slots 30 (on the connection component 14 ) that, together, make up a locking mechanism according to an embodiment of the present invention. In the locking mechanism illustrated in FIGS. 2 and 3 , when one or more of the tabs 28 is engaged with one or more of the slots 30 , the locking mechanism prevents the telescoping component 20 from moving relative to the connection component 14 . In the embodiment of the present invention illustrated in FIGS. 2 and 3 , the telescoping component 20 is prevented from moving relative to the connection component 14 both when in the extended position illustrated in FIG. 3 and in the retracted position illustrated in FIG. 2 . However, alternate embodiments of the present invention allow for the use of additional or fewer tabs and/or slots at various positions in the floor stand 10 . In order to release the locking mechanism, force is typically used to push the tabs 28 out of the slots 30 . However, alternate release mechanisms are also within the scope of the present invention.
[0030] According to another embodiment of the present invention, a method of retractably supporting a medical device is provided. The method typically includes connecting a connection component to a medical device. This connecting step may be implement, for example, using the above-discussed connection component 14 and medical device 12 . More specifically, this connecting step may be implemented using, for example, a chest drainage unit.
[0031] According to certain embodiments of the present invention, the above-mentioned method also includes moving a telescoping component connected to the connection component to an extended position relative to the connection component. This moving step typically substantially stabilizes the medical device in a vertical position relative to the floor on which the connection component and/or telescoping component are sitting. This moving step can also, according to certain embodiments of the present invention, substantially level the medical device. According to certain embodiments of the present invention, this moving step is implemented by sliding the above-discussed telescoping component 20 relative to the above-discussed connection component 14 .
[0032] Certain embodiments of the above-discussed method of retractably supporting a medical device according to the present invention further include receiving a protrusion extending from a surface of the medical device (e.g., the protrusion 18 illustrated in FIGS. 1-3 ) in a receiving portion of the connection component configured to receive the protrusion. This step may be implemented, for example, using the cut-out sections that make up the receiving portion 16 illustrated in FIG. 4 .
[0033] The above-discussed method may also include preventing the telescoping component from moving relative to the connection component, particularly either when the telescoping component is in the above-discussed extended or retracted position. This preventing step may be implemented, for example, using the tabs 28 and slots 30 discussed above or some other locking mechanisms that will become apparent to one of skill in the art upon practicing one or more embodiments of the present invention.
[0034] The above-discussed method may also include rotating the connection component relative to the medical device. As mentioned above, the telescoping component may be connected to the connection component. Thus, this rotating step may be implemented, for example, by rotating the entire floor stand 10 illustrated in FIGS. 1-4 relative to the bottom surface 19 of the medical device 12 . According to certain embodiments of the present invention, this rotating step allows the floor stand 10 illustrated in FIGS. 1-4 to be moved between a first position where the floor stand 10 is completely beneath the bottom surface 19 of the medical device 12 and a second position wherein the floor stand is substantially perpendicular to the side surfaces 21 , 23 of the medical device 12 .
[0035] The many features and advantages of the 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 invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations 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, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
|
A floor stand for a relatively small medical device. The floor stand stabilizes and/or levels the medical device when the device is on the floor. When the device is being carried or moved, the floor stand is completely underneath the device, so as to minimize the possibility of the stand coming into contact with an exterior person or item. Also, a method of stabilizing and/or leveling a small medical device.
| 0
|
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional Application No. 60/480,844 filed Jun. 23, 2003, which is incorporated by reference as if fully set forth herein.
FIELD OF INVENTION
[0002] The present invention relates generally to wireless communication systems. More particularly, the invention is useful for wireless communication systems which use measurement-based radio resource management.
BACKGROUND
[0003] The purpose of radio resource management (RRM) in wireless communication systems is to efficiently manage the use of resources over the air interface, (i.e. radio resources). Intelligent management of radio resources is essential for maximizing the air interface capacity, ensuring connection reliability and network stability and reducing the battery consumption of wireless transmit/receive units (WTRUs).
[0004] Typical RRM functions include: 1) call admission control, which accepts or rejects requests for new radio links based on the system load and quality targets; 2) handover control, which ensures that a call (connection) is not dropped when a WTRU moves from the coverage area of one cell to the coverage area of another cell; 3) power control, which maintains interference levels at a minimum while providing acceptable link quality; 4) radio link maintenance, which ensures that quality of service requirements for individual radio links are satisfied; and 5) congestion control, which maintains network stability in periods of high congestion.
[0005] RRM functions are triggered, and make decisions, based upon a variety of inputs. Among these inputs, air interface measurements observed by the WTRU and the Node B are extensively used. Air interface measurements can originate from either the WTRU or the Node B. WTRU measurements and radio link specific Node B measurements are referred to as dedicated measurements. Cell-specific Node B measurements are referred to as common measurements. Both types of measurements are employed to precisely evaluate the current state of the radio environment. For example, interference measurements can be used to decide the allocation of physical resources in a timeslot or frequency band.
[0006] Typical measurements which RRM functions rely upon for evaluating the status of the radio environment include: interference signal code power (ISCP); received power measurements (both individual radio link and received total wideband power (RTWP)); received signal strength indicator (RSSI); transmission power, (including individual radio link power and total power); and signal-to-interference ratio (SIR) measurements. These measurements are just several examples of the many measurements that are applicable with the proposed invention.
[0007] As will be described hereinafter, some of these measurements can be predicted and a combination of their latest reports and their predictions can be used when the system is in a transient phase.
[0008] Unfortunately, there is a drawback in the manner in which current RRM functions are performed. There are several conditions that may cause the aforementioned measurements to be unavailable or invalid. First, it is possible that measurements are simply not reported, or measurement reports are corrupted over the air interface. For example, WTRU measurement reports are eventually encapsulated into transport blocks (TBs) to which cyclic redundancy check (CRC) bits are attached. The Node B physical layer determines whether an error occurred by examining the CRC bits. In the event of an error, the Node B physical layer can either deliver the erroneous TB to upper layers with an error indication, or simply indicate to upper layers that an erroneous TB was received on a particular transport channel or a set of transport channels. Such a scenario is particularly relevant when considering WTRU measurements since they are sent over the air interface.
[0009] Secondly, measurements generally have an age threshold, after which the measurement is considered invalid. If measurement reports are not frequent enough, it is possible that valid measurements will eventually become invalid, and thus unavailable to RRM functions.
[0010] Finally, it is possible that measurements are simply invalid because the radio link or the system has entered a transient phase that is undergoing stabilization. For example, interference measurements are unstable for a certain period of time, (up to ½ second), following the configuration or reconfiguration of a radio link due to the transient phase of the power control. Such measurements should not be used to trigger RRM functions or to make decisions since the current state of the radio link or the system is unstable.
[0011] Accordingly, an improved system and method for obtaining measurements for more effective radio resource management is needed.
SUMMARY
[0012] The present invention is a radio resource control system and method which manage air interface resources. According to the present invention, a wireless communication system obtains RRM data by determining availability and validity of certain system measurements. First it is determined whether actual system measurements and predicted measurements are available, and it is also determined whether the actual system measurements are valid. Depending upon the results of the determination, a selective combination of actual air interface measurements, predicted values and default values are used. Alternatively, the radio resources for which the RRM measurement is desired may not be allocated for use.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] A more detailed understanding of the invention may be had from the following description of preferred embodiments, given by way of example and to be understood in conjunction with the accompanying drawing wherein:
[0014] FIG. 1 is a flow diagram showing the use of different types of values for RRM functions in accordance with the present invention;
[0015] FIGS. 2A and 2B are time varying weighting functions used in accordance with the present invention; and
[0016] FIG. 3 is a centralized measurement control unit made in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] The preferred embodiments are described herein in conjunction with an application of the invention for voice or data utilizing regular and HSDPA transmissions according to the Third Generation Partnership Project (3GPP) wideband code division multiple access (W-CDMA) communication system, which is an implementation of a Universal Mobile Telecommunications System (UMTS). Although 3GPP terminology is employed throughout this application, the 3GPP system is used only as an example and the invention can be applied to other wireless communications systems where measurement-based RRM is feasible.
[0018] As used throughout the current specification the terminology ‘wireless transmit/receive unit” (WTRU) includes, but is not limited to, a user equipment, mobile station, fixed or mobile subscriber unit, pager, or any other type of device capable of operating in a wireless environment. These exemplary types of wireless environments include, but are not limited to, wireless local area networks and public land mobile networks. The terminology “Node B” includes, but is not limited to, a base station, site controller, access point or any other type of interfacing device in a wireless environment.
[0019] FIG. 1 is a flow diagram of a procedure 20 for determining measurement values for use by RRM functions in accordance with the present invention. First, actual measurements and predictive values are received and stored in a database along with a timestamp of when they were received (step 22 ). These measurements and values are received from different RRM functions such as call admission control, handover control, power control and radio link maintenance. Regardless of whether they are actual system measurements or predictive values, (such as, for example, in the case of the call admission control function which predicts the system impact upon acceptance of a new call), they are stored in a database. The RNC maintains the database of both the measurements and values and when they were stored.
[0020] Each time the RNC receives a measurement or value, it stores it in the database along with a timestamp corresponding to the time at which it is received. By doing so, the RNC can subsequently determine if measurements or values are available (i.e. stored in the database) and if so, if they are valid with respect to their age, (i.e. their age is less than a certain age threshold).
[0021] If an RRM measurement request has not been received as determined at step 30 , no further action is taken other than to continue to receive and store actual measurements and predictive values at step 22 . If a request for an RRM measurement has been received as determined at step 30 , the RNC reviews the database for the requested RRM measurement to determine whether the requested RRM measurement is available. Measurements may be unavailable, (i.e. they are not stored in the database), either because no measurement report was sent or the measurement report was corrupted over the air interface. If actual system measurements are not available as determined at step 34 , a determination is made as to whether predictive values are available (step 36 ).
[0022] The predictive values (M PREDICTED ) are determined as follows. When certain RRM functions perform an action, they can predict what certain system measurements, (such as interference or power), will be once the action is performed. For example, one RRM function is the Call Admission Control (CAC) algorithm. The CAC algorithm predicts what the interference and power will become once a call is added. If the predicted levels are acceptable, then the call is added; if the predicted levels are unacceptable, then the call is denied. In accordance with the present invention, these predicted interference and power values (along with other types of predicted values) are then stored and used as predicted values for interference and power. Since the prediction of RRM values is well known in the prior art for many different types of RRM functions, and the particular prediction method is not central to the present invention, it will not be described in detail hereinafter.
[0023] If predictive values are available, the predictive values are used (step 38 ), and if not, a default value is used (step 40 ).
[0024] A default value is a predetermined value which is established by historical conditions and or a series of measurements or evaluations. In essence, a default value is a predetermined value which is pre-stored and retrieved when desired. The default value is typically chosen such that RRM functions behave in a conservative way.
[0025] If actual system measurements are available as determined at step 34 , then it is determined whether the actual system measurements are valid (step 42 ). As aforementioned, with respect to the validity of actual system measurements, these measurements may be invalid because they are too old, or may be invalid because the system is in a transient phase and hence, the measurements do not accurately represent the state of the system.
[0026] With respect to the age of a measurement, when a measurement report is received in the RNC database, it is assigned a timestamp. The timestamp corresponds to the time at which the measurement report was received. When the measurement is retrieved from memory, its timestamp is read. If the timestamp indicates that the measurement is older than a certain measurement age threshold (e.g. 1 second), then the measurement is deemed invalid.
[0027] With respect to the invalidity of a measurement because it is taken when the system is in a transient period, as aforementioned, each RRM function is associated with one or more RRM measurements. Each time an RRM function performs an action on the system, it determines the time at which the action was taken. This time corresponds to the start of the “transient period”. The transition period lasts for a certain duration, after which point the system is considered stable again. The duration of the transient period depends on the type of action that was performed by the RRM function. The duration of the transient period is a design parameter.
[0028] If a particular RRM measurement is taken during the transient period of the RRM function, it is deemed to be invalid. This can be determined in several ways. In a first alternative, associated with each RRM measurement stored in the database is an indication of whether or not the RRM measurement was taken during the transient period. Although these measurements are stored, they will be deemed invalid.
[0029] In a second alternative, a timestamp for the beginning of each RRM transient is stored separately. When an RRM measurement is retrieved from the database, its timestamp may be compared to the timestamp of the transient period. If the timestamp of the retrieved RRM measurement is within the transient period, (i.e. the timestamp of the beginning of the RRM transient plus the duration of the transient), the retrieved RRM measurement is determined to be invalid.
[0030] In a third alternative, actual measurements can be declared invalid by simply determining if a predicted measurement is in the database and if so, determining its timestamp. This alternative assumes that the transient period begins exactly when predicted measurements are written to the database. These alternatives are intended to be illustrative, not limiting, as there are many different ways that such a determination of invalidity may be effected.
[0031] The system determines the validity of an actual measurement in view of both age of the actual measurement and the stability of the system. If the actual measurement is valid as determined at step 42 , then the actual measurement is used (step 44 ).
[0032] If the actual measurement is deemed not valid at step 42 , a determination is made as to whether a predictive value is available (step 46 ). If a predictive value is available as determined at step 46 , the actual measurement is combined with the predictive value (step 48 ).
[0033] The combination of actual measurements and predictive values as performed at step 48 will now be described. Although those of skill in the art realize that they are many different ways to combine the values, in one preferred embodiment, the present invention uses a combination of actual measurements (M ACTUAL ) and predicted values (M PREDICTED ) as follows:
M ( t )=α( t )· M PREDICTED +(1−α( t ))· M ACTUAL ; Equation (1)
where α(t) is a time-varying weighting function and t represent the amount for time elapsed since the initiation of the transient period (i.e. transient period starts at t=0). M(t) represents the combined measurement at time t which is provided to the RRM function. Typically, α is a monotonically decreasing function between one (1) and zero (0). Preferably α should equal 1 at t=0, immediately following the beginning of the transient period and α should equal 0 at the end of the transient period, once actual measurements are considered stable.
[0035] Example α weighting functions are shown in FIGS. 2A and 2B for a transient phase of 1 second duration. In FIG. 2A , the variation over time is a substantially straight line function, whereas in FIG. 2B the variation over time results in α initially diminishing at a slow rate, followed by a rapidly diminishing rate. This may be approximated by an exponential or geometric change, depending on the nature of α.
[0036] It is possible that succeeding actions take place during the transient period, (i.e. before α has reached zero). When a subsequent action is taken by an RRM function, the system enters a “new” transient period. Since certain RRM functions typically predict what a value would be following an action that is taken at time t 1 , the predicted value is based on M (t 1 ). In this case, M PREDICTED is made based on M (t 1 ), where t 1 is the time when the succeeding action is triggered.
[0037] Furthermore, t is reset to zero at the completion of the succeeding action, (i.e. a new transient period is started). If a new transient period is started, any subsequent RRM function that acts at t 2 would use t 1 as the beginning of the transient phase. As a result, t in Equation 1 would be t=t 2 −t 1 .
[0038] Referring back to FIG. 1 , if it has been determined that the actual measurement is not valid as determined at step 42 and predictive values are not available as determined at step 46 , then the RNC may implement one of the following four options (step 50 ): 1) use a default value as in step 40 ; 2) combine the actual measurement with a default value; 3) add a margin to the actual measurement; or 4) declare the resources at issue to be unavailable.
[0039] With respect to the first option, use of the default value, this was explained with reference to step 40 .
[0040] With respect to the second option, combining the actual measurement and a default value, the RNC combines these in different ways depending upon the reason why the measurement is invalid. If the measurement is invalid because the latest actual measurement in the database is too old, then an equation similar to Equation 1 can be used:
M ( t )=α( t )· M ACTUAL +(1−α( t ))· M DEFAULT . Equation (2)
[0041] In Equation 2, the time-decaying α term is applied to M ACTUAL and t is the elapsed time since the measurement was stored in the database. Preferably this α function differs from the one used in Equation 1 in that it is chosen to decay much more slowly.
[0042] If the actual measurement is declared invalid because the system is in a transient state, but fresh actual measurements are available, a weighted combination of the actual measurement and the default value is used:
M=A·M ACTUAL +B·M DEFAULT ; Equation (3)
where A+B=1 and the weighting factors A and B are configurable parameters that are optimized based on simulations or observations of the system. Note that different measurements could have different weighting factors.
[0044] With respect to the third option of adding a margin to the actual measurement, preferably a time-varying error margin is added to the actual measurement, as described by:
M=M ACTUAL ±MARGIN; Equation (4)
where MARGIN is a time-varying margin which is large at time zero, immediately following the initiation of the transient period, and monotonically decreases toward zero as the transient period ends. As is the case with Equation (1), Equation (4) is executed when the actual measurements are available, but are deemed not to be valid due to a transient period or an expired timestamp. Note that this option is only valid in the case where measurements or metrics monotonically increase or decrease towards the converged value. In the case where measurements or metrics oscillate around the converged value, this option is not optimum.
[0046] This option has the advantage that predictive measurements need not be presumed to exist during the transient period. It is further possible to execute Equation (1) when predictive measurements are available and execute Equation (4) when MARGIN is considered the best “prediction”.
[0047] With respect to the last option of step 50 regarding declaring resources to be unavailable, if it has been determined that actual measurements, predictive values, adding a margin to an actual measurement or a combination of any of these options is undesirable, the system may simply decline to send an RRM measurement and those resources for which the RRM measurement was requested will be deemed by the assistant to be unavailable. Accordingly, those resources will not be used.
[0048] The result of the determination as to whether to use the actual value at step 44 , a predictive value at step 38 , a default value at step 40 , a combined actual measurement with a predictive value at step 48 , or one of the options in step 50 , is then used to provide the requested RRM measurement.
[0049] To facilitate the management of measurements, a centralized measurement control unit is utilized at the RNC. The centralized measurement control unit implements the following functions: 1) storing received measurements within a central structure; and 2) measurement processing, including measurement filtering, tracking measurement age and validity (e.g. assigning timestamp upon reception, and age threshold comparison), and selecting between or combining predicted values and actual measurements.
[0050] A centralized measurement control unit 80 made in accordance with the present invention is shown in FIG. 3 . The measurement control unit 80 includes a measurement setup unit 81 , a measurement reception and storing unit 82 , a measurement processing unit 83 and a measurement output unit 84 .
[0051] The measurement setup unit 81 implements the measurement setup procedures with respect to the WTRU and the Node B. It is responsible for the setup and configuration of measurements. More specifically, it communicates with the Node B and the WTRU RRC layers to setup, modify and end measurements, giving all measurement configuration details (e.g. averaging period, reporting criterion/period).
[0052] The measurement reception and storing unit 82 stores the actual and predicted WTRU and Node B measurements in an organized structure. This includes assigning timestamp information upon reception of a measurement in order to track the age of the measurement.
[0053] The measurement processing unit 83 filters received measurements, verifies measurement validity and/or availability and combining actual measurements, predicted values and default as appropriate. The measurement processing unit 83 is responsible for all of the measurement processing that is described in the present invention.
[0054] The measurement output unit 84 provides proper measurements to RRM functions upon request, (i.e. providing actual measurements when valid, predicted measurements when unavailable or invalid or a combination of actual measurements, predicted values and default values, such as are illustrated in FIG. 1 at steps 38 , 40 , 44 , 48 and 50 ). Moreover, this measurement output unit 84 can optionally be responsible for triggering RRM functions when measurements exceed a predetermined threshold.
|
A radio resource control unit which monitors air interface resources, includes an air interface measurement unit for obtaining air interface measurements; a storage unit which stores air interface measurements and a corresponding timestamp; and a processing unit, for processing the air interface measurements. At least a portion of the interface measurements may be predicted values.
| 7
|
BACKGROUND OF THE INVENTION
[0001] The present invention relates to supercharger seals and in particular to equalizing a pressure difference across a supercharger rotor shaft seal.
[0002] Power production of an internal combustion engine is ultimately limited by the amount of air pumped through each engine cylinder. Fuel systems can at best provide an optimal amount of fuel to burn with the air contained in the cylinder, and adding more fuel than required for a stoichiometric air-fuel ratio does not result in more energy being produced. The power production of non-supercharged engines is thus limited by the engine's ability to draw air into each cylinder, referred to the Volumetric Efficiency (VE) of the engine, where 100 percent VE is equivalent to complete filling of the cylinder at bottom dead center at one atmosphere of pressure. While some engines achieve greater than 100 percent VE using tuned intake manifolds providing a ram effect, the effects are generally limited to a small RPM range which the intake is tuned to.
[0003] Power production may also be realized by raising the RPM that an engine is operated at, thereby pumping more air through the engine. Unfortunately, high RPM operation requires cam lobe designs which are inefficient at low RPM, and is also stressful on engine parts.
[0004] An alternative method for increasing power production is to pump (or force) air into the engine. This approach is commonly called supercharging because more air is forced into each cylinder than 100 percent VE produces. For many years, supercharging was limited to special applications because of the power required to operate the supercharger (i.e., the parasitic draw of the supercharger) resulting in reduced fuel economy under all operating conditions.
[0005] One known supercharger is a screw compressor type supercharger employed to pump air into the engine at greater than atmospheric pressure to increasing horsepower. Screw compressor superchargers employ a pair of rotating screw elements (or rotors), within a confined cylindrical housing. The rotating screw elements draw air from a throttle body at a rear end of the housing and push the air progressing toward a forward end of the housing thereby compressing the air. The compressed air then flows into an intake manifold of the internal combustion engine. Providing the compressed air (commonly referred to as boost) and a corresponding amount of fuel, dramatically increases engine horsepower production and allows immediate and tremendous acceleration.
[0006] Twin screw type superchargers draw air into the rear of the supercharger and compress the air as it travels from the rear to the front of the supercharger between supercharger rotors, resulting in high pressures at the front of the supercharger. Because the rear of the supercharger must be open to provide a passage for air to enter the supercharger housing, the rotor (or timing) gears are generally at the front of the supercharger, along with rotor shaft bearings, and lubricating oil is present to lubricate the rotor gears and bearings. Front rotor shaft seals are necessary to prevent hot compressed air in the front of the housing from escaping from the housing and heating the lubrication oil, thereby reducing the effectiveness of the oil and causing gear and/or bearing failure, and to prevent the lubricating oil from leaking into the interior of the supercharger.
[0007] An unresolved weakness of twin screw superchargers has been the reliability of front rotor shaft seals at high boost levels. While the seals work well at between eight and twenty pounds of boost, increased wear has been observed above twenty pounds of boost. In the past, when boost was typically below twenty pounds the seal failure was not a significant problem. However, modern twin screw superchargers often produce greater than twenty pounds of boost and as a result, seal reliability has become a significant issue. Further, during part boost or no boost, the front rotor shaft seals are known to fail under vacuum and allow the lubricating oil to enter the supercharger interior.
BRIEF SUMMARY OF THE INVENTION
[0008] The present invention addresses the above and other needs by providing a pressure equalization system which reduces or eliminates a pressure differential across supercharger rotor shaft seals. Under high boost, rotor shaft seals often fail, allowing hot compressed air into an oil lubricated space containing rotor bearings and gears (and vented to ambient pressure), reducing oil lubricating effectiveness and resulting in increased wear and failure. Under low or non boost operation the pressure differential is reversed causing the lubricating oil to leak into the supercharger interior and accelerated rotor seal wear. The pressure equalization system includes flow restrictive seals on both rotor shafts, separated from the rotor shaft seals by vented spaces, thereby isolating the rotor shaft seals from boost or vacuum in the supercharger interior and reducing or eliminating the pressure differential across the rotor shaft seals. Maintaining close to atmospheric pressure on both sides of the rotor shaft seals during boost and vacuum operation reduces wear and failures.
[0009] In accordance with one aspect of the invention, there is provided a combination of the close clearance between rotor ends and an outlet end wall, flow restrictive seals, and the vented intermediate spaces between the flow restrictive seals and rotor shaft seals. The combination of elements reduces a pressure differential across the rotor shaft seals and thereby allows high boost without increased wear and supercharger failure. The reduction of the pressure differential further prevents damage and wear during negative boost (vacuum) conditions.
[0010] In accordance with another aspect of the invention, there are provided flow restrictive seals and vented spaces between the flow restrictive seals and rotor shaft seals. The combination of the flow restrictive seals and the vented spaces allows use of lower friction rotor shaft seals, and a reduced pressure differential across the rotor shaft seals further reduces friction, thereby reducing the creation of heat by the rotor shaft seals and the power consumption by the rotor shaft seals.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0011] The above and other aspects, features and advantages of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
[0012] FIG. 1A is a side view of a supercharged engine according to the present invention.
[0013] FIG. 1B is a top view of the supercharged engine according to the present invention.
[0014] FIG. 1C is a front view of the supercharged engine according to the present invention.
[0015] FIG. 2A is a side view of a supercharger and intake manifold according to the present invention.
[0016] FIG. 2B is a top view of the supercharger and intake manifold according to the present invention.
[0017] FIG. 3 is a cross-sectional view of the supercharger and intake manifold according to the present invention taken along line 3 - 3 of FIG. 2B .
[0018] FIG. 4 is a cross-sectional view of the supercharger outlet end wall taken along line 4 - 4 of FIG. 2A .
[0019] FIG. 5 is a cross-sectional view of the supercharger outlet end wall taken along line 5 - 5 of FIG. 4 .
[0020] FIG. 6 is a detailed view of the supercharger outlet end seals according to the present invention.
[0021] FIG. 7 shows a top view of the supercharger with the outlet end wall vented to the supercharger air intake.
[0022] FIG. 8 shows the outlet end wall vented to a filter.
[0023] Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing one or more preferred embodiments of the invention. The scope of the invention should be determined with reference to the claims.
[0025] A side view of a supercharged engine 10 according to the present invention is shown in FIG. 1A and a top view of the supercharged engine 10 is shown in FIG. 1B . The supercharged engine 10 includes a screw compressor type supercharger 12 attached to an intake manifold 20 . The screw compressor type supercharger 12 compresses air received through a throttle body 16 and provides the compressed air to the supercharged engine 10 through the intake manifold 20 and into the engine 10 . The screw compressor type supercharger 12 is driven by a belt 14 connecting a crankshaft pulley to a supercharger pulley.
[0026] A side view of the screw compressor type supercharger 12 according to the present invention is shown in FIG. 2A and a top view of the screw compressor type supercharger 12 is shown in FIG. 2B . A supercharger pulley 18 is attached to the screw compressor type supercharger 12 at a front (outlet) end 12 a of the supercharger, and the throttle body 16 is attached at a rearward end 12 b . While the supercharger is shown as having the outlet end to the front, belt drives may also be provided to position the inlet end of the supercharger to the front and the supercharger driven from the rear and both the belt and inlet can be at the same end, and such variations are intended to come within the scope of the present invention.
[0027] A cross-sectional view of the screw compressor type supercharger 12 taken along line 3 - 3 of FIG. 2B is shown in FIG. 3 . A first rotor 24 and a second rotor 26 are rotatably housed in an interior of a housing 13 of the screw compressor type supercharger 12 . The rotors 24 and 26 are turned by the pulley 18 and gears 47 a and 47 b (see FIG. 4 ) and draw ambient air 28 through the throttle body 16 and through the rear (inlet) end 12 b and into the screw compressor type supercharger 12 . The ambient air is compressed as it passes through the screw compressor type supercharger 12 by the rotors 24 and 26 . The compressed air 29 is pumped through compressed air passage 30 and the intake manifold 20 into the engine 10 .
[0028] Known superchargers include rotor shaft seals 45 between the rotors 24 and 26 , and the rotor shaft bearings 48 , and a outer shaft seal 49 between a gear space 46 at the outlet end 12 a of the supercharger 12 containing the rotor gears 47 a and 47 b , and the pulley 18 . The rotor shaft seals 45 may be single or double lip seals. The rotor gears 47 b and 47 b reside in the space 46 between the seals 45 and seal 49 and the rotor shaft bearings 48 are exposed to the space 46 . The space 46 contains lubricating oil for lubricating the gears 47 a and 47 b and the bearings 48 . The rotor shaft seals 45 are intended to prevent compressed air inside the interior 13 a of the supercharger 12 from escaping into the space 46 and prevent the lubricating oil in the space 46 from entering the interior 13 a of the supercharger 12 .
[0029] Under part or no load, the supercharger 12 internal pressure is reduced and is often below atmospheric pressure (i.e., positive vacuum). Under part load the absolute pressure inside the supercharger may be as low as 0.5 bars, and coasting, as low as 0.05 bars, resulting in a pressure difference across the rotor shaft seals 45 tending to urge the lubricating oil into the interior 13 a of the supercharger 12 . As the pressure difference grows, the friction between the seal lips and the seal ring increases which is a primary cause of seal wear.
[0030] Further, the power produced by a supercharging internal combustion engine 10 is increased by increasing the supercharger 12 boost pressure. Increasing the boost pressure results in increased pressure and temperature at the outlet end 12 a of the supercharger 12 . If the boost pressure is very high, for example, greater than twenty pounds, the increased pressure has resulted in the hot compressed air in the interior 13 a of the supercharger 12 escaping past the seals 45 (see FIG. 5 ) past the bearings 48 and into the space 46 at the outlet end 12 a of the supercharger 12 which contains supercharger rotor (or timing) gears 47 a and 47 b , thereby causing increased wear and eventually failure of the seals 45 , the bearings 48 , and the gears 47 a and 47 b . One solution to the potential leakage of the hot compressed air into the space 46 is to add flow restrictive seals between the rotors 24 and 26 and the bearing 45 . Unfortunately, merely adding such seals does not sufficiently limit the flow of the hot compressed air into the space 46 to prevent wear and failure.
[0031] Single lip seals might be used, with the lips opening outward under boost, away from the rotor shafts and against the seal seat, and seal wear is not a problem, but the compressed air flowing from the supercharger interior into the space 46 carries lubricating oil out of the space 46 through the vent 53 .
[0032] Another potential measure is to controllably vent the space 46 to ambient air through a vent 53 to allow the hot compressed air to escape the space 46 in a controlled manner, for example, not blowing the lubricating oil onto the supercharger pulley 18 and belt 14 . However, such vent 53 still allows the escape of the lubricating oil under high boost when the hot compressed air pushes past the sealing lips of the shaft seals 45 and into the space 46 and create a mist of the hot compressed air and the lubricating oil from space 46 through the vent 53 to the ambient air. Such vent 53 also does not address the flow of lubricating oil from the space 46 into the supercharger interior 13 a under vacuum.
[0033] A top cross-sectional view of the supercharger outlet end 12 a according to the present invention, taken along line 4 - 4 of FIG. 2A , is shown in FIG. 4 , a front cross-sectional view of the supercharger outlet end wall 44 taken along line 5 - 5 of FIG. 4 is shown on FIG. 5 , and a detailed cross-sectional view of the seals 45 and 51 is shown in FIG. 6 . The supercharger 12 according to the present invention addresses the above problems by providing a close clearance 41 between ends of the rotors 24 and 26 and outlet end wall 44 , flow restrictive seals 51 , and vented intermediate spaces 43 between the seals 51 and the shaft seals 45 . The clearance 41 is preferably approximately 0.2 mm. Both sides of the rotor shaft seals 45 are thus vented to ambient air pressure.
[0034] The combination of the close clearance 41 and the flow restrictive seals 51 limits the escape of the hot compressed air to the bearings 48 , gears 47 a and 47 b , and lubrication oil. The vents 50 and 53 keep the pressure in both the spaces 43 and 46 straddling the rotor shaft seals 45 near ambient air pressure and thus at about the same pressure, thereby limiting any flow past the rotor shaft seals 45 . The novel synergistic combination of the close clearance 41 , the flow restrictive seals 51 , and the vented intermediate spaces 43 between the seals 51 and the seals 45 , allow high boost without increased wear and supercharger failure by reducing the pressure difference across the rotor shaft seals 45 during both high boost and negative boost (vacuum) conditions.
[0035] The flow restrictive seals 51 rotate with the rotor shafts 25 and have a flange 51 a residing in recesses in the rotor side of the outlet end wall 44 , and a cylindrical portion 51 b reaching further into the outlet end wall 44 . The outer diameter of the flange 51 a includes a sealing surface 42 for sealing against a cooperating surface of the outlet end wall 44 . The radial clearance between the sealing surface 42 and the recess in the outlet end wall 44 is extremely small and is preferably approximately 0.05 mm. The sealing surface 42 preferably includes several “sharp” edges 42 a which allow the sealing surface 42 to contact the recesses in outlet end wall 44 without seizing or creating friction. The restrictive seals 51 are preferably made from hardened steel or the equivalent and the sealing surfaces 42 are preferably a labyrinth type seal to provide low friction while restricting the flow of air past the seal by providing a restrictive path for escaping air. A combination of a tight clearance 41 between ends of the rotors 24 and 26 and a rear face 44 b of the outlet end wall 44 , and the labyrinth sealing surfaces 42 , allows only a small flow of the hot compressed air inside the supercharger interior 13 a at the outlet end 12 a to escape into an annular space 43 between the rotors 24 and 26 and the rotor shaft seals 45 in the outlet end wall 44 .
[0036] A passage 50 intersects both of the spaces 43 and vents the spaces 43 to ambient air pressure or to near ambient air pressure. Under high boost, an airflow 60 flows from the spaces 43 and under low or no boost (or vacuum), and the air flow 60 flows into the spaces 43 . The space 46 on the opposite side of the shaft seals 45 is also vented to ambient air by a passage 53 . Because spaces on both sides of the shaft seal 45 are vented to ambient air pressure or to near ambient air pressure, the present invention addresses both the pressure difference across the rotor shaft seals 45 at high load (boost in the supercharger interior 13 a ) as well as part or no load (vacuum in the supercharger interior 13 a ). The labyrinth sealing surfaces 42 allow a very small clearance to reduce the air flows into the spaces 43 and through the passage 50 , thereby not reducing performance under boost and providing safe operation. The labyrinth seal preferably has a radial clearance of approximately 0.05 mm. The passage 50 is drilled in the outlet end wall 44 , and communicating with the two spaces 43 for draining of those to the ambient pressure at high boost and pressurizing spaces 43 from the ambient at low or no boost.
[0037] A top view of the supercharger 12 according to the present invention showing a hose 62 connecting the passage 50 to the superchargers inlet manifold 64 downstream the air mass flow meter 66 and upstream the throttle body 16 is shown in FIG. 7 .
[0038] An alternative embodiment with the hose 62 connected to a filter 68 is shown in FIG. 8 . Because the air flow through the passage 50 is small it is often acceptable to let ambient air to enter the passage 50 directly via the small filter 68 . The filter 68 prevents particles from entering into the supercharger 12 , while providing ambient pressure at the spaces 43 . At high boost, space 43 will be drained down to the ambient pressure through an outflow through the filter 68 , thereby having a cleaning effect on the filter 68 .
[0039] While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims.
|
A pressure equalization system reduces or eliminates a pressure differential across supercharger rotor shaft seals. Under high boost, rotor shaft seals often fail, allowing hot compressed air into an oil lubricated space containing rotor bearings and gears (and vented to ambient pressure), reducing oil lubricating effectiveness and resulting in increased wear and failure. Under low or non boost operation, the pressure differential is reversed causing the lubricating oil to leak into the supercharger interior and accelerated rotor seal wear. The pressure equalization system includes flow restrictive seals on both rotor shafts, separated from the rotor shaft seals by vented spaces, thereby isolating the rotor shaft seals from boost or vacuum in the supercharger interior and reducing or eliminating the pressure differential across the rotor shaft seals. Maintaining close to atmospheric pressure on both sides of the rotor shaft seals during boost and vacuum operation reduces wear and failures.
| 5
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to Japanese Patent Application No. 2010-192239 filed on Aug. 30, 2010 and U.S. Provisional Application No. 61/379,984 filed on Sep. 3, 2010, the contents of which are hereby incorporated by reference into the present application.
TECHNICAL FIELD
[0002] The present invention relates to a battery pack of an electric power tool, and more particularly to a battery pack having lithium-ion cells.
DESCRIPTION OF RELATED ART
[0003] JP 2008-518798 A discloses an electric power tool powered by a battery pack. The battery pack of this electric power tool has a plurality of lithium-ion cells. The lithium-ion cell makes it possible to obtain a high output voltage and merits a high energy density. With the technique described in JP 2008-518798 A, since the lithium-ion cells are used in the battery pack, an output-to-weight ratio of the electric power tool (including the battery pack; same hereinbelow) is increased.
SUMMARY OF THE INVENTION
[0004] It is preferable that an electric tool has a high output-to-weight ratio or output-to-volume ratio. For this reason, it is necessary not only to use lithium-ion cells in a battery pack, but also to increase the output-to-weight or output-to-volume ratio of the electric power tool.
[0005] To meet the above-mentioned demand, it is necessary to increase the output voltage of the battery pack, without changing the size or number of the lithium-ion cells used therein. Thus, in accordance with the present invention, lithium-ion cells with a small internal resistance are used in the battery pack of the electric power tool. Where the internal resistance of a lithium-ion cell is small, the internal voltage drop in the lithium-ion cell decreases. Since a comparatively high current flows in electric power tools, the internal voltage drop caused by the lithium-ion cells also becomes comparatively large. In particular, in a battery pack in which a plurality of lithium-ion cells is connected in series, the internal voltage drop caused by the lithium-ion cells can surpass the output voltage of one lithium-ion cell or the plurality of lithium-ion cells. By suppressing such an internal voltage drop, it is possible to increase the working voltage of the battery pack (output voltage during conduction), without changing the size or number of the lithium-ion cells used therein. Thus, the output-to-weight or output-to-volume ratio of the electric power tool can be increased.
[0006] The inventors have verified that lithium-ion cells having an internal resistance equal to or higher than 30.3 milliohm have been used in the battery packs of conventional electric power tools. Therefore, by using lithium-ion cells having an internal resistance equal to or less than 30 milliohm, it is possible to increase the output-to-weight and output-to-volume ratio over those of the conventional products. The abovementioned value of 30.3 milliohm is obtained by measuring the internal resistance of the conventional lithium-ion cell having a diameter of 18 millimeters and a length of 65 millimeters. Therefore, in accordance with the present invention, a lithium-ion cell that has a diameter equal to or less than 18 millimeters and a length equal to or less than 65 millimeters and also has an internal resistance equal to or less than 30 milliohm is preferred.
[0007] On the basis of the above-described findings, it is preferred that the battery pack for an electric power tool disclosed in the present description have at least one lithium-ion cell, wherein the lithium-ion cell has an internal resistance equal to or less than 30 milliohms. In this case, it is preferred that the lithium-ion cell have a diameter equal to or less than 18 millimeters and a length equal to or less than 65 millimeters. With such a configuration, the output of the battery pack can be increased, without changing the size or number of lithium-ion cells with respect to that of the conventional product. As a result, the output-to-weight and output-to-volume ratio of the electric power tool can be increased.
[0008] In the above-described electric power tool, lithium-ion cells of a small size can be used. Usually, the decrease in size of lithium-ion cells results in the increased internal resistance thereof. Where the diameter of the above-mentioned conventional lithium-ion cell (diameter 18 millimeters, length 65 millimeters, internal resistance 30.3 milliohms) is reduced to 14 millimeters, the internal resistance thereof becomes 49.2 milliohms. Alternatively, where the length of the conventional lithium-ion cell is assumed to decrease to 45 millimeters, the internal resistance thereof becomes 43.6 milliohms. Therefore, where a lithium-ion cell with a diameter equal to or less than 14 millimeters and a length equal to or less than 65 millimeter is used, it is preferred that this lithium-ion cell have an internal resistance equal to or less than 49 milliohms. Further, where a lithium-ion cell with a diameter equal to or less than 18 millimeters and a length equal to or less than 45 millimeter is used, it is preferred that this lithium-ion cell have an internal resistance equal to or less than 40 milliohms. As a result, the output-to-weight and output-to-volume ratio of the electric power tool can be increased with respect to those of the conventional product.
[0009] It is preferable that each of the abovementioned battery packs has a plurality of lithium-ion cells connected in series. Where the plurality of lithium-ion cells is connected in series, the working voltage of the battery pack can be increased. Even when the plurality of lithium-ion cells is connected in series, since the internal resistance of each lithium-ion cell is comparatively small, so the internal resistance of the battery pack can be suppressed to a comparatively low value.
[0010] For example, a battery pack having ten lithium-ion cells connected in series can be used. In this case, the nominal voltage of the battery pack can be 36 V and the nominal capacity of the battery pack can be equal to or higher than 1 Ampere-hour.
[0011] As described hereinabove, where lithium-ion cells with a low internal resistance are used, the working voltage of the battery pack rises and the output of the electric power tool can be increased. However, where the battery pack using the lithium-ion cells with a small internal resistance is used as a power supply of the conventional electric power tool, a high current supplied by the battery pack can damage the constituent components of the conventional electric power tool. For this reason, the battery pack in accordance with the present invention should be used only with specially designed electric power tools, and it is preferred that the use for the conventional electric power tool be prohibited. Meanwhile, the electric power tool that can use the battery pack in accordance with the present invention can also use, without any problem, the battery packs of the conventional electric power tools.
[0012] Based on the above-described findings, the present invention provides the below-described electric power tool system. This electric power tool system includes a first electric power tool powered by a first battery pack and a second electric power tool powered by a second battery pack. The first and second battery packs include the same number of lithium-ion cells. The first battery pack accommodates lithium-ion cells with an internal resistance lower than that of the lithium-ion cells of the second battery pack. Thus, the first battery pack corresponds to the above-described battery pack in accordance with the present invention, and the second battery pack corresponds to the battery pack of the conventional electric power tool. In this case, it is preferred that the first battery pack be configured capable of being detachably attached to the main body of the first electric power tool. It is also preferred that the second battery pack be configured capable of being detachably attached to the main body of the second electric power tool and also capable of being detachably attached to the main body of the first electric power tool.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a side view of an electric power tool according to an embodiment.
[0014] FIG. 2 shows a battery receiving portion of the electric power tool according to the embodiment, as viewed from the front surface (from the left side in FIG. 1 ).
[0015] FIG. 3 is a perspective view of a battery pack of the electric power tool according to the embodiment.
[0016] FIG. 4 is a front view of the battery pack of the electric power tool according to the embodiment.
[0017] FIG. 5 illustrates schematically the compatibility of the battery pack with the electric power tool according to the embodiment and the conventional electric power tool.
[0018] FIG. 6 is a graph illustrating the results obtained in measuring the internal resistance of a lithium-ion cell.
[0019] FIG. 7 illustrates measurement conditions for the internal resistance of the lithium-ion cell.
[0020] FIG. 8 illustrates outer dimensions and effective dimensions of the lithium-ion cell. FIG. 8(A) shows schematically a vertical section of the lithium-ion cell. FIG. 8(B) is a cross-sectional view taken along the B-B line in FIG. 8(A) that shows schematically the transverse section of the lithium-ion cell.
[0021] FIG. 9 shows a battery receiving portion of the conventional electric power tool, as viewed from the front surface.
[0022] FIG. 10 is a perspective view of a battery pack of the conventional electric power tool.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Representative, non-limiting examples of the present invention will now be described in further detail with reference to the attached drawings. This detailed description is merely intended to teach a person of skill in the art further details for practicing preferred aspects of the present teachings and is not intended to limit the scope of the invention. Furthermore, each of the additional features and teachings disclosed below may be utilized separately or in conjunction with other features and teachings to provide improved battery packs for electric power tools, as well as methods for using and manufacturing the same.
[0024] Moreover, combinations of features and steps disclosed in the following detail description may not be necessary to practice the invention in the broadest sense, and are instead taught merely to particularly describe representative examples of the invention. Furthermore, various features of the above-described and below-described representative examples, as well as the various independent and dependent claims, may be combined in ways that are not specifically and explicitly enumerated in order to provide additional useful embodiments of the present teachings.
[0025] All features disclosed in the description and/or the claims are intended to be disclosed separately and independently from each other for the purpose of original written disclosure, as well as for the purpose of restricting the claimed subject matter, independent of the compositions of the features in the embodiments and/or the claims. In addition, all value ranges or indications of groups of entities are intended to disclose every possible intermediate value or intermediate entity for the purpose of original written disclosure, as well as for the purpose of restricting the claimed subject matter.
[0026] An electric power tool 10 according to an embodiment will be explained below with reference to the drawings. As shown in FIGS. 1 and 2 , the electric power tool 10 is provided with a main body 12 and a battery pack 50 that supplies power to the main body 12 of the electric power tool 10 . A tool holder 14 that can be detachably attached to the tool, a main switch 16 operated by the user, and a grip 18 held by the user are provided at the main body 12 . A battery receiving portion 20 that can detachably receive the battery pack 50 is provided at the lower end of the grip 18 . A motor or a circuit substrate (not shown in the figure) for driving the tool holder 14 is accommodated inside the main body 12 . The electric power tool 10 of the present embodiment is, by way of example, an electric power driver, and a driver bit (not shown in the figure) is mounted on the tool holder 14 .
[0027] The battery pack 50 has a housing 52 and ten lithium-ion cells 70 housed in the housing 52 . The ten lithium-ion cells 70 are electrically connected in series. The nominal voltage of each lithium-ion cell 70 is 3.6 V. Therefore, the nominal voltage of the entire battery pack 50 is 36 V. The rated voltage of the electric power tool 10 is also 36 V. A connector portion 60 is provided at the upper surface of the housing 52 . The connector portion 60 is detachably engaged with the battery receiving portion 20 of the main body 12 .
[0028] As shown in FIG. 2 , a pair of rails 22 is formed at the battery receiving portion 20 of the main body 12 . Further, as shown in FIGS. 3 and 4 , a pair of rails 62 is also formed in the connector portion 60 of the battery pack 50 . The pair of rails 62 of the battery pack 50 is slidably engaged with the pair of rails 22 of the main body 12 . As a result, the battery pack 50 is physically connected to the main body 12 .
[0029] As shown in FIG. 2 , the battery receiving portion 20 of the main body 12 is provided with a positive terminal 26 and a negative terminal 28 . The positive terminal 26 and the negative terminal 28 are electrically connected to the circuit board and motor located inside the main body 12 . As shown in FIGS. 3 and 4 , the connector portion 60 of the battery pack 50 is provided with a positive terminal 66 and a negative terminal 68 . The positive terminal 66 and the negative terminal 68 are electrically connected to the ten lithium-ion cells 70 that are connected in series. Where the battery pack 50 is attached to the battery receiving portion 20 of the main body 12 , the positive terminal 66 and the negative terminal 68 of the battery pack 50 are electrically connected to the positive terminal 26 and the negative terminal 28 , respectively, of the main body 12 . As a result, the battery pack 50 is electrically connected to the main body 12 , and the discharge power of the ten lithium-ion cells 70 is supplied to the circuit board and motor located inside the main body 12 .
[0030] The attachment structure of the battery pack in the electric power tool 10 according to the above-described embodiment is essentially similar to the attachment structure of a battery pack 150 in a conventional electric power tool 110 shown in FIGS. 9 and 10 . Thus, in the conventional electric power tool 110 , a battery receiving portion 120 of a main body 112 is also provided with a pair of rails 122 , a positive terminal 126 , and a negative terminal 128 , and a housing 152 of the battery pack 150 is provided with a pair of rails 162 , a positive terminal 166 , and a negative terminal 168 . In this case, similarly to the battery pack 50 of the present embodiment, the conventional battery pack 150 shown in FIG. 10 has ten lithium-ion cells connected in series, and the nominal voltage thereof is 36 V. Thus, the rated voltage of the conventional electric power tool 110 is also 36 V.
[0031] As shown in FIGS. 2 , 3 , and 4 , in the electric power tool 10 of the present embodiment, a rib 64 is formed at the connector portion 60 of the battery pack 50 , and a groove 24 for receiving the rib 64 is formed at the battery receiving portion 20 of the main body 12 . By contrast, as shown in FIGS. 9 and 10 , in the conventional electric power tool 110 , no portion corresponding to the abovementioned rib 64 is present at the connector portion 160 of the battery pack 150 , and no site corresponding to the abovementioned groove 24 is present at the battery receiving portion 120 of the main body 112 . Therefore, as shown schematically in FIG. 5 , the battery pack 50 of the present embodiment is configured attachable only to the main body 12 of the present embodiment and cannot be attached to the main body 112 of the conventional electric power tool 110 . By contrast, the main body 12 of the present embodiment is configured suitable for use not only with the battery pack 50 of the present embodiment, but also with the battery pack 150 of the conventional electric power tool 110 .
[0032] As compared with the conventional electric power tool 110 , the electric power tool 10 of the present embodiment uses new lithium-ion cells 70 with a low internal resistance. The internal resistance of the new lithium-ion cell 70 is improved to 26.8 milliohms. The new lithium-ion cell 70 is a cylindrical lithium-ion cell and has a diameter of 18 millimeters and a length of 65 millimeters. By using the lithium-ion cells 70 with a low internal resistance, it is possible to inhibit the decrease in internal voltage of the battery pack 50 during conduction. As a result, the working voltage of the battery pack 50 is increased and the output performance of the electric power tool 10 is improved. More specifically, since a high current is supplied from the battery pack 50 to the main body 12 , the maximum torque that can be outputted by the electric power tool 10 is increased. Furthermore, since the power loss in the battery pack 50 is reduced, the interval in which the electric power tool 10 can be used is extended.
[0033] The nominal voltage of the battery pack 50 of the present embodiment is equal to the nominal voltage of the conventional battery pack 150 , but the actual output voltage during conduction of the battery pack 50 of the present embodiment is higher than that of the conventional battery pack 150 . Therefore, where the battery pack 50 of the present embodiment is used in the conventional electric power tool 110 , the electric current supplied by the battery pack 50 can exceed the level allowed for the main body 112 of the conventional electric power tool 110 and constituent components thereof can be damaged. For this reason, as mentioned hereinabove, the battery pack 50 of the present embodiment is configured such that the attachment thereof to the main body 112 of the conventional electric power tool 110 is impossible and the use thereof on the conventional electric power tool 110 is prohibited (see FIG. 5 ).
[0034] The inventors have measured the internal resistance for three products A, B, C of the conventional lithium-ion cells that have been developed for electric power tools. The conventional three products A, B, C are all cylindrical lithium-ion cells and have a diameter of 18 millimeters and a length of 65 millimeters. According to the measurement results obtained by the inventors, the internal resistance of the conventional product A is 30.3 milliohms, the internal resistance of the conventional product B is 40.0 milliohms, and the internal resistance of the conventional product C is 50.9 milliohms. These measurement results confirmed that among the conventional cylindrical lithium-ion cells that have been used in electric power tools, there is no cell having a diameter equal to or less than 18 millimeters, a length equal to or less than 65 millimeters, and an internal resistance equal to or less than 30 milliohms. The internal resistance of lithium-ion cells slightly varies depending on the measurement method used. A method for measuring the internal resistance according to the present description will be explained below in greater detail.
[0035] In the electric power tool 10 of the abovementioned embodiment, the size (diameter: 18 millimeters and length: 65 millimeters) of the new lithium-ion cells 70 can be reduced. Typically, where the size of lithium-ion cells is reduced, the internal resistance thereof increases. FIG. 6 shows the relationship between the diameter of a lithium-ion cell (abscissa) and the internal resistance thereof (ordinate). In FIG. 6 , a graph X shows the internal resistance of the new lithium-ion cell 70 , a graph A shows the internal resistance of the conventional product A, a graph B shows the internal resistance of the conventional product B, and a graph C shows the internal resistance of the conventional product C. Among the internal resistance values shown in FIG. 6 , the internal resistance value at a diameter of 18 millimeters is a measured value, and the values at other diameters are estimated values determined by calculations from the measured value. The method for calculating the estimated values will be described below in greater detail.
[0036] As shown in FIG. 6 , the internal resistance increases as the diameter of the lithium-ion cell decreases. However, in the case of the new lithium-ion cell 70 used in the present embodiment, although the cell diameter is reduced to 14 millimeters, the internal resistance thereof is restricted to a value equal to or less than 43.1 milliohms. This value is on par with the internal resistance of the conventional products A, B, C having the diameter of 18 millimeters. Therefore, with the new lithium-ion cells 70 used in the present embodiment, it is possible to reduce the size and weight of the electric power tool 10 including the battery pack 50 , while maintaining the output performance identical to that of the conventional electric power tool 110 . In the case of the conventional lithium-ion cells A, B, C, where the diameter is reduced to 14 millimeters, the internal resistance increases to become equal to or greater than 49.2 milliohms.
[0037] When the size and weight of the electric power tool 10 are to be reduced, not only the diameter of the lithium-ion cells 70 , but also the length of the lithium-ion cells 70 may be decreased. In the case of the lithium-ion cells 70 used in the present embodiment, even when the length is reduced to 45 millimeters, the internal resistance is restricted to a value equal to or less than 38.3 milliohms. This value is on par with the internal resistance of the conventional products A, B, C with the length of 65 millimeters. Therefore, with the new lithium-ion cells 70 used in the present embodiment, the size and weight of the electric power tool 10 including the battery pack 50 can be reduced, while maintaining the output performance identical to that of the conventional electric power tool 110 . In the case of the conventional lithium-ion cells, A, B, C, where the length is reduced to 45 millimeters, the internal resistance thereof is increased to at least 43.6 milliohms. These values are also estimated values calculated by the below-described calculation method.
[0038] As described hereinabove, with the electric power tool 10 of the present embodiment, where the new lithium-ion cells 70 with a low internal resistance are used, the output performance of the electric power tool 10 is improved without increasing the size or weight of the electric power tool 10 . Alternatively, by decreasing the new lithium-ion cells 70 in size, it is possible to decrease the size or weight of the electric power tool 10 , while maintaining the output performance identical to that of the conventional electric power tool 110 . Further, since the power loss in the battery pack 50 is reduced, the interval in which the electric power tool 10 can be used is extended. Further, even when the battery pack 50 is charged, the power loss is small and the increase in temperature of the new lithium-ion cells 70 is suppressed.
(Method for Measuring the Internal Resistance)
[0039] A method for measuring the internal resistance in the present embodiment will be explained below. With this measurement method, first, a discharge depth (charge level) of a lithium-ion cell is set to 50%. More specifically, after the lithium-ion cell is appropriately charged, the quantity of electricity corresponding to a half of the nominal capacitance is discharged. The terminal voltage of the lithium-ion cell is then measured, while discharging the lithium-ion cell. In this case, the ambient temperature is maintained at 25±−1° C., and the temperature of the lithium-ion cell is also 25±1° C. As shown in FIG. 7 , when the lithium-ion cell is discharged, the discharge current changes with time. More specifically, in the first 1 sec, the discharge current is adjusted to 10 A, and in the subsequent 5 sec, the discharge current is adjusted to 20 A. The specific feature of this measurement method is that the lithium-ion cell is discharged at a high current, with consideration for the use in an electric power tool. While the lithium-ion cell is thus discharged, the current C 1 and voltage V 1 are measured after 1 sec has elapsed, and the current C 2 and voltage V 2 are measured after 6 sec have elapsed. The internal resistance of the lithium-ion cell is determined from the slope of the current-voltage line between the two points in which measurements have been conducted. Thus, the internal resistance R is represented by the following formula.
[0000] R= ( V 1− V 2)/( C 2− C 1)×1000 [mΩ]
(Method for Calculating the Estimated Value of Internal Resistance)
[0040] A method for calculating the estimated value of internal resistance in the present embodiment will be explained below. As shown in FIG. 8 , an electrode assembly 72 having a positive electrode sheet and a negative electrode sheet wound with a separator being interposed therebetween is accommodated in the lithium-ion cell 70 , and the internal resistance of the lithium-ion cell 70 is inversely proportional to the surface area of the electrode assembly 72 spread on a plane. In this case, the surface area of the electrode assembly 72 spread on a plane is proportional to the height h 1 of the electrode assembly 72 accommodated in the lithium-ion cell 70 and also proportional to the transverse cross-sectional area S of the electrode assembly 72 accommodated in the lithium-ion cell 70 . In this case, the difference h 2 between the height H of the lithium-ion cell 70 and the height h 1 of the electrode assembly 72 is 7 millimeters. The diameter d 1 of the cavity formed in the center of the electrode assembly 72 is 5 millimeters. The share of structural resistance fraction created by the collector or the like in the internal resistance of the lithium-ion cell 70 is 5 milliohms.
[0041] Therefore, it can be calculated that when the new lithium-ion cell 70 having the diameter of 18 millimeters, the length of 65 millimeters, and the internal resistance of 26.8 milliohms, is reduced in diameter to 14 millimeters, the internal resistance thereof will become 43.1 milliohms. Alternatively, it can be calculated that when the new lithium-ion cell 70 is reduced in length to 45 millimeters, the internal resistance thereof will become 38.3 milliohms. Likewise, it can be calculated that when the lithium-ion cell that is the conventional product A having the diameter of 18 millimeters, the length of 65 millimeters, and the internal resistance of 30.3 milliohms, is reduced in diameter to 14 millimeters, the internal resistance thereof will become 49.2 milliohms. Alternatively, it can be calculated that when the lithium-ion cell that is the conventional product A is reduced in length to 45 millimeters, the internal resistance thereof will become 43.6 milliohms.
[0042] The embodiments of the present invention are described above in detail, but these embodiments are merely exemplary and place no limitation on the patent claims. Thus, the technical scope of the claims includes various modifications and changes of the above-described specific examples. In particular, the actual diameter and length of the battery cells do not necessarily strictly match the dimensions (diameter: 18 millimeters and length: 65 millimeters) explained in the present detailed description of the invention, and a certain difference in dimensions (several millimeters) may be present.
|
A battery pack of an electric power tool comprises ten lithium-ion cells. The ten lithium-ion cells are connected in series. Each lithium-ion cell has a diameter equal to or less than 18 millimeters, a length equal to or less than 65 millimeters, and an internal resistance equal to or less than 30 milliohms. Because the battery pack has a high voltage in operation and is therefore able to supply large current, the battery pack is preferably configured incapable of being used in a conventional electric power tool that cannot operate under such a large current.
| 1
|
FIELD OF THE INVENTION
[0001] The invention is related to use of friction reducers in oilfield treatments. Specifically, the invention relates to dispensing of such friction reducers downhole in gravel packing operations.
BACKGROUND OF THE INVENTION
[0002] Gravel packing is used as a means of controlling sand production and to consolidate and prevent the movement of failed sandstone and/or increase the compressive strength of the formation sand. It can also serve as a filter to help assure that formation fines and formation sand do not migrate with the produced fluids into the wellbore. In a typical gravel pack completion, gravel is mixed with a carrier fluid and is pumped in a slurry mixture through a conduit, often drill pipe or coiled tubing, into the wellbore. The carrier fluid in the slurry is returned to the surface through a separate tubular or an annulus area, leaving the gravel deposited in the formation, perforation tunnels and wellbore where it forms a gravel pack.
[0003] High friction pressure is a known problem in gravel packing used in sand control and for supporting the matrix surrounding the wellbore, especially for high rate water packs in long open-hole intervals, such as those longer than 3000 ft. (915 m). High friction pressure is undesirable because it can result in high pressures in open hole sections that can exceed the fracturing pressure of the formation. Unintended fracturing during a gravel pack treatment leads to incomplete packing and loss of gravel to the formation, ultimately impairing productivity. If no friction reducing additive is used, when pumping through a 8.5 inch (21.6 cm) casing with 5.5 inch (14 cm) production tubing, for example, the pressure can rise up to that of water, namely up to 110 psi/1000 ft in the tubing (18 kPa/m of pipe) or up to 80 psi/1000 ft (14.5 kPa/m of casing) in the annulus when pumped at 20 barrels per minute (0.053 m 3 /s). For wells at high depths, such as 20,000 ft. (6090 m), or 30,000 ft. (9144 m), excessive friction pressure can alter the well design in terms of limiting the drilled length of an horizontal zone, or in other cases being the difference between being able to effectively pumping a gravel packing or not when the pumping power at surface is limited.
[0004] Known methods to reduce friction pressure include the use of polymer-based gravel packing fluids and friction reducers, chemical additives known to reduce the friction pressure of flowing fluids. These polymers and friction reducing agents are added at the surface with the gravel packing fluids. The conventional polymeric friction reducing agents can degrade when exposed to high shear zones in the pipes or downhole tools due to shear induced degradation during the treatment, however, allowing pressures to increase over time.
[0005] Additionally, polymer materials that are combined with the gravel packing fluids at the surface to reduce friction can impair the flow through the gravel pack after the gravel packing operation is completed. Fluids from the reservoir may also reduce the effectiveness of the friction reducers added at the surface. The majority of the friction occurs between the washpipe and the screen in the return flow of fluid during the gravel packing treatment.
[0006] New methods are therefore needed for reducing friction in such types of treatments to overcome these and other obstacles.
SUMMARY OF THE INVENTION
[0007] The invention is directed to a method of introducing friction reducing agents within a wellbore penetrating a subterranean formation during a gravel packing operation. Specifically, the introduction is accomplished by providing a length of tubing located downhole within the wellbore for conducting fluids within the wellbore through the tubing during circulating of gravel packing fluids introduced from the surface within the wellbore. At least a portion of the tubing is surrounded by a screen for screening out particulate matter during the gravel packing operation. An annular space is defined between an interior of the screen and the exterior of the tubing. A friction reducing agent is dispensed from a dispensing apparatus that locates downhole with the tubing. The dispensing apparatus includes a housing and a chamber disposed within the housing that has one or more outlets that open into the annular space defined by the screen and tubing for dispensing the friction reducing agent. The dispensing apparatus further includes a piston and a trigger mechanism for actuating the piston. When the trigger mechanism is activated to actuate the piston, the friction reducing agent is dispensed through the one or more outlets at a position downhole remote from the surface during the circulating.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying figures, in which:
[0009] FIG. 1 shows a prior art packing tool disposed in a wellbore;
[0010] FIG. 2 shows a longitudinal cross section of a tubing section having a friction reducing agent dispensing apparatus for deployment of friction reducing chemicals in accordance with an embodiment of the invention;
[0011] FIG. 3 shows an enlarged view of a section of the tool of FIG. 2 ;
[0012] FIG. 4 shows an enlarged view of a section of FIG. 2 ;
[0013] FIG. 5 shows a cross section of a tool, illustrating fill and bleed ports, in accordance with an embodiment of the invention;
[0014] FIG. 6 shows an injection port in accordance with one embodiment of the invention;
[0015] FIG. 7 shows a modified poppet valve in accordance with one embodiment of the invention;
[0016] FIG. 8 shows a downhole tool, illustrating the introduction of a friction reducing agent from a dispensing apparatus of the invention;
[0017] FIG. 9 shows a friction reducing agent dispensing apparatus having a mechanical trigger mechanism in accordance with one embodiment of the invention; and
[0018] FIG. 10 shows a flow chart illustrating a method in accordance with one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0019] In the present invention, friction reducing agents are dispensed downhole in gravel packing operations. In high rate water packing treatments, gravel is placed in the annulus between a wellbore and a screen. In these treatments the gravel is suspended, carried, displaced and deposited by means of turbulent flow of a low viscosity aqueous fluid, as opposed to low rate gravel packing treatments where the fluid is viscosified by means of high concentrations of polymers such as hydroxyethyl cellulose (HEC) or viscoelastic surfactants (VES).
[0020] Friction pressure is of high concern in all gravel packing treatments, because contrary to other stimulation methods such as acidizing or fracturing, where the fluid is pumped into the reservoir, in gravel packing operation the fluid is partially circulated back to surface. This essentially doubles the pipe length through which the fluid is pumped. In addition the re-circulated fluid is pumped back into the well during the treatment, increasing the exposure time of the fluid to shear. This is especially important in high rate water packing treatments, as friction pressure exponentially increases for a given fluid with the pumping rate. Pumping rates may range from about 1 to about 100 barrels (about 0.0026 m 3 /s to about 0.25 m 3 /s) per minute, more particularly, from about 5 to about 30 barrels per minute (about 0.013 m 3 /s to about 0.08 m 3 /s)
[0021] Although low friction pressure is key for the placement of both low rate and high rate gravel packing treatments, the high concentrations of viscosifiers used in the former allow for lower friction pressures than those of brine to be obtained. For high rate water packs the fluid viscosity is not enough to ensure gravel suspension, and the friction pressure in the tubulars, annulus between borehole and screen, and in the production tubing is similar to that of water. In particular, friction reducing agents may be released downhole in high rate water pack treatments by means of the various embodiments of the present invention. The friction reducing agents dispensed downhole may be used in combination with friction reducing agents that are added at the surface or may be used without any surface added friction reducing agents.
[0022] Friction reducing agents to be used in gravel packing applications in accordance with the invention may be provided in the form of a solution, suspension, emulsion, gel or the like. The friction reducing agents may be polymers, including generally high molecular weight linear polymers or polymers that have been slightly crosslinked or drag reducing surfactant formulations or a combination of these. As used herein with reference to polymers, “high molecular weight” is meant to encompass those polymers having a molecular weight of from about 5 to about 25 million or more. These polymers may be pumped at low enough concentrations such that they do not significantly increase the viscosity of the fluid. Suitable polymers may include guar or a guar derived polymer. Examples of suitable synthetic polymers and copolymers include polymethylmethacrylate, polyethyleneoxide, polyacrylamide, polymethacrylamide, partially hydrolyzed polyacrylamide, cationic polyacrylamide derived polymers such as those obtained by radical polymerization of dimethylamino ethyl methacrylate (DMAEMA), 2-(methacryloyloxy)-ethyltrimethylammonium chloride (MADQUAT), methacrylamidopropyl trimethyl ammonium chloride (MAPTAC), or diallyldimethylammonium chloride (DADMAC), or anionic polymer such as polyAMPS (poly 2-acrylamido-2-methylpropane sulfonic acid), and the like.
[0023] Examples of suitable conventional friction reducers are those polyacrylamide derivatives commonly used in the field supplied as concentrated emulsified conventional drag reducing formulation, containing around 30% of active vinyl polymer. Suitable levels of friction reduction can be obtained with this chemical at concentrations of the order of about 0.75 ml/L to about 2 ml/L in water. Other polymers include high-molecular weight polysaccharides composed of mannose and galactose sugars, or guar derivatives such as hydropropyl guar (HPG), carboxymethyl guar (CMG), and carboxymethylhydroxypropyl guar (CMHPG). Cellulose derivatives such as hydroxyethylcellulose (HEC) or hydroxypropylcellulose (HPC) and carboxymethylhydroxyethylcellulose (CMHEC) may also be used. Any useful polymer may be used in either crosslinked form, or without crosslinker in linear form. Polymer based friction reducer concentrates are typically diluted at concentrations ranging between 0.1 mL/L and 5 mL/L, and more typically between 0.3 mL/L and 2.5 mL/L.
[0024] Bacterial origin polymers such as xanthan, diutan, and scleroglucan, three biopolymers, may also be useful as a friction reducing agent. Such friction reducing biopolymers are described in U.S. patent application Ser. No. 11/835,891, filed Aug. 8, 2007, which is herein incorporated by reference in its entirety.
[0025] The friction reducing agent may include viscoelastic surfactants (VES) or mixtures of viscoelastic surfactants, with or without other friction reducing polymers. Nonlimiting examples of suitable viscoelastic surfactant materials are described in U.S. Pat. Nos. 5,979,557 (Card et al.); 6,435,277 (Qu et al.) and 6,703,352 (Dahayanake et al.), which are each incorporated herein by reference in their entireties. The viscoelastic surfactants may include cationic surfactants, amphoteric surfactants, zwitterionic surfactants, including betaine surfactants, anionic surfactants and combinations of these.
[0026] The friction reducing fluid may comprise friction reducing surfactant formulations in combination with one or more polymeric or monomeric friction reducing enhancers. Such friction reduction enhancers and friction reduction materials are described in U.S. patent application Ser. No. 11/833,449, filed Aug. 3, 2007, which is incorporated by reference herein in its entirety. The surfactant friction reduction enhancers are used in concentrations of from about 1 mL/L to about 10 mL/L, and more typically from about 2.5 mL/L to about 6 mL/L, which may be in active concentrations of less than 4 g/L. Suitable friction reducing surfactants may include cationic surfactants, amphoteric surfactants, zwitterionic surfactants, anionic surfactants and combinations of these. Specific examples of suitable friction reducing surfactants, when used with a primary friction reduction enhancer, include cetyl trimethyl ammonium chloride and tallow trimethyl ammonium chloride. The polymeric friction reduction enhancers are polymers, which may be either cationic or anionic.
[0027] Optionally, a monomeric friction reduction enhancer may also be used in combination with the friction reducing surfactant. Such monomeric drag reduction enhancers are organic counterions, and may include monomers or oligomers of the polymeric drag reduction enhancer. An example of these friction reduction enhancers is (sodium) polynaphthalene sulfonate, as the polymeric friction reduction enhancer, and (sodium) naphthalene sulfonate, as the monomeric friction reduction enhancer.
[0028] Co-surfactants, which may have slightly different chemical natures from the main surfactant, may also be used. Thus, for example, the co-surfactant may be cationic if the main surfactant is anionic. Co-solvents, such as isopropyl alcohol, glycerol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether, may also be used.
[0029] In certain embodiments, dispersed solids may also be contained and dispensed from the canister. These solids may be suspended in a carrier fluid, in the form of suspensions or emulsions.
[0030] The friction reducing agent may be compatible with one or more heavy brines, such as seawater, NaCl, KCl, NaBr, CaBr 2 , CaCl 2 , etc. In such instances, the friction reducing agent would not cause precipitation in such brines and still be effective as a drag reducing agent. The choice of brine can also result in an improvement of the friction reduction capability of a given friction reducer, such as the polymer or surfactant based friction reducing agents.
[0031] The friction reducing agents may be released through a friction reducing agent dispensing apparatus that locates downhole with the tubing of the well. The friction reducing agents may be released downhole from such dispensing apparatus in response to various conditions. These may include increased pressures required for circulation of fluids due to 1) changes in the fluid hydrostatic head that can be altered by means of varying brine density of reduced gravel concentration in the wellbore; 2) fluid flow rate; and 3) reduced effectiveness of the friction reducing agents pumped at the surface, which may be caused by shear induced degradation or contact with fluids being produced from the reservoir, or with solids being deposited on the wellbore face during the drilling process.
[0032] Release of the friction reducing agents downhole in accordance with the invention may result in a pressure drop (DR) of from up to 50%, 60%, 70% or more. Such percentages of friction reduction is normally estimated from measurements of pressure in the well as a comparison of the pressure differential for the friction reducing fluid (ΔP f ) as compared to the pressure differential of brine or water (ΔP w ) (as determined by similar measurements or engineering correlations) and reported according to the following formula (I) below:
[0000]
%
DR
=
Δ
P
w
-
Δ
P
f
Δ
P
w
×
100
(
1
)
[0033] For pumping friction reducers at the surface, the selection of the most appropriate friction reducer among those commercially available is easily carried out currently by those skilled in the art taking into consideration parameters such as brine type, density, well dimensions (depth, casing and tube size), gravel packing tool ID and length, available high rate pumping horse power at surface, active concentration and viscosity of the friction reducer concentrate, available metering pumps and flow control devices, etc. Special attention may be given when water is replaced by heavy brines to the compatibility between brine and friction reducer, to ensure appropriate levels of performance are achieved.
[0034] The selection of the friction reducing agent to be pumped downhole may be carried out following analysis, although other parameters specific to the stability and effectiveness of the friction reducer concentrate, its viscosity and pumpable concentration at downhole pressure and temperature are of concern, as well as the specific design of the tool deployed to deliver the friction reducer downhole.
[0035] The dispensing apparatuses in accordance with embodiments of the invention may be disposed on a downhole tool, tubing or pipe, such as a wash pipe of a sand control service tool. Such devices may include mechanisms for triggering the deployment of the reagents at the desired time. Devices used to dispense reagents or chemicals for various purposes, for example, to break fluid loss control agents in gravel packing operations or the like have been described in U.S. patent application Ser. No. 11/639,031, filed Dec. 14, 2006, which is incorporated herein by reference in its entirety. For brevity of description, “canister” will be broadly used to describe various apparatuses of the invention that include chambers for storing and dispensing reagents, chemicals, fluids, or the like.
[0036] In accordance with embodiments of the invention, a canister for dispensing friction reducing agents downhole may be incorporated into a downhole tool, for example in the collar or housing of a downhole tool or tubing. Various downhole tools and tubing strings can potentially be modified to have a chamber (container or canister) for deployment of friction reducing agents and other chemicals and reagents in accordance with embodiments of the invention. While embodiments of the invention may be used with various downhole tools or tubings, for clarity, the following description mainly uses tools and tubings used in gravel packing to illustrate embodiments of the invention.
[0037] An example of a downhole tool used in gravel packing may be found in U.S. Pat. No. 6,220,353 issued to Foster et al., which discloses a full bore set down (FBSD) tool assembly for gravel packing in a well. This patent is assigned to the present assignee and is incorporated by reference in its entirety. FIG. 1 shows a schematic of a service string 3 disposed in a wellbore 1 . The service string 3 includes a perforating gun 11 aligned with the zone to be produced, a bottom packer 5 , a sand screen 6 , a gravel pack tool assembly 10 , and a tool assembly packer 7 . The service string 3 is supported by a tubing string 8 extending to the surface. In this embodiment, the perforating guns are fired to perforate the production zone. Then, the service string 3 is lowered to align the packers 5 , 7 above and below the perforations, and then the packers 5 , 7 are set to isolate the production zone and define an annulus area between the service string 3 and the casing 2 . The gravel packing is then performed and the zone produced. The friction reducing dispensing apparatus in accordance with the invention may be incorporated with such prior art packing tools.
[0038] A typical gravel pack operation includes three operations (among others) referred to as the squeeze operation, the circulating operation, and the reverse operation. In the squeeze operation, the gravel slurry is forced out into the formation 4 by pumping the slurry into the production zone while blocking a return flow path. The absence of a return flow path causes the pressure to build and force the slurry into the formation 4 . When the void spaces within the formation 4 are “filled,” the pressure will rise quickly, referred to as “tip screen out.” Upon tip screen out, the next typical step is to perform a circulating operation in which the gravel slurry is pumped into the annular area between the sand screen 6 and the casing 2 . In the circulating position, the return flow path is open and the return fluid is allowed to flow back to the surface. The sand screen 6 holds the gravel material of the gravel slurry in the annular area, but allows fluids to pass therethrough. Thus, circulating the gravel slurry to the sand screen 6 deposits the gravel material in the annular area. However, during the circulating operation, when the deposited gravel material reaches the top of the sand screen 6 , the pressure will rise rapidly, indicating screen out and a full annulus. Note that an alternative manner of operating the tool is to perform the squeeze operation with the tool assembly 10 in the circulate position and with a surface valve (not shown) closed to prevent return flow. Using this method, the shift from the squeeze operation to the circulate operation may be made by simply opening the surface valve and without the need to shift the tool.
[0039] When the annulus is packed, the string may be pulled from the wellbore 1 . However, to prevent dropping of any gravel material remaining in the service string 3 and the tubing 8 into the well when pulling the string from the well, the gravel in the tubing 8 and service string 3 is reverse circulated to the surface before the string is removed. This procedure of reverse circulating the remaining gravel from the well is referred to as the reverse operation. In general, the flow of fluid is reverse circulated through the tubing 8 to pump the gravel remaining in the tubing string 8 and service string 3 to the surface.
[0040] Canisters in accordance with embodiments of the invention may be used with various downhole tools or tubings, such as the tool assembly 10 shown in FIG. 1 . The general features of a canister of the invention may include: a chamber (e.g., an annular chamber), a piston that can slide in the chamber, a mechanism to activate (push) the piston, and one or more outlets (ports) to dispense the content stored in the chamber into the annular space defined by the interior of the screen and the exterior of the tubing.
[0041] FIG. 2 shows an example of a downhole tubing string (e.g., a wash pipe) incorporating a canister of the invention. FIGS. 3 and 4 show sections of the same tool in expanded views. In this particular example, the downhole tool or tubing is a wash pipe, which is shown as having a box×pin joint. However, in other embodiments, the canisters may be incorporated into other downhole tools or tubings.
[0042] As shown in FIGS. 2-4 , a downhole tool 20 comprises: an upper sub 21 with a premium flush thread, a crossover 22 containing a modified poppet valve 23 (which will be described in more detail with reference to FIG. 7 ) for activation at selected depth (or pressure), a mandrel 24 , a free-floating piston 25 located inside a pressure-containing housing 26 and mounted on the outside (od) of the mandrel 24 , and a lower sub 27 containing one or more injection ports 28 to allow the friction reducing agents to be dispersed. As shown in FIG. 6 , the injection port 28 includes a check valve 61 to allow the chemicals to be dispensed outward, while preventing outside fluids from entering the canister. The space between the housing 26 and mandrel 24 defines a chamber 29 for storing the friction reducing agents. Note that in some embodiments, the housing 26 and the mandrel 24 may be an integral part. In this case, the chamber 29 may be viewed as disposed inside the wall of the housing 26 .
[0043] The lower sub 27 may also contain a fill port and a bleed port and a premium flush thread. FIG. 5 shows a transverse section of the lower sub 27 , illustrating the fill port 51 and the bleed port 52 . Note that the fill port 51 and the bleed port 52 may also be disposed at other locations of the canister, for example in the upper sub 21 or in the housing 26 between the upper sub 21 and the lower sub 27 . The fill port 51 and the bleed port 52 allow the chemicals to be filled in the annular chamber 29 between the housing 26 and the mandrel 24 and in front of the piston 25 .
[0044] FIG. 7 shows an expanded view of a modified poppet valve 23 that may be used with canisters of the invention. The poppet valve 23 has an opening 73 that faces the lumen of the tubing. In the closed state, the spring 72 pushes a plug to seal the opening 73 . When the pressure inside the tubing is high enough to push open the opening 73 , the pressure will be conducted to the conduit 74 to push the piston (shown as 25 in FIG. 2 ) to dispense the friction reducing agents. Note that the poppet valve shown in FIG. 7 is an example. Other devices, including mechanically operated ones, may also be used. For example, the poppet valve may be replaced with any valve (e.g., a ball valve or a sleeve valve) that is suitable for downhole use. Such other valves may be opened and closed by operating a shifting tool, which may be attached in the lumen of the tubing.
[0045] As shown in FIG. 2 , a canister of the invention may be incorporated into a housing of a downhole tubing or a tool (including a collar). In this particular embodiment, the piston and the chamber for storing the friction reducing agents or other chemicals have an annular shape—along the circumference of the housing. However, other embodiments may have different shapes. For example, the annular shape as shown in FIG. 2 may be divided into two semispherical shapes or a plurality of tubular shapes in the wall of the housing. While the example in FIG. 2 has the canister designed inside the housing of the wash pipe, in other embodiments, a canister of the invention may be a separate part disposed on the inside (lumen) or outside of a tubing or a downhole tool.
[0046] A canister of the invention may be dimensioned to suit the purposes of the selected operations. How to determine a suitable dimension is known to one skilled in the art. For example, a canister in accordance with embodiments of the invention for use in gravel packing may be designed to dispense a selected volume (e.g., from about 5 in 3 (82 cc) to about 100 in 3 (1638 cc) or more of a chemical per foot (0.3 m) of screen run). The typical active concentration of friction reducer concentrates ranges from about 25 to about 40 wt. %. These concentrations are typically diluted at concentrations ranging from about 0.1 ml/L to about 5 ml/L, and more typically from about 0.3 ml/L to about 2.5 ml/L for polymer based friction reducers, and ranges from about 1 ml/L to about 10 ml/L, and more typically from about 2.5 ml/L to about 6 ml/L for surfactant based friction reducers. Only a portion of the treatment fluid may require friction reducer, however, as friction pressure does not become prohibitive in many treatments until the development of the beta wave. In certain instances, the friction reducer would only be reduced at the tail end of the gravel packing treatment, requiring significantly less chemical and ensuring only the portion of the treatment that required friction reduction was dosed.
[0047] The polymer based friction reducers can degrade when exposed to high shear during long enough periods of time. When the friction reducer is pumped at surface, this degradation results in gravel packing applications with higher friction pressures than initially designed for.
[0048] The method of the invention allows for the friction reducer to be released downhole at the time it is most required, and in the place where it is needed. The release of friction reducer downhole allows for effective friction reduction in the horizontal section and during the return flow.
[0049] The canisters can be placed in the wash pipe of the gravel packing string, downstream of the packer, or where enough space is available, upstream of the packer. Pressure difference measurements monitored across the two flow paths of the packer may be used as a trigger pressure for the canister, both upstream and downstream the packer.
[0050] Canisters for use with the friction reducing agents are intended to be used downhole. Therefore, such canisters may be constructed to withstand the downhole conditions, such as high pressures (e.g., 9000 psi or 62,000 kPa) and high temperatures (e.g., 250° F. or 121° C.). The canisters of the invention may be incorporated in the housing wall or in a configuration that does not substantially reduce the opening of the lumen, as shown in FIG. 2 . Common wash pipes may have diameters between 2 and 4 in (about 5-10 cm) for use in cased holes.
[0051] With reference to FIG. 8 , an openhole gravelpack assembly 78 employing a canister in accordance with the invention is shown. A gravel slurry is pumped down tubing section 80 within an encased hole section 82 and enters the annulus 84 of the openhole section 85 via crossover section 86 , as indicated by the arrows 88 . The gravel slurry deposits gravel along the annulus 84 until a gravel pack is formed within the annulus. Clean fluid from the slurry leaks through the screen assembly 90 and returns through the annular space between the screen 90 and washpipe 89 . Return flow of the clean fluid enters the end 94 of the washpipe 89 and flows through the washpipe 89 into the annulus of the encased hole section 82 through the crossover 96 , as shown.
[0052] When the fluid pressure within the annulus between the screen 90 and washpipe exceeds a preselected level or another trigger mechanism or condition is reached, a canister 98 containing a friction reducing agent is triggered to release the friction reducing agent into the clean fluid within the annular space between the interior of the screen 90 and the exterior of the washpipe 89 , as shown at 100 .
[0053] With reference to FIG. 2 and FIG. 7 , one example of specific operations of a canister for release of friction reducing agents during gravel packing operations is as follows. When pumping the gravel packing fluids, the pressures required to pump or circulate the fluids may increase during the gravel packing operation. This may be due, for example, to the degradation of friction reducers initially added at the surface to the gravel packing fluids, fluid density or flow rate changes, or even fluid temperature. This increases the internal pressure within the internal lumen of the tube that includes the canister. The increased pressure inside the tubing pushes open the poppet valve (shown as 23 in FIG. 2 and FIG. 3 ). Referring to FIG. 7 , the hydraulic pressure 75 pushes against a plug that blocks the opening 73 of the poppet valve, allowing the pressure to be transduced to the conduit 74 to push the piston (shown as 25 in FIG. 2 and FIG. 3 ). The poppet valve may be adjusted to operate under the pressure expected downhole. When the piston 25 is pushed, it slides along the annular chamber 29 to push out the friction reducing agents stored in the annular chamber 29 . The friction reducers are thus dispensed through injection ports 28 into the annular space defined between an interior of the screen and the exterior of the tubing.
[0054] In addition to pressure activation, the activation of the canister may also be accomplished by mechanical means. Activation by mechanical means may be used to release the friction reducing agent in response to increased pressure, and in response to other conditions, such as increase fluid flow rate. As shown in FIG. 7 , a mechanical device may generate a mechanical force to push against the opening 73 of the poppet valve. The mechanical means, for example, may be a shifting tool arranged on the inside (lumen) of the tool. The shifting tool may be pulled or pushed to activate the canisters. The use of a shifting tool to activate a device downhole is well known in the art.
[0055] FIG. 9 shows a schematic illustrating one embodiment of a mechanical means that can be used to control the activation of a canister of the invention. As shown, a stopping mechanism 91 prevents the piston 93 from sliding to the right. The piston 93 is biased to move to the right in this illustration by a biasing spring 92 (or a similar mechanism). If a shifting tool (or other device) is used to release the stopping mechanism 91 , the free-floating piston 93 in the canister will start to move to dispense the content of the canister. This is only one example of how a mechanical means may be used with a canister of the invention. One of ordinary skill in the art would appreciate that other variations are possible without departing from the scope of the invention.
[0056] In accordance with some embodiments of the invention, multiple canisters may be incorporated in a single wash pipe (or other tubings) or a downhole tool. The multiple canisters (or cartridges) may be filled with same or different friction reducing agents, chemicals or reagents. These cartridges may have individual pistons for deploying chemicals when pressured against or shifted by set down or pull force by using a shifting tool.
[0057] FIG. 10 illustrates a general process for performing a downhole operation using a canister of the invention. As shown, a tool for performing the downhole operation is first set downhole (step 101 ). The tool includes a canister of the invention, which may store the friction reducing agents for use downhole. Then, some operations may be performed using the tool (step 102 ). When deployment of the friction reducing agent is desired, the canister is activated (step 103 ). Activation of the canister, as noted above, may be accomplished by various means. After deployment of the friction reducing agents, the downhole operations may be continued if needed (step 104 ). Afterwards, the tool may be pulled out of the hole. The process illustrated in FIG. 10 is for illustration purpose only. One of ordinary skill in the art would appreciate that modifications to this process are possible without departing from the scope of the invention.
[0058] The addition of friction reducing agents downhole may be “on demand” by a signal from the surface. The canisters allow concentrated friction reducers to be released in the zones of their intended use. This may also save time and costs because there is no need to pump a large volume from the surface. Canisters of the invention may be constructed on any downhole tool or tubings. They can be configured to have minimal impact on the normal operations downhole or to have minimal impact on fluid flow resistance. Multiple canisters may be used, allowing deployment of different chemicals in different zones and/or different times, including some with non-friction reducing agents.
[0059] While the invention has been shown in only some 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 and modifications without departing from the scope of the invention. Accordingly, it is appropriate that the appended claims be construed broadly and in a manner consistent with the scope of the invention.
|
A method of introducing friction reducing agents within a wellbore penetrating a subterranean formation during a gravel packing operation is accomplished by providing a length of tubing located downhole within the wellbore for conducting fluids within the wellbore through the tubing during circulating of gravel packing fluids introduced from the surface within the wellbore. At least a portion of the tubing is surrounded by a screen for screening out particulate matter during the gravel packing operation. An annular space is defined between an interior of the screen and the exterior of the tubing. A friction reducing agent is dispensed from a dispensing apparatus that locates downhole with the tubing. The dispensing apparatus includes a housing and a chamber disposed within the housing that has one or more outlets that open into the annular space defined by the screen and tubing for dispensing the friction reducing agent. The dispensing apparatus further includes a piston and a trigger mechanism for actuating the piston. When the trigger mechanism is activated to actuate the piston, the friction reducing agent is dispensed through the one or more outlets at a position downhole remote from the surface during the circulating.
| 4
|
BACKGROUND
Most TDMA based wireless personal area network (WPAN) or wireless local area network (WLAN) technologies divide a fixed time period into contention free periods and contention periods. For example, in the Institute for Electrical and Electronic Engineers (IEEE) 802.15.3c standard, the fixed time period is called superframe (SF), the contention free period is called CTA (channel time allocation) period, and the contention period is called CAP (contention access period). CTAs are scheduled by a central controller called a PNC (piconet controller) and a CTA is exclusively allocated to a pair of devices. CAP periods are also allocated by the PNC, but the difference from the CTA is that any device can access the medium during CAP periods by contending with each other (e.g., through CSMA/CA). A PNC may be also known as an Access Point (AP) and SF may be also known as Beacon Interval (BI) in the IEEE 802.11 standard. Similarly, CAP may be also known as Contention-Based Period (CBP) and CTA may be also known as Service Period (SP).
Since a CTA is allocated exclusively to a subset of devices in the network, other devices not involved in the communications in that CTA can go to sleep to minimize their energy consumption. However, during CAPs, all the active devices (i.e., the devices which are not in a sleep state) in the network are required to stay awake and cannot go to sleep because any device may try to communicate with any other device, including the PNC, during the CAPs. Therefore, active devices and PNC cannot save power during CAPs.
A similar problem is also present in two other mechanisms. The first is related to CTA truncation and extension. The CTA truncation is a mechanism that releases an unused CTA time period and the CTA extension is a mechanism that extends CTA time if additional time is needed. Since a device that wants to truncate or to extend CTA needs to inform or request to the PNC, the availability of the PNC has to inform the devices. Otherwise, the devices may transmit a CTA truncation or extension messages to the PNC without knowing that the PNC is unavailable.
The second is during the polling period for the dynamic bandwidth allocation mechanism. During the polling period of the dynamic bandwidth allocation, the PNC polls associated devices during unused channel time of a superframe to obtain bandwidth requests from the devices for the purpose of dynamic allocation of the unused channel time. For this period, the PNC needs information whether the devices will be available or not (e.g., device may be in power saving mode). Otherwise, the PNC may transmit polling messages to the devices without knowing that the devices are not available.
Thus, a strong need exists for techniques for device and piconet controller availability notification in wireless personal area and wireless local area networks.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject matter regarded as the invention is particularly pointed out and distinctly claimed in the concluding portion of the specification. The invention, however, both as to organization and method of operation, together with objects, features, and advantages thereof, may best be understood by reference to the following detailed description when read with the accompanying drawings in which:
FIG. 1 illustrates a Channel Time Request (CTRq) frame format according to one embodiment of the present invention;
FIG. 2 illustrates a CTA information element according to one embodiment of the present invention;
FIG. 3 illustrates a PNC availability IE format according to one embodiment of the present invention;
FIG. 4 illustrates a PNC availability information field format according to one embodiment of the present invention.
FIG. 5 illustrates a DEV Availability IE format according to one embodiment of the present invention;
FIG. 6 illustrates a DEV availability information field format according to one embodiment of the present invention; and
FIG. 7 illustrates a DEV Availability IE format according to one embodiment of the present invention.
It will be appreciated that for simplicity and clarity of illustration, elements illustrated in the figures have not necessarily been drawn to scale. For example, the dimensions of some of the elements are exaggerated relative to other elements for clarity. Further, where considered appropriate, reference numerals have been repeated among the figures to indicate corresponding or analogous elements.
DETAILED DESCRIPTION
In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those skilled in the art that the preset invention may be practiced without these specific details. In other instances, well-known methods, procedures, components and circuits have not been described in detail so as not to obscure the present invention.
Although embodiments of the invention are not limited in this regard, discussions utilizing terms such as, for example, “processing,” “computing,” “calculating,” “determining,” “establishing”, “analyzing”, “checking”, or the like, may refer to operation(s) and/or process(es) of a computer, a computing platform, a computing system, or other electronic computing device, that manipulate and/or transform data represented as physical (e.g., electronic) quantities within the computer's registers and/or memories into other data similarly represented as physical quantities within the computer's registers and/or memories or other information storage medium that may store instructions to perform operations and/or processes.
Although embodiments of the invention are not limited in this regard, the terms “plurality” and “a plurality” as used herein may include, for example, “multiple” or “two or more”. The terms “plurality” or “a plurality” may be used throughout the specification to describe two or more components, devices, elements, units, parameters, or the like. For example, “a plurality of stations” may include two or more stations.
Embodiments of the present invention provide mechanisms and techniques that may provide information whether devices and a PNC will be active during the following periods:
1) CAP;
2) Dynamic bandwidth allocation; and
3) CTA truncation or extension period.
In an embodiment of the present invention, this information may be provided on a superframe basis so that the PNC or the devices can go to sleep during these periods without performance degradation.
Further, embodiments of the present invention provide a mechanism that enables a PNC to inform the availability of the PNC to associated devices in the network at the start of a superframe. Whether the PNC will stay awake or go to sleep during a part of a superframe depends on whether there are any services to provide in the network or not during that period of time. The PNC shall stay awake if there are services to provide in the network to maintain the network performance; otherwise the PNC will go to sleep to minimize its energy consumption.
The information concerning whether the PNC has to be involved in the communications between the devices during a specific superframe may be provided by the devices in the network. For example, if a device wants to communicate with the PNC during a CAP, the device may inform the PNC that during the CAP it will try to communicate with the PNC. With this information from the device, the PNC shall stay awake during the CAP; otherwise it may go to sleep.
This can also be applied to the mechanisms such as CTA truncation and extension in a very similar manner. Since the PNC has to be involved in the CTA truncation and extension, if the devices expect their CTAs to be truncated or extended, this information needs be delivered to the PNC when the devices are requesting a CTA allocation. If the device sends a CTA request (bandwidth allocation request) with an indication that it plans to truncate or extend its allocated CTA, the PNC shall stay awake during that CTA; otherwise, the PNC can go to sleep.
Turning now to FIG. 1 , generally as 100 , is an example of the CTA request frame format. As can be seen, a device would indicate to the PNC through the Truncatable and Extensible fields that it plans to truncate or extend this particular CTA. The PNC would then use this information to stay awake or go to sleep during this particular CTA.
After a CTA request, the PNC needs to update its scheduling information and broadcast it in its next superframe. The frame format used for this purpose is shown in FIG. 2 at 200 . As can be seen, the PNC also includes in its schedule the information whether or not a given CTA is truncatable and/or extensible.
Once the information is provided by the devices to the PNC, the PNC provides the PNC availability information to the devices. For example, the PNC availability information can be delivered in an information element (IE) (e.g. “PNC Availability IE” (PAIE)) from the PNC to the devices. The availability of the PNC may be specified either for all the CAPs in the superframe or for each CAP separately. For CTAs, the PNC availability will be specified for each CTA implicitly by the CTA IE as shown in FIG. 2 . If the PNC sets either Truncatable or Extensible bit (shown in FIG. 2 ) of a CTA block to 1, the PNC shall stay awake during that CTA period; otherwise the PNC may go to sleep during that period.
An example of PAIE frame format is shown in FIG. 3 , generally as 300 , and the PNC availability information field is shown in FIG. 4 , generally as 400 . If the PNC is available during the CAPs in the superframe, the CAP bit is set to 1; otherwise it is set to 0.
Some embodiments of the present invention also provide a mechanism that provides the availability information of the devices to the PNC so that the PNC knows which devices are available during the CAPs or the polling period of the dynamic bandwidth allocation mechanism.
Similar to PAIE (PNC Availability IE) provided above, further embodiments of the present invention provide device availability information that may be conveyed in an IE (e.g. “DEV Availability IE” (DAIE)) and delivered from the devices to the PNC. The availability of the devices may be specified either for all the CAPs in the superframe or for each CAP separately. The availability of the devices may be separately specified for the polling period of the dynamic bandwidth allocation. An example of DAIE frame format is shown in FIG. 5 , generally as 500 , and the DEV availability information field is shown in FIG. 6 , generally as 600 . If the DEV is available during the CAPs in the next superframe, the CAP bit is set to 1; otherwise it is set to 0. If the DEV is available for the polling, the dynamic bandwidth request bit is set to 1; otherwise it is set to 0.
We may also specify the index of the superframe in which a device will be available during the CAPs or for polling by adding another field indicating the index of the superframe as provided generally as 700 of FIG. 7 .
While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents may occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
|
An embodiment of the present invention provides a method, comprising notifying of device and piconet controller (PNC) availability in wireless personal area network (WPAN) and/or wireless local area networks (WLAN) at the start of a superframe, wherein whether the PNC will stay awake or go to sleep during a part of the superframe depends on whether or not there are any services to provide in the WPAN and/or WLAN during a given period of time, and wherein the PNC shall stay awake if there are services to provide in the WPAN and/or WLAN to maintain network performance, otherwise the PNC will go to sleep to minimize its energy consumption.
| 8
|
CROSS REFERENCE TO OTHER APPLICATIONS
This application is a continuation-in-part of patent application Ser. No. 210,197, filed on Nov. 26, 1980 and entitled "Control System for Sewing Machine", now pending, which is a continuation-in-part of patent application Ser. No. 168,525, filed July 4, 1980 and entitled "Control System For Sewing Machine", now U.S. Pat. No. 4,359,953.
TECHNICAL FIELD
The present invention relates generally to a control system to adapt a sewing machine for semi-automatic operation. More particularly, this invention is directed to an adaptive sewing machine control system incorporating a microprocessor controller in combination with a stitch counter, an edge sensor and stitch length control apparatus to achieve more precise seam lengths and end points.
BACKGROUND ART
In the sewn goods industry, where various sections of material are sewn together to fabricate products, reasonably precise seam lengths and/or end points are often necessary for proper appearance and function of the finished products. For example, the top stitch seam of a shirt collar must closely follow the contour of the collar and terminate at a precise point which matches with the opposite collar. In the construction of shoes, accurate seam lengths must be maintained when sewing together the vamps and quarter pieces to achieve strength as well as pleasing appearance. Seams with imprecise lengths and/or end points can result in unacceptable products or rejects, thus causing waste and further expense.
Achieving consistently accurate seam lengths and/or end points at high rates or production, however, has been a long standing problem in the industry. Sewing machines traditionally have been controlled by human operators. Rapid coordination of the operator's eyes, hands and feet is necessary to control a high speed industrial sewing machine. Considerable practice, skill and concentration are required to sew the same type of seam with consistent accuracy time and time again.
Since such sewing operations tend to be repetitive and, therefore, lend themselves to automation, systems have been developed heretofore for automatically controlling sewing machines. U.S. Pat. Nos. 4,108,090; 4,104,976; 4,100,865 and 4,092,937, assigned to the Singer Company, are representative of such devices. Each of these patents discloses a programmable sewing machine with three operational modes: manual, auto and learning. Control parameters are programmed into the system as the operator manually performs the initial sewing procedure for subsequent control of the sewing machine in the auto mode.
While these programmable sewing machines have several advantages over manually controlled machines, they are not without their disadvantages. The prior systems rely upon overall stitch counting to determine seam lengths and/or end points, variations in which can be caused by several factors. First, cloth or fabric is a relatively elastic material which can be stretched or contracted by the operator during the sewing procedure, thereby causing changes in average stitch lengths which can accumulate into a significant deviation over the length of a seam. Second, slippage can occur as the material is advanced between the presser foot and feed dog of the sewing machine, thereby causing further deviations in the length of the seam. Also, such slippage can vary in accordance with the speed of the sewing machine. Third, any deviations between the paths of the desired seams versus the paths of the seams as programmed can also contribute to inaccurate seam lengths. Variations in seam lengths become greatest with long seams and elastic material.
Thus, although the programmable sewing machines of the prior art offer higher speeds of operation, they have not been completely satisfactory in those applications where precise seam lengths and end points are required.
Another approach to the problem of stopping a sewing machine precisely and consistently at a given point was generally proposed in an article entitled "Fluidics for the Apparel Industry", Journal of the Apparel Research Foundation, Vol. 3, 1969. This article suggested that a sensor might be mounted in the presser foot of the sewing machine for sensing the edge of the material in order to initiate countdown of a preset number of stitches for stopping the machine at the desired point. This proposal, however, does not take into account the fact that edge conditions are dependent upon the seam and type of workpiece. No single preset number of stitches works well with pieces of different shapes or similar pieces of different sizes. As far as Applicants are aware, this proposal never has been embodied in a programmable sewing system.
U.S. patent application Ser. No. 168,525, filed July 14, 1980 and entitled "Control System for Sewing Machine" and Ser. No. 210,197, filed Nov. 26, 1980, and entitled "Control System for Sewing Machine", both assigned to assigner, disclose apparatus for improving the accuracy of seam lengths. However, even with the improved apparatus disclosed in these applications, the accuracy of the stitch length or seam end point is approximately ±1/2 stitch length. For many garments, this accuracy is not satisfactory and may result in unacceptable visual defects, as for example, shirt collars which have uneven seam end points.
A need therefore has arisen for an improved adaptive sewing machine control system utilizing a combination of stitch counting, edge detection techniques and stitch length control to obtain more accurate seam lengths and/or end points.
SUMMARY OF INVENTION
The present invention comprises a sewing machine control system which substantially improves the seam length accuracy to ±1/4 stitch length or better.
In accordance with the invention, there is provided a system including a microprocessor controller which can be programmed with a taught a sequence of sewing operations by the operator in one mode, while sewing the initial piece, for automatically controlling the machine during subsequent sewing of similar pieces of the same or different sizes in another mode. The semi-automatic system herein does not rely upon either pure stitch counting or material edge detection alone, but rather utilizes a combination of these techniques together with other features to achieve more accurate seam length and end point control. The present system further includes apparatus for varying the length of the last stitch sewn in order to improve the seam end point accuracy.
More specifically, this invention comprises a microprocessor-based control system for an industrial sewing machine. The system has manual, teach and auto modes of operation. In the preferred embodiment, one or more sensors are mounted in front of the presser foot for monitoring edge conditions of the material at the end of each seam. In the teach mode, operating parameters are programmed into the controller by the operator while manually sewing the first piece. For each seam, the number of stitches x sewn at the time of the last status change in the sensors, the sensor pattern after x stitches had been sewn, and the total number of stitches y sewn in the seam are recorded along with sewing machine and auxiliary control inputs. In the auto mode, the number of stitches sewn in each seam is monitored as the count passes a window set up around x until the characteristic sensor pattern including edge detection is seen, at which time y-x additional stitches are sewn to complete the seam. The amount of stitch completion at the time of detection of the material edge in monitored, and the reverse mechanism of the sewing machine is actuated in order to control the length of the last seam stitch to the desired length.
BRIEF DESCRIPTION OF DRAWINGS
A more complete understanding of the invention can be had by reference to the following Detailed Description taken in conjunction with the accompanying Drawing, wherein:
FIG. 1 is a perspective view of a programmable sewing system incorporating the invention;
FIG. 2 is a front view illustrating placement of the edge sensor relative to the sewing needle;
FIG. 3 is a sectional view taken along lines 3--3 of FIG. 2 in the direction of the arrows;
FIG. 4 is an end view of the sewing system illustrating the automatic control apparatus of the sewing machine reverse mechanism;
FIG. 5 is a graph illustrating the degrees of rotation of a sewing machine motor plotted against the length of a resulting stitch;
FIG. 6a illustrating the prior art sewing of a seam wherein the end of the last stitch ends exactly at the desired offset from the edge of the material;
FIG. 6b illustrates a graphical representation of the prior art sewing of a seam wherein the end of the last stitch passes the desired offset from the material edge by one-half stitch length;
FIG. 6c is a graphical illustration of the prior art sewing of the seam wherein the end of the last stitch terminates approximately one-half stitch length from the desired offset from the material edge;
FIG. 7a is a graphical illustration illustrating the sewing of a seam in accordance with the present invention in which the end of the last stitch terminates approximately one-fourth stitch length past the desired offset from the material edge;
FIG. 7b is a graphical illustration of the present invention wherein the end of a last stitch terminates approximately one-fourth stitch away from the desired offset from the material edge; and
FIG. 8 is a flow chart illustrating the operation of the present invention to provide plus and minus one-fourth stitch accuracy.
DETAILED DESCRIPTION
Referring now to the Drawings, wherein like reference numerals designate like or corresponding parts throughout the views, FIG. 1 illustrates a semi-automatic sewing system 10 incorporating the invention. System 10 is a microprocessor-based system adapted to extend the capabilities of a sewing machine by enabling the operator to perform sewing procedures on a manual or semi-automatic basis, as will be more fully explained hereinafter.
System 10 includes a conventional sewing machine 12 mounted on a work stand 14 consisting of a table top 16 supported by four legs 18. Sewing machine 12, which is of conventional construction, includes a spool 20 containing a supply of thread for stitching by a reciprocable needle 22 to form a seam in one or more pieces of material. Surrounding needle 22 is a vertically movable presser foot 24 for cooperation with movable feed dogs (not shown) positioned within table top 16 for feeding material past the needle.
A number of standard controls are associated with sewing machine 12 for use by the operator in controlling its functions. A handwheel 26 is attached to the drive shaft (not shown) of machine 12 for manually positioning needle 22 in the desired vertical position. Sewing speed is controlled by a speed sensor 15 which is actuated by a foot treadle 28, which functions like an accelerator. Vertical positioning of presser foot 24 can be controlled by heel pressure on foot treadle 28 which closes a switch 19 in speed sensor 15, which in turn causes the presser foot lift actuator 30 to operate. A leg switch 32 is provided for controlling the sewing direction of machine 12 by causing operation of reverse sew lever actuator 17. An important aspect of the present invention is the stop member 13 which prevents the reverse sew lever actuator 17 from being fully operated as will be subsequently described.
A toe switch 34 located adjacent to foot treadle 28 controls a conventional thread trimmer (not shown) disposed underneath the throat plate 36 of machine 12. Foot switch 38 on the other side of foot treadle 28 comprises a one-stitch switch for commanding machine 12 to sew a single stitch.
It will thus be understood that sewing machine 12 and its associated manual controls are of substantially conventional construction, and may be obtained from several commercial sources. For example, suitable sewing machines are available from Singer, Union Special, Pfaff, Consew, Juki, Columbia, Brother or Durkopp Companies.
In addition to the basic sewing machine 12 and its manual controls, system 10 includes several components for adapting the sewing machine for semi-automatic operation. One or more sensors 40 are mounted in laterally spaced-apart relationship in front of needle 22 and presser foot 24. A drive unit 42 comprising a variable speed direct drive motor, sensors for stitch counting and an electromagnetic brake for positioning of needle 22, is attached to the drive shaft of sewing machine 12. A main control panel 44 supported on a bracket 46 is provided above one corner of work stand 14.
On one side of work stand 14 there is a pneumatic control chassis 48 containing an air regulator, filter and lubricator for the sewing maching control sensors, pneumatic actuators and other elements of system 10. All of these components are of known construction and are similar to those shown in U.S. Pat. Nos. 4,108,090; 4,104,976; 4,100,865 and 4,092,937, the disclosures of which are incorporated herein by reference.
A controller chassis 50 is located on the opposite side of work stand 14 for housing the electronic components of system 10. Chassis 50 includes a microprocessor controller 51, appropriate circuitry for receiving signals from sensors and carrying control signals to actuators, and a power module for providing electrical power at the proper voltage levels to the various elements of system 10. The microprocessor controller 51 may comprise a Zilog Model Z-80 microprocessor or any suitable unit having a read only memory (ROM) and random access memory (RAM) of adequate storage capacities. An auxiliary control panel 52 is mounted for sliding movement in one end of chassis 50. Operation and function of the foregoing components will become more clear in the following paragraphs.
Referring now to FIGS. 2 and 3, further details of edge sensors 40 and their cooperation with needle 22 can be seen. If desired, only one edge sensor 40 can be used with sewing machine 12; however, complex shaped parts may require two or even three edge sensors located in laterally spaced-apart relationship in front of the needle. Sensors 40 can be mounted directly on the housing of sewing machine 12, or supported by other suitable means. As illustrated, each sensor 40 comprises a lamp/photosensor which projects a spot of light 40a onto a reflective tape strip 54 on throat plate 36. The status of each sensor 40 is either "on" or "off" depending upon whether the light beam thereof is interrupted, such as by passage of the trailing edge or discontinuity of the particular piece of material.
It will be appreciated that a significant feature of the present invention comprises usage of at least one and possibly a plurality of sensors 40 positioned in mutually spaced relationship ahead of needle 22 of sewing machine 12. Sensors 40 indicate whether or not the end of a particular seam is being approached. The condition of at least one sensor 40 changes as the trailing material edge passes thereunder to indicate approach of the seam end point. Sensors such as the Model 10-0672-02 available from Clinton Industries of Carlstadt, N.J., having been found satisfactory as sensors 40; however, infrared sensors and emitters, or pneumatic ports in combination with back pressure sensors could also be utilized, if desired. Any type of on/off sensor capable of detecting the pressure or absence of material a preset distance in front of needle 22 can be utilized with apparatus 10 since the exact mode of their operation is not critical to practice of the invention. Sensors 40 can be mounted directly on the housing of sewing machine 12 or on an adjustable mounting assembly.
Circuitry is provided in chassis 50 which detects the output of sensors 40 in order to generate electrical signals representative of the material edge. The controller 51 is responsive to such edge detection for allowing a selected number of stitches to be sewn after the edge detection. The controller 51 also determines the amount of the currently sewn stitch which has been completed at edge detection. The amount of the stitch is determined in response to the sewing machine motor rotation. In response to the amount of the stitch sewn at edge detection, the controller 51 controls the reverse mechanism of the machine in order to control the length of the last stitch sewn.
As described in the previously identified co-pending patent applications, the present system may first be operated in a teaching mode and thereafter operate in an automatic mode. The system may be taught in the teaching mode to sew x-y stitches after the material edge is detected. Thereafter, when the system is operated in the automatic mode, the edge of the material will be automatically detected by the sensor and the machine will then automatically sew x-y stitches and then terminate the seam. In this manner, automatic operation of the system may be provided in order to increase the speed and accuracy of the system without required human intervention. The present system operates is essentially the same manner as the systems described in the two co-pending patent applications, with additional improvements and accuracy being provided by the present invention as will be subsequently shown.
In operation of the system thus described, as a seam is sewn by the machine, the number of stitches from the starting point are counted by the encoder within drive unit 42. The reflective tape 54 will be covered by the material and the beams of the sensors 40 are blocked by the material. When the edge of the material moves past the reflective tape 54, the sensor beams are reflected from the reflective tape 54 and sensed. This provides the system with an indication of the location of the edge of the material. The system may then sew a predetermined number of stitches in order that the seam ends at a preselected location. In addition, auxiliary devices such as stackers, trimers, guides, and zig-zag lever actuators may be controlled in response to the material edge detection.
For a more detailed understanding and description of the operation of the system shown in FIGS. 1-3, reference is made to the co-pending patent applications Ser. Nos. 168,525 and 210,197, previously noted. The Specifications and Drawings of these applications are incorporated herein and may be referred to for a more detailed description of the operation of the system.
In the operation of the system described in copending patent applications Ser. Nos. 168,525 and 210,197, it was not possible to obtain accuracy better than plus or minus one-half stitch is determining the absolute end point of a seam. With the utilization of the present system to be described, accuracy in terminating a seam may be provided within plus or minus one-fourth stitch.
Referring to FIG. 4, an enlarged view of the reverse sew lever actuator assembly is illustrated. A pneumatic cylinder 1 is actuated in response to the leg switch 32 in order to pivot the reverse sew lever 17 about a pivot point 23. Alternatively, cylinder 21 may be actuated by a switch in chassis 48 as will be subsequently described. The lever 17 is illustrated in the solid line position in its normal operating position in the forward sew mode. When the cylinder 21 is actuated, the lever 17 is pivoted about pivot point 23 in order to place the machine in the reverse sew mode. Without the stop member 13, the lever 17 would normally be moved to the reverse sew mode as illustrated by the dotted line position 17'. However, because of the stop member 13, the lever 17 may only be moved to the dotted line position 17" adjacent the stop member 13. Consequently, according to the present invention, the reverse sew lever actuator is limited to approximately one-quarter its normal movement. This enables the sewing operation of the machine to be controlled to a greater accuracy then without the stop member 13.
FIG. 5 is a graph illustrating the length of a stitch displacement versus the rotation of the motor of the sewing machine. In an industrial sewing machine, the transport mechanism comprises a feed dog and presser foot. The amount by which the material being sewn is advanced for each stitch, termed stitch length, can be controlled by mechanical adjustments on the sewing machine. FIG. 5 illustrates the interval over 360° rotation of the sewing machine motor during which the stitch formation occurs. The interval over which the stitch formation occurs varies depending upon the machine type, such as drop feed, needle feed, top feed and the like. FIG. 5 illustrates material advancement over approximately 120° of the motor rotation of a typical sewing machine such as shown in FIG. 1. As shown in FIG. 5, the stitch is not begun until the motor has rotated approximately 60°. The stitch is then formed until it is completed after the sewing machine motor has completed approximately 180° rotation. The last 180° rotation of the sewing machine motor enables the machine to ready for the formation of the next stitch. The interval of the motor rotation is dynamically detected by the controller 51 over which stitch formation occurs, in order to determine the percentage of the stitch completed at edge detection.
FIGS. 6a-6c illustrate the operation of prior art devices such as are exemplified by the stitch controllers disclosed in Ser. Nos. 168,525 and 210,197, previously noted. FIG. 6a illustrates the sewing of a seam comprising a number of stitches utilizing a conventional sewing machine. In the example shown in FIG. 6a, the seam was started at the correct location relative to the material edge so that the end of the last stitch occurred exactly on the desired offset from the material edge. For example, if it were desired to end the seam one-quarter inch from the material edge, the operation shown in FIG. 6a was such that the seam ended exactly one-quarter inch from the material edge.
FIG. 6b illustrates the operation of a prior art device wherein the seam was started too close to the material edge, or wherein problems in material compaction or stretch occurred. Thus, the seam ended approximately one-half stitch past the desired offset from the material edge. If in the above example, the stitch length was 1/4 inch, the seam would end approximately one-eighth inch from the material edge, rather than the desired one-quarter inch from the material edge. It will be understood that it is not always possible to begin a seam at the exact desired position, and thus provisions must be made to end the seam as closely as possible to the desired offset from the material edge. With prior devices, it was not generally possible to obtain better than plus one-half stitch accuracy in case the exact starting point was not obtained during sewing. Even when the exact starting point is obtained, due to material stretching and the like, inaccuracies relative to the desired offset from the material edge often occur in actual sewing.
FIG. 6c illustrates the sewing of the seam wherein the seam ended approximately one-half stitch away from the desired offset from the material edge. In the previously noted example, the ending of the seam shown in FIG. 6c might be three-eighths inch away from the material edge rather than the desired one-fourth inch from the material edge.
It will be understood that the examples shown in FIGS. 6a-6c provided an accuracy of plus or minus one-half stitch length because it was not possible to vary the length of the stitch. In accordance with the present operation, the length of a stitch may be varied in order to provide greater accuracy. Such improved accuracy is required in certain sewing operations, such as top stitched collars, in order to provide the desired visual characteristics of the garment.
FIGS. 7a-7b illustrate operation of the present invention wherein accuracy of plus or minus one-fourth stitch may be provided. In accordance with the present invention, the edge detector described and shown in FIGS. 1-3 detects the edge of the material in order that the seam length can be stopped at a given distance from the material edge. The present system is originally taught by the operator to sew a given number of stitches y-x in a seam after the edge of the material is detected. When the operation is repeated in the automatic sewing mode, as described in the prior patent applications noted above, the system will sew until the edge is detected, and will then sew y-x stitches before terminating the seam. Depending upon the percentage of the stitch which has been sewn at the time of detection of the material edge, the last stitch sewn may be varied in order to provide increased accuracy to this seam termination.
The present system provides the capability to sew a specified number x of stitches, a specified number of stitches plus one additional stitch (x+1), or a specified number of stitches plus one-half additional stitch (x+1/2). An important aspect of the present invention is the ability to sew x+1/2 additional stitches by utilization of the reverse mechanism on the sewing machine as shown in FIG. 4.
The reverse mechanism operates in a linear fashion such that when then the mechanism is fully actuated as shown by position 17' in FIG. 4, a stitch is sewn in the reverse direction. The stitch length in the reverse direction will roughly correspond to the stitch length normally sewn in the forward direction when the lever is not depressed. If the reverse lever is approximately fifty percent depressed, the material is not advanced nor reversed during the stitch formation and a "condensed" stitch with zero length is formed. If the reverse lever 17 is moved only approximately twenty-five percent of its full range of movement, due to the positioning of the stop member 13, a forward stitch fifty percent of the normal stitch length is formed. Consequently, the addition of the stop member 13 causes a one-half length stitch to be sewn when the cylinder 21 actuates the reverse sew lever 17.
The controller 51 determines whether or not x, x+1/2 or x+1 additional stitches shall be taken after the sensor detects the material edge. The system periodically interrogates the edge sensor of the system during the formation of each stitch to determine if the sensor detects the material edge during the stitch. Sewing is continued until the sensor detects the edge. If the sensor detects the edge during the first twenty-five percent formation of the stitch being sewn, the system will sew x additional stitches after the current stitch is completed. If the sensor detects the edge of the material in the interval of twenty-five to seventy-five percent formation of the stitch length, the system will sew x+1/2 additional stitches. If the sensor detects the material edge during the last twenty-five percent of the stitch length, the system will sew x+1 additional stitch.
The x+1/2 and x+1 stitch cases are alike in that the system sews x+1 additional stitchs in both cases. However, in the x+1/2 case, the reverse mechanism 17 is actuated during the final stitch with the reverse mechanism constrained by the stop 13 such that the lever 17 cannot travel more than approximately twenty-five percent of its maximum travel. This causes the last stitch to be approximately one-half the normal stitch length.
FIGS. 7a and 7b illustrate how operation of the present system can improve the accuracy of the seam end point. In FIG. 7a, the seam was started at a point that the end of stitch 69 is slightly over 1/4 stitch away from the desired offset. Thus, the last stitch is varied in length by 1/2 such that the seam ends within 1/4 stitch of the desired offset. In FIG. 7b, the length of the last stitch is also reduced by one-half such that the seam ends approximately one-fourth stitch length away from the desired offset from the material edge.
FIG. 8 illustrates a flow diagram illustrating the operation of the present invention. The steps are implemented by suitable programming of the microprocessor controller 51. The program is suitable for adaptation to the Zylog Z-80 microprocessor and may be written into Z-80 assembly language in a manner known to the art.
At step 70, one stitch is taken. A determination is made at step 72 as to whether or not the edge sensor shown in FIGS. 2 and 3 has changed state during the last switch. If not, another stitch is taken at step 70. If it is determined that the sensor has changed during the last stitch, thereby indicating the detection of the material edge, D act is set in a register at step 74. D act is equal to the encoder count which represents the motor rotation angle when the sensor changed.
At step 76, a determination is made by the program as to whether or not D stop -D start is greater than or equal to zero. D start equals the encoder count value when the stitch movement begins. D stop equals the encoder count value when the stitch movement ends. If the decision at step 76 is no, the motor angle values D act , D stop and D start are adjusted at step 78 for numerical analysis reasons. Specifically, steps 76 and 78 are provided to enable the system to accommodate various machines having different feeding intervals during the rotation of the motor. At step 78, D start is set to zero, D stop is set to D stop +(360°-D start ) and D act is set to D act +360°-D start ).
If D stop -D start is greater than or equal to zero, the determination is made at step 79 as to whether or not D act is less than or equal to D T/4 +D start . In other words, the decision is made at step 79 as to whether or not the material edge was detected when the stitch was less than twenty-five percent completed. If the answer is yes, x additional stitches are taken by the system at step 80. If the edge of the material was not detected within the first one-quarter of the stitch length, a decision is made at step 82 as to whether or not D act is less than or equal to 3D/4T+D stop . In other words, a decision is made at step 82 as to whether or not the material edge was detected in the last twenty-five percent of the stitch. If so, x+1 additional stitches are taken at step 84 by the system.
If it is determined at steps 78 and 82 that the material edge was detected between twenty-five percent and seventy-five percent of the completion of the switch, x additional stitches are taken at step 86 and then the reverse mechanism is actuated at step 88 and one additional stitch is taken. This provides an additional one-half stitch to provide improved accuracy to the system.
It will be understood that the reverse mechanism could be actuated a greater or lesser amount than approximately twenty-five percent in order to decrease or increase the length of the stitch taken by the system. Moreover, it will be understood that instead of decreasing the last stitch length by one-half, the last two stitches could be reduced in length to three-fourths of their original length. Other variations involving reduction of the length of the stitch by movement of the reverse lever for predetermined amounts will be accomplished by the present invention.
It will thus be seen that the present system periodically interrogates the edge sensor as stitches are being formed in order to determine the state of formation of a stitch when the edge of the material is detected. Depending upon the amount of stitch formed at the time of edge detection, a predetermined number of additional stitches plus one stitch if necessary are taken by the system with the length of one or more of the stitches varied in order to provide improved accuracy.
Whereas the present invention has been described with respect to specific embodiments thereof, it will be understood that various changes and modifications will be suggested to one skilled in the art, and it is intended to encompass such changes and modifications as fall within the scope of the appended claims.
|
An adaptive semiautomatic sewing system (10) comprises a sewing machine (12), a drive unit (42) including a variable speed motor and encoder for counting stitches sewn and for sensing the rotation of the motor, at least one material edge sensor (40) mounted ahead of the needle (22) of the sewing machine, and a microprocessor controller (51) coupled to the sewing machine controls. The system (10) has manual, teach and auto modes of operation. In the teach mode, control parameters for each seam are stored as the operator sews the initial piece. Accurate control of seam lengths and end points is achieved by initiating countdown of a variable number of final stitches responsive to detection of the material edges by the sensors (40). In dependence upon the amount of the stitch which has been sewn upon edge detection, the reverse lever (17) is moved against stop member (13) in order to reduce the length of the last stitch sewn in order to improve the accuracy of the seam end point.
| 3
|
This is a divisional of application Ser. No. 911,866, filed Jul. 10, 1992, now U.S. Pat. No. 5,380,817, granted Jun. 13, 1994.
FIELD OF THE INVENTION
This invention relates to a process for preparing polysuccinimides. In particular, the present invention relates to a process for preparing polysuccinimides from aspartic acid, and optionally other amino acids, in poly(alkylene glycol).
BACKGROUND OF THE INVENTION
Several methods are known for obtaining polysuccinimide, which when hydrolyzed to form the corresponding poly(amino acid) is useful as an absorbent, hard-surface cleaner, water-treatment additive for boiler waters and cooling towers and as a detergent additive acting as a builder, anti-filming agent, dispersant, sequestering agent and encrustation inhibitor. However, all of the previously known methods for preparing polysuccinimide suffer from the drawbacks of excessively long process times, expensive starting materials, or require the handling of solid materials which poses many difficulties in a manufacturing environment.
U.S. Pat. No. 5,057,597 to Koskan discloses a solid-phase process for preparing polysuccinimide by fluidizing an amino acid with agitation in a nitrogen atmosphere at a temperature of at least 180° C. for three to six hours. The resultant polysuccinimide is then hydrolyzed to form a poly(amino acid).
U.S. Pat. No. 4,839,461 to Boehmke, et al. discloses a process for preparing poly(aspartic acid) by combining maleic acid or maleic anhydride and an ammonia solution in a molar ratio of 1:1-1.5. The mixture is then heated to 120°-150° C. and the resulting solution of ammonium salt and maleic acid is evaporated, leaving a crystal mash. The crystal mash is then melted, during which time the waters of condensation and crystallization distill off. A porous mass of poly(aspartic acid) results. The entire process requires six to eight hours to complete.
Japanese Patent 52-0088773 B assigned to Ajinomoto, discloses a solvent-based process for the preparing poly(aspartic acid). The process described therein utilizes a hydrohalic acid salt of aspartic acid anhydride in one or more organic solvents. The solvents disclosed are organic acids such as propionic acid, butyric acid, and valeric acid; alcohols such as tert-butyl alcohol and tert-amyl alcohol, esters such as ethyl acetate and butyl acetate; ketones such as methyl isobutyl ketone and cyclohexanol; ethers such as tetrahydrofuran and dioxane; halogenated hydrocarbons such as ethylene dichloride and dichlorobenzene; hydrocarbons such as toluene, xylene and decalin; and amides such as dimethylformamide. These solvents may impart additional hazards, expense, odor, toxicity and removal steps to obtain the final product.
The prior art methods for the synthesis of polysuccinimides and poly(amino acids) are time consuming, complex or use large volumes of volatile organic solvents or inert gases. As used hereinafter and in the appended claims, "polysuccinimides" refers to polymeric materials which contain succinimide moieties in the polymer chain and may contain other moieties, and "polysuccinimide" refers to polymeric materials which contain only such moieties.
It is an object of the present invention to provide a solvent process for producing polysuccinimides.
It is a further object of the present invention to provide a solvent process for producing polysuccinimides which does not require a product separation step.
SUMMARY OF THE INVENTION
The present invention provides a process for preparing polysuccinimides by:
a) forming a polymerization mixture of poly(alkylene glycol), aspartic acid and, optionally, one or more other amino acids;
b) heating the mixture to an elevated temperature; and
c) maintaining the mixture at the elevated temperature to form polysuccinimides.
DETAILED DESCRIPTION OF THE INVENTION
The poly(alkylene glycols) useful in the present invention are those which are fluid at the reaction temperature. Suitable poly(alkylene glycols include poly(tetramethylene glycol), poly(ethylene glycol), and poly(propylene glycol). The poly(alkylene glycol) can also be terminated at one or both ends by carboxylic acids, alkyl groups of from 1 to 30 carbon atoms, or amines, or alkylamines of from 1 to 10 carbon atoms, or any combination thereof. Preferably the poly(alkylene glycol) is diethylene glycol, poly(ethylene glycol), methyl-terminated poly(ethylene glycol), or poly(propylene glycol). The molecular weight of the poly(alkylene glycol)is up to about 30,000, preferably from about 300 to about 20,000, and most preferably from about 1,000 to about 15,000. The poly(alkylene glycol) is added to the polymerization mixture at a level of from 2 to about 90 percent by weight relative to the aspartic acid, preferably from about 20 to about 90, and most preferably from about 30 to about 85 percent by weight relative to the aspartic acid.
In addition to aspartic acid, polysuccinimides can be made by the process of the present invention with up to 80 percent by weight (based on the weight of aspartic acid) of one or more other amino acids. Preferred other amino acids are alanine, lysine, asparagine, glycine and glutamic acid. When used, it is preferred that the one or more other amino acid are present at a level of from 5 to about 70 percent, and most preferably from about 10 to about 60 percent by weight based on the weight of aspartic acid.
The atmosphere of the polymerization is preferably substantially free of oxygen, including the oxygen present in air. An atmosphere substantially free of oxygen is preferred since, at the temperatures needed for the polycondensation reaction to occur, the poly(alkylene glycols) will oxidize, discolor or degrade. Suitable means for achieving an atmosphere substantially free of oxygen is by blanketing, sweeping or bubbling the reactor with an inert gas, preferably nitrogen, or conducting the polymerization at reduced pressure.
The elevated temperature for the process of the present invention must be high enough to provide polycondensation. The preferred temperature will vary with the operating conditions. For example, the preferred temperature may increase as the ratio of aspartic acid to poly(alkylene glycol) increases, or as the pressure at which the polycondensation is conducted increases. However, the preferred temperature may decrease, for example, in the presence of azeotropic solvents. In general, the preferred elevated temperature is from about 120° to about 300° C.
The polysuccinimides are formed by a condensation reaction. It is therefore desirable to remove the by-products, such as water or alcohol, which are liberated in order to drive the reaction toward completion. Suitable means of removing water include addition of one or more azeotropic solvents to the polymerization mixture such as toluene, xylene, or tetralin, and removing the azeotropic distillate from the polymerization mixture. Another means of removing the water is by adding to the polymerization mixture one or more drying agents such as aluminosilicates. Another means of removing the water is by bubbling an inert gas through the polymerization mixture, or sweeping an inert gas over the surface of the polymerization mixture. Another means of removing the water is by conducting the polymerization under reduced pressure.
The polymerization can be conducted as a batch or continuous process. Suitable reactors include batch tank reactors, continuous stirred tank reactors, plug-flow reactors, pipe reactors and scraped-wall reactors. The temperature of the reaction must be sufficient to drive off the water which is liberated in the condensation reaction. This temperature will vary according to whether an azeotropic solvent is employed and the pressure at which the polymerization is conducted which can be subatmospheric, atmospheric or supraatmospheric.
The products which result from the process of the present invention are solutions, suspensions or dispersions of polysuccinimides in poly(alkylene glycol). Poly(alkylene glycols) are useful in many of the applications for the poly(succinimides) such as, for example, in detergent formulations. Thus, there is no need for a separation step to isolate the poly(succinimides) from the poly(alkylene glycol) when the product is used in a detergent application. If desired, the poly(succinimides) can be hydrolyzed by any conventional means to form the corresponding poly(amino acids), such as poly(aspartic acid). A preferred means of hydrolysis is by contacting the product with an aqueous alkaline solution such as sodium hydroxide or sodium carbonate.
EXAMPLE 1
Preparation of Poly(succinimide)
To a 100 milliliter three-neck round bottom flask equipped with a magnetic stirring bar, Dewar condenser, and an inlet and outlet for nitrogen was added 5.0 grams of L-aspartic acid and 5.0 grams of poly(ethylene glycol), methyl ether having a molecular weight of 350. The flask was continuously swept with nitrogen and immersed in an oil bath maintained at 200° C. for 15 hours then cooled to room temperature. Analysis by 1 H NMR spectroscopy indicated that no aspartic acid remained. The polysuccinimide was hydrolzed with dilute aqueous sodium carbonate to form poly(aspartic acid). Analysis by 1 H NMR spectroscopy confirmed that poly(aspartic acid) was formed.
|
A process is provided for preparing polysuccinimides by forming a polymerization mixture of poly(alkylene glycol), aspartic acid and, optionally, one or more other amino acids; heating the mixture to an elevated temperature; and maintaining the mixture at the elevated temperature to form polysuccinimides.
| 2
|
FIELD OF THE INVENTION
[0001] The invention relates to frac packers which can be used in downhole environments, retrieved, and reconditioned for further use rather than requiring the time and expense to drill out, and thus destroy, the tool after use.
BACKGROUND OF THE INVENTION
[0002] To “frac” a well involves the introduction of media, typically containing a proppant, into a zone surrounding the wellbore to create flow conduits in the surrounding earth. In the interest of cost reduction, it is desirable to carry out such an operation as quickly as possible, and with as few trips up and down the wellbore as possible. For frac operations, it is necessary to introduce a seal in the wellbore to prevent the frac fluid from travelling further downhole than the desired frac zone.
[0003] However, wells often have multiple production zones as well as multiple zones where performing the frac operation is desirable. Therefore, the seal which is introduced into the wellbore must be, or is certainly preferably, removable to allow free communication with the wellbore below. Various combinations of devices have been used to accomplish these goals. For example, drillable frac packers are used which allow a single tool to perform the needed tasks. However, these tools require expensive surface support equipment in order to be drilled out after the frac operation is completed. Drilling out such tools is time consuming, and therefore expensive, and can result in undesirable damage to the inside of the wellbore. Further, tool cost using this approach is driven up because the tools themselves must be considered as expendable.
[0004] Another approach is to use a packer in combination with a separate, retrievable bridge plug, with the two tools straddling the frac zone. However, such an approach requires two separate tools to perform a single task, adding cost and complexity to the process. Accordingly, it is desirable to provide a single, retrievable frac packer tool, which can be reconditioned and reused rather than being used once and being destroyed.
[0005] Further, because these tools are often used in wells with multiple frac zones, it is desirable to provide a frac tool which provides bi-directional flow control, thereby providing the capability of not only sealing off the well down-hole of the packer from pressure from above during the frac operation, but also allowing flow from below to be selectively closed off. It is further desirable to provide such tools with flagging media, such as dyes, so that tools used in different frac zones may contain differentiating markings within the flagging media, and thus provide the surface operators with confirmation of the existence of production flow at different levels in the wellbore.
[0006] The interests of keeping costs down additionally makes it desirable to provide a retrievable frac packer which is sufficiently compact and lightweight to allow it to be run-in on wireline, coiled tubing, or other deployment methods and which has the flexibility to be settable either by wireline, hydraulic pressure, or other setting methods, including combinations of hydraulic and mechanical methods.
[0007] Accordingly, it is an object of the invention to provide a retrievable frac packer which provides a single-tool capable of allowing the frac operation to proceed, but which may be retrieved and reconditioned for repeated use.
[0008] It is a further object of the invention to provide such a tool that can also be retrieved in groups of two or more tools at a time, reducing the number of downhole trips required to retrieve the tools when there are multiple frac zones in a well.
[0009] It is another object of the invention to provide a retrievable frac packer that provides bidirectional flow control.
[0010] It is yet another object of the invention to provide a retrievable frac packer that can provide confirmation to surface operators of the downhole level or levels which are producing product flow.
[0011] It is still a further object of the invention to provide a retrievable frac packer which can be run-in on wireline, coiled tubing, or another type of tool string, and which can be set by either wireline, hydraulic methods, or other setting methods.
SUMMARY OF THE INVENTION
[0012] The invention is a frac packer that comprises an annular body comprising a circumferential seal that can be set by compression. When the tool is run downhole, the seal is in the “un-set” position, allowing clearance between the tool and the surrounding casing. A check valve is provided within the annular body to preclude downhole flow of fluid through the tool once the tool is set in the desired position.
[0013] At the desired depth, the tool is set by wireline control, hydraulic pressure, mechanical means, or a combination of these techniques to compress and engage the circumferential seal with the inner wall of the surrounding casing. Compression pressure is applied to the seals by an upper compression member in slidable engagement with the annular body of the tool, and by a lower compression member in slidable engagement with the annular body of the tool. Downward travel of the lower compression member may be resisted by mechanical stops. However, in the preferred embodiment, the lower compression member is biased upward by mechanical means, such as a spring, to provide improved sealing force and to assist in the release of the tool after the frac operation. If the tool is to be utilized in wells in which multiple tools will be retrieved simultaneously, such a mechanical biasing is necessary to insure that the tools will release properly and move further down the wellbore to retrieve a deeper set frac packer, and retrieve properly.
[0014] A slip is preferably present in slideable engagement with the annular body of the tool on the downhole side of the seal, so that the compression setting of the tool also activates the slip into locking engagement with the casing in the wellbore, thus securing the tool against slippage within the casing before, during, or after the frac operation.
[0015] Once compressed into sealing engagement with the well casing, the position of the upper compression member relative to the annular body of the tool is locked by a selectively releasable latch, such as a ratcheting mechanism, so that the seal is held in sealing engagement with the well casing during the frac operation. Release of the latch is preferably accomplished by mechanical means, such as a shear means, like studs or screws, so that the tool may be released from its sealing engagement with the well casing by a jarring effect or other mechanical force controllable from the surface.
[0016] Inside the annulus of the annular body of the tool, a first check valve is positioned to allow fluid flow from the downhole end of the tool upward, but not from the uphole end of the tool downward. Thus, flow can be allowed through the tool from below if necessary, while simultaneously sealing the environment downhole of the tool from pressure above the tool during the frac operation.
[0017] The tool may also be configured with a second check valve positioned in opposed configuration to and uphole of the first check valve, creating a region within the annulus of the tool through which no flow may occur. This second check valve preferably comprises a degradable ball seal, which will degrade at a calculated time to allow upwardly-directed flow through the tool, or a mechanically releasable seal which will open when frac pressure reaches the tool.
[0018] In conjunction with such a second check valve, the tool may be configured with a flagging media, such as a dye package, so that when flow begins through the tool the flagging media will be released to flow to the surface. In this configuration, multiple tools with differently-marked flagging media may be used in multiple commingled production zones to provide confirmation at the surface of which of the commingled zones are flowing.
[0019] In the preferred embodiment, the downhole end of the annular body of the tool is provided with a grip capable of latching onto the uphole end of another of such tools. Thus, when frac operations are completed in a wellbore with multiple zones, each tool may be released in turn, then moved downhole to latch onto and release the next lower tool. In this way, multiple tools may be retrieved simultaneously, reducing the number of trips required to clear the tools from the wellbore.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1A is a sectional view of one embodiment of the retrievable frac packer of the present invention in the run-in position.
[0021] FIG. 1B is a sectional view of the embodiment depicted in FIG. 1A , with an optional flagging media package added.
[0022] FIG. 1C is a sectional view of the embodiment depicted in FIG. 1A , with a second check valve incorporated.
[0023] FIG. 2A is sectional view of an alternative embodiment of the retrievable frac packer depicted in FIG. 1A , with the first check valve replaced with an alternative sliding sleeve and sealing ball valve.
[0024] FIG. 2B is an expanded sectional view of the alternative check valve of FIG. 2A , with the sliding sleeve of the valve in its initial position.
[0025] FIG. 2C is an expanded sectional view of the alternative check valve of FIG. 2A , with the sliding sleeve of the valve in its final position.
[0026] FIG. 3A is a sectional view of the retrievable frac packer of FIG. 1C , shown in the set position.
[0027] FIG. 3B is a sectional view of the retrievable frac packer of FIG. 3A , shown with the degradable ball having dissolved and with flow occurring through the tool.
DETAILED DESCRIPTION
[0028] Referring to FIGS. 1A and 1B , one embodiment of the retrievable frac packer of the present invention is shown. The retrievable frac packer 10 comprises an annular body 12 , which can be run-in to an appropriate position in a well casing 14 . Compressible seal 16 is positioned to be placed into sealing engagement with the inner wall 18 of the well casing 14 . Upper compression member 20 is moveable by wireline control, hydraulic setting means, or a combination of hydraulic and mechanical means (not shown) to force upper linkage 22 downward against the compressible seal 16 .
[0029] Such movement will also force lower compression member 24 downward, compressing mechanical biasing spring 26 , and applying upward force against compressible seal 16 . The downward movement of lower compression member 24 also will force slip 28 outward into mechanical engagement with the inner wall 18 of the well casing 14 .
[0030] Downward movement of upper compression member 20 also engages latch 30 into a locking position by moving ratchet arm 32 into locking engagement with ratchet base 34 . Spring 36 applies biasing force to aid in holding ratchet arm 32 into a locked position once set. Sliding push sleeve 37 allows the downward force to be transmitted to seal base sleeve 39 through a path other than through shear means 38 , protecting shear means 38 from excessive force during the setting operation.
[0031] When release of the retrievable frac packer 10 from its set position is desired, an upward jar may be applied, shearing shear means 38 . This in turn will allow the upward movement of upper linkage 22 , which interlocks with ratchet arm 32 , thus releasing latch 30 and allowing upper compression member 20 to move upward. Bias force from compression spring 26 further assists in this upward movement, relieving pressure against compressible seal 16 and allowing slip 28 to release its mechanical engagement with the inner wall 18 of well casing 14 .
[0032] First check valve 42 allows the retrievable frac packer 10 to protect the region below from hydraulic pressures above so that frac operations may proceed. However, first check valve 42 also allows flow testing of the well to occur without removing the retrievable frac packer 10 from the well. For such purposes, a flagging media such as dye pack 44 may be carried downhole within the annulur body of the retrievable frac packer 10 . In a multiple production zone well, multiple retrievable frac packers 10 may be inserted into different production zones with uniquely-marked flagging media, providing confirmation on the surface of which zones are flowing.
[0033] Referring to FIG. 1C , an alternative embodiment of the retrievable frac packer 10 is shown incorporating a second check valve 46 . In this embodiment, second check valve 46 incorporates a degradable ball 48 , allowing the retrievable frac packer 10 to be run in to the well as a bridge plug. After a calculated time in the well environment, the degradable ball 48 will dissolve, allowing the retrievable frac packer 10 to operate as described above.
[0034] Referring to FIG. 2 , an alternative embodiment of the retrievable frac packer 10 of FIGS. 1A-1C is shown. First check valve 42 of FIG. 1 is replaced by a sliding sleeve valve 242 . For run-in, sliding sleeve valve 242 seals in both directions, and allows retrievable frac packer 210 to be run-in as a bridge plug. Once in position, hydraulic pressure may be applied, for example, at the same time frac operations are conducted above the retrievable frac packer 210 , sliding sleeve 250 into an open position 252 and allowing sliding sleeve valve 242 to function in the same manner as first check valve 42 of FIG. 1 .
[0035] Referring now to FIGS. 3A and 3B , retrievable frac packer 310 is shown in the set position. Upper compression member 320 has been moved downward relative to the annular body 312 of retrievable frac packer 310 . Compressible seal 316 is in sealing contact with the inner wall 318 of the well casing 314 . Latch 330 is set by the interlocking of ratchet arm 332 with ratchet base 334 , preventing loss of compression force against compressible seal 316 . Slip 328 is also forced outward into mechanical engagement with the inner wall 318 of well casing 314 , resulting from the downward movement of lower compression member 324 relative to the annular body 312 of retrievable frac packer 310 .
[0036] As shown in FIG. 3A , the initial setting of retrievable frac packer 310 allows frac operations to proceed. First check valve 342 and compressible seal 316 prevent fluid flow downhole of the retrievable frac packer 310 during frac operations. After the degradable ball 348 has dissolved, second check valve 346 “opens,” and flow may be tested prior to removal of the retrievable frac packer 310 , as shown in FIG. 3B . Upward flow pressure opens first check valve 342 , allowing test production flow to proceed up the wellbore.
[0037] The above examples are included for demonstration purposes only and not as limitations on the scope of the invention. Other variations in the construction of the invention may be made without departing from the spirit of the invention, and those of skill in the art will recognize that these descriptions are provide by way of example only.
|
A retrievable frac packer is provided which allows frac operations to be conducted with a single, retrievable tool, with the capability of providing positive zone production indications during production testing.
| 4
|
[0001] The present invention relates to an extrudable composition that can be cross-linked in air, and also to a method of cross-linking said composition.
BACKGROUND OF THE INVENTION
[0002] This composition is for use in the manufacture of sheathing material for medium and low-voltage power cables or for telecommunications cables. These cables carry direct current (DC) or alternating current (AC). Medium-voltage cables are generally constituted by a conductive core surrounded by an insulating structure that is coaxial thereabout. The structure comprises at least a semiconductive first layer placed in contact with the core of the cable, itself surrounded by an electrically insulative second layer, in turn covered by a semiconductive third layer. The outer layers are sheaths which serve to protect the cable. Low-voltage cables (voltage lower than 20 kilovolts (kV)) have a conductive core surrounded by an insulating structure which is coaxial thereabout and covered in a sheath. This composition is also usable as an insulating material.
[0003] In the event of a short circuit occurring in a cable, temperatures locally rising to 200° C. can be observed. At these temperatures and under stress, the material is subject to deformation or creep. This elongation when hot is evaluated using the so-called “hot set test” (HST) under conditions which are defined in standard NF EN 60811-2-1. Compositions are being sought which present good results in the “hot set test”.
[0004] Document WO-88/05449 proposes in its examples 11 and 12 an extrudable composition which comprises a mixture of a copolymer of an ethylenically-unsaturated compound and an unsaturated ester containing an acrylate such as ethylene butylacrylate (EBA) (example 11) or an ethylene methylacrylate (EMA) (example 12) with a hydrolizable silane compound having no ethylenic unsaturation, such as a 3-amino-propyltrimethoxysilane (MEAM) and also with a thermoplastic polymer having no functional groups such as a polyethylene homopolymer, e.g. low density polyethylene (LDPE).
[0005] The resulting material presents good adhesion on metals or polar substances and it is used for this purpose in cables. However that material is not cross-linkable.
[0006] Document EP-A-0 802 224 describes an extrudable composition that is cross-linkable, and that is constituted by a mixture comprising a thermoplastic polymer material, a hydrolizable silane compound, a non-cross-linked elastomer, and a cross-linking agent. The thermoplastic polymer material and the hydrolizable silane compound respectively carry mutually reactive functional groups so that they react together selectively. The elastomer is cross-linked dynamically and selectively by the cross-linking agent in the mixture. The thermoplastic polymer material carrying reactive functional groups is a commercially-available substance, preferably polyethylene grafted by maleic anhydride. The silane compound is preferably amino-alcoxysilane. The amine groups of the silane compound react selectively with the maleic anhydride groups of the polyethylene, and the alcoxy groups of the silane compound react with the surface hydroxyl groups of the filler. The elastomer is an ethylene vinyl acetate (EVA) copolymer which is cross-linked dynamically and selectively by the cross-linking agent.
[0007] The special feature of that composition is the choice of basic components in the mixture which have specific and different reaction kinetics, thereby enabling the composition to be made in a single stage. As a result, the choice of basic components is very restricted and the cost thereof is high.
OBJECTS AND SUMMARY OF THE INVENTION
[0008] An object of the present invention is to propose an extrudable composition that is cross-linkable in air to give a cross-linked material which is recyclable and which is simpler to manufacture, and which is of lower cost than known compositions.
[0009] In a first aspect, the present invention thus provides a composition that is extrudable and cross-linkable in air, comprising a mixture:
[0010] of a copolymer of an ethylenically-unsaturated compound and an unsaturated ester;
[0011] of a hydrolizable silane compound having no ethylenic unsaturation and containing functional groups; and
[0012] of a thermoplastic polymer;
[0013] wherein said functional groups of said ester are selectively reactive with functional groups of said silane compound, and wherein said thermoplastic polymer has no functional groups.
[0014] The invention is based on the discovery that under certain conditions it would appear that a selective reaction occurs between the functional groups of the ester of the copolymer and the reactive functional groups carried by the silane.
[0015] The composition of the invention comprises a thermo-plastic polymer that has no functional groups liable to interfere with the reaction between the silane and the copolymer involved in cross-linking the composition. This thermoplastic copolymer confers good mechanical properties on the composition of the invention since it contributes to reinforcing its structure.
[0016] The present invention makes it possible to use a vast range of silane compounds. In addition, it does not require recourse to polymers having special functional groups, and consequently it makes it possible to use a vast range of polymers, and in particular polymers that are the most widespread and the least expensive.
[0017] The present invention makes it possible to obtain a composition having good resistance to creep at high temperature.
[0018] In addition, a composition of the invention makes it possible to obtain finished products which can be recycled. It also makes it easy to obtain finished products that are very flexible, for example cables based essentially on (poly)vinyl acetate.
[0019] In a second aspect, the present invention provides a method of preparing a composition which enables the composition of the invention to be cross-linked, and including in particular a “dynamic cross-linking” step.
[0020] This step serves in particular to lengthen the chains of the polymer and of the copolymer and thus reduce the number of chains. In this way, this step makes it possible to improve compatibility between the polymer and the copolymer by promoting cross-linking of the composition.
[0021] In another aspect, the present invention provides a cable whose insulation and/or sheath contain the composition obtained by the method.
DETAILED DESCRIPTION OF THE INVENTION
[0022] Other characteristics and advantages of the invention are described below in detail in the following description which is given by way of non-limiting illustration.
[0023] Composition of the invention
[0024] A composition of the invention comprises in particular a copolymer of an ethylenically-unsaturated compound and an unsaturated ester.
[0025] The selective reaction between the silane and the ester on which the invention is based can be illustrated by the following scheme:
SiX 4 +4RCOO4′→Si(OR′) 4 +4RCOX
[0026] in which:
[0027] X represents a functional group carried by the silane SiX 4 ; and
[0028] RCCOR′ represents a fragment of the copolymer of an ethylenically-unsaturated compound and an unsaturated ester.
[0029] In the invention, the unsaturated ester of the copolymer generally satisfies the formula R 1 COOR 2 in which:
[0030] R 1 is an alkyl group preferably having 1 to 4 carbon atoms; and
[0031] R 2 is an alkylene group preferably having 2 to 4 carbon atoms.
[0032] Advantageously, the functional groups of the ester of the invention can comprise acetates. Acetates promote the above-mentioned reaction, unlike other groups such as acrylates.
[0033] A composition of the invention preferably also comprises a cross-linking agent which can be a peroxide, a phenolic resin, a sulfur-containing derivative, or a mixture of these compounds, in particular. The composition of the invention generally contains 0.5 to 7 parts by weight and preferably 0.5 to 3 parts by weight of said cross-linking agent.
[0034] In the invention, the ethylenically-unsaturated compound is preferably ethylene.
[0035] As examples of copolymers entering into the composition of the invention, mention can be made of ethylene vinyl acetate copolymers (EVA), ethylene vinyl propionate copolymers, ethylene allyl acetate copolymers, and ethylene allyl propionate copolymers.
[0036] It is preferable to use an ethylene vinyl acetate copolymer (EVA) containing up to 80% by weight vinyl acetate, and more specifically an EVA containing 10% to 70% by weight vinyl acetate.
[0037] Concerning proportions, the composition of the invention generally comprises 25 to 95 parts and preferably 30 to 85 parts by weight of copolymer.
[0038] In an embodiment, the hydrolizable silane having no ethylenic unsaturation of the invention can be a tri-alcoxysilane or a tetralcoxysilane, such as tetraethoxy-silane.
[0039] It is preferable to use a silane containing an amino function, such as aminotrialcoxysilane. As an example of such a silane, mention can be made of aminopropyltri-ethoxysilane and of aminopropyltrimethoxysilane.
[0040] The composition of the invention generally comprises 0.5 to 5 parts and preferably 0.7 to 4 parts by weight of the silane compound.
[0041] The term “silane compound having groups that are selectively reactive with the ester functional groups of the copolymer” as used in the present invention means a compound which, under reaction conditions, is capable of reacting essentially with the ester functional groups of the copolymer in the scheme specified above. Thus, it is understood that the composition can include other reactive compounds, providing they do not interfere significantly with the selective reaction between the reactive groups of the silane and of the copolymer.
[0042] The thermoplastic polymer having no functional groups can be a homopolymer of an olefin having 2 to 6 carbon atoms and a polymer of 2 olefins each having 2 to 6 carbon atoms, the olefins being constituted, for example, by ethylene, propylene, butene, pentene, hexene, isobutylene, methyl-butene, methyl-pentene, dimethyl-butene, or ethyl-butene. In general, polyethylene is used, and preferably high density polyethylene (HDPE).
[0043] The proportion of polymer having no functional group in the composition generally lies in the range 0.5 to 75 parts by weight.
[0044] In a preferred embodiment, the composition of the invention can also include a filler.
[0045] This filler is preferably a filler that is not surface-reactive, such as chalk, carbon black, non-reactive magnesia, or natural or synthetic clay.
[0046] The proportion of this non-surface-reactive filler in the composition is not crucial. It generally lies in the range 0 to 230 parts by weight and usually in the range 0 to 180 parts by weight.
[0047] The composition of the invention does not require the use of fillers having reactive surfaces, and consequently it makes it possible to employ a vast range of fillers, and in particular those which are the most widely available and the least expensive.
[0048] In a variant, the composition of the invention can also contain a filler that is surface-reactive, of the type used in application EP-A-0 802 223 in the name of the Applicant. This filler can be reactive magnesia, alumina, kaolin, or mica. Since the filler is surface-reactive, it can interfere with the reaction between the silane and the copolymer.
[0049] In general, the content of said surface-reactive filler is less than 250 parts by weight, and preferably less than 160 parts by weight.
[0050] The composition is preferably free of any surface-reactive filler.
[0051] Advantageously, the composition of the invention can also include a catalyst for the reaction between the silane functional group(s) and the ester functional groups of the copolymer.
[0052] Such a catalyst can be based on an amine, a tin salt, or a molecule containing at least one atom of tin.
[0053] The proportion of catalyst in the composition of the invention generally lies in the range 0 to 500 parts per million (ppm) and more usually in the range 0 to 100 ppm.
[0054] Naturally, the composition of the invention can include various additives of the kind commonly used in fabricating cross-linked copolymers. As examples of such additives, mention can be made antioxidants, flame retarders, anti-UV agents, plasticizers, and coloring agents.
[0055] The proportions of these various additives in the composition of the invention generally lie in the range 0 to 5 parts by weight and usually in the range 0.1 to 2 parts by weight.
[0056] Once the composition of the invention has been cross-linked, it presents no significant elongation after 15 minutes (min) at 200° C. under a stress of 0.2 mega Pascals (MPa) which are the conditions defined by standard NF EN 60811-2-1, after being stored in ambient air without taking special precautions for a period of one week.
[0057] Its hardness on the Shore A scale is preferably less than 95.
[0058] It preferably presents breaking elongation greater than 130% and more preferably of not less than 150%.
[0059] The ultimate tensile strength of the cross-linked composition of the invention is preferably greater than 7 MPa.
[0060] Method of the Invention
[0061] A cross-linked composition of the invention can be prepared in a single dynamic cross-linking step in the presence of the copolymer and of the thermoplastic polymer.
[0062] Under such circumstances, shear is created by kneading the copolymer and the thermoplastic polymer during a “compounding” step of preparing the mixture, e.g. in an extruder having two contra-rotating screws, or in an internal mixer.
[0063] The addition of a peroxide or some other cross-linking agent then enables the compatibility of the various polymers to be improved by lengthening the chains of the polymer and of the copolymer, and thus reducing the number of chains. This reduces the number of cross-linking bridges required for cross-linking the material of the invention.
[0064] Dynamic cross-linking is generally initiated at a temperature higher than 150° C. and preferably lying in the range 170° C. to 230° C. and under a large amount of shear, i.e. greater than 20 s −1 and preferably lying in the range 50 s −1 to 250 s −1 .
[0065] The silane can be incorporated during the compounding, and it is preferably incorporated during the step of extruding the composition. Thereafter, cross-linking which has started under the above-specified temperature and shear is then generally allowed to continue in ambient air. Cross-linking is allowed to continue in ambient air for a period lying in the range a few hours to a few days.
[0066] Finished Products
[0067] The dynamic cross-linking is preferably performed under conditions that make it possible to obtain a cross-linked composition having hardness on the Shore A scale of less than 95.
[0068] The composition of the invention is advantageously extruded in a manner that is appropriate for producing a variety of semifinished products which, once cross-linking has been completed, become finished products benefitting from the mechanical properties and the ability to withstand high temperatures that are possessed by the composition of the invention once cross-linked.
[0069] Examples of such finished products include power cables in which the insulation and/or the sheath is constituted by the cross-linked composition of the invention.
[0070] The insulation and/or the sheath does not present significant elongation after 15 min at 200° C. under 0.2 MPa of stress, conditions defined by standard NF EN 60811-2-1, after being stored in air without taking special precautions for one week.
[0071] Their hardness on the Shore A scale is preferably less than 95; their breaking elongation is preferably greater than 130%, and more preferably not less than 150%. Their ultimate tensile strength is preferably greater than 7 MPa.
EXAMPLES
[0072] The following examples are given purely by way of non-limiting illustration.
Example 1
[0073] A formulation of the invention was mixed, extruded, and allowed to cross-link in ambient air without special precautions, and then its ultimate tensile strength (UTS in MPa), its breaking elongation (BE in %), and its resistance (or non-resistance) to creep or deformation in application of standard NF EN 60811-2-1 (HST) and its Shore A hardness in application of standard NF 51-109 were all measured. The composition of the formulation and the results of the measurements are summarized in the following table:
COMPONENTS Lepraven 500 83 HDPE 47100 17 Magnifin H10 100 Santonox TBMC 0.5 Trigonox 145-45pd 1.4 Aminopropyltriethoxysilane 1.5 PROPERTIES UTS (MPa) 10.5 BE (%) 210 HST (200° C./0.2 MPa/15 min) yes Shore A hardness 74
[0074] It can be seen that the thermomechanical properties and the resistance to creep or deformation are good. Shore A hardness is low, which is advantageous, particularly for use as cable insulation or as a cable sheath. In addition, the resulting composition possesses good resistance to hot pressing (110° C.).
[0075] This cross-linked composition can subsequently be reworked (extruded again) after at least three months' storage in ambient air, and it conserves mechanical properties similar to those described above.
Example 2
[0076] In a manner analogous to Example 1, a formulation of the invention was mixed, extruded, and allowed to cross-link in ambient air without taking special precautions, and then its ultimate tensile strength (UTS in MPa), its breaking elongation (BE in %), its resistance (or non-resistance) to creep or deformation in accordance with standard NF EN 60811-2-1 (HST), and its Shore A hardness in accordance with standard NF 51-109, were all measured.
[0077] The composition of the formulation and the results of the measurements are summarized in the following table:
COMPONENTS Elvax 260 20 Elvax 40/03 60 HDPE 47100 20 Hydrofy G1.5 150 Santonox TBMC 0.5 Trigonox 145-45pd 1 Aminopropyltriethoxysilane 2 PROPERTIES UTS (MPa) 13 BE (%) 150 HST (200° C./0.2 MPa/15 min) yes Shore A hardness 92
Example 3
[0078] A formulation of the the prior art was mixed, extruded, and allowed to cross-link in ambient air without taking special precautions, and then its ultimate tensile strength (UTS in MPa), its breaking elongation (BE in %), its resistance (or non-resistance) to creep or deformation in accordance with standard NF EN 60811-2-1 (HST), and its Shore A hardness in accordance with standard NF 51-109, were all measured.
[0079] The composition of the formulation and the results of the measurements are summarized in the following table:
COMPONENTS Elvax 260 20 Elvax 40/03 60 HDPE 47100 20 Hydrofy G1.5 150 Santonox TBMC 0.5 Trigonox 145-45pd 1 Aminopropyltriethoxysilane 2 PROPERTIES UTS (MPa) 12 BE (%) 160 HST (200° C./0.2 MPa/15 min) no Shore A hardness 92
[0080] Without subsequent processing (passing through an oven or a pool), the cross-linking of this material was still not complete after one week.
Example 4
[0081] A low-voltage power cable was made having an outer sheath constituted by the cross-linked composition of the present invention.
[0082] The components specified in Example 1 were mixed in a mixer (continuous or discontinuous mixers are suitable) and then the composition was extruded, a technique which serves to transform the granules or strips of the compound into a finished or semifinished product in the form of a coating for a cable. The material was transported by means of a screw from the feed zone to the die. The material plasticized under the action of the mixing imparted by rotation of the screw and heat delivered from the outside. Its pressure rose progressively along the screw, thus forcing the material to pass through the die to give it a permanent shape on leaving the die. By using a die head of appropriate shape, that technique serves to cover copper wires or wires that have already been insulated.
[0083] Its ultimate tensile strength (UTS in MPa), its breaking elongation (BE in %), its resistance (or non-resistance) to creep or deformation in accordance with standard NF EN 60811-2-1 (HST), and its Shore A hardness in accordance with standard NF 51-109, were all measured. The results of the measurements are given in the following table:
PROPERTIES UTS (MPa) 13 BE (%) 150 HST (200° C./0.2 MPa/15 min) yes Shore A hardness 92
[0084] The sheath-forming material of the cable was suitable for subsequent reworking, i.e. it could be extruded again to form a new sheath after the cable had been in use for six months or more. The sheath made with the recycled material conserves mechanical properties similar to those of the initial sheath.
[0085] The hydrolizable silane compound having no ethylenic unsaturation, such as amino silane, can be introduced into the composition during the “compounding” step of preparing the mixture, or else during the extrusion.
Example 5
[0086] A formulation of the invention was mixed, extruded, and allowed to cross-link in ambient air without taking special precautions, and then its ultimate tensile strength (UTS in MPa), its breaking elongation (BE in %), its resistance (or non-resistance) to creep or deformation in accordance with standard NF EN 60811-2-1 (HST), and its Shore A hardness in accordance with standard NF 51-109, were all measured.
[0087] The composition of the formulation and the results of the measurements are summarized in the following table:
COMPONENTS Lepraven 700 66 EVA 265 (with 26.5% vinyl 33 acetate) HDPE 47100 0.5 Magnifin H10 120 Santonox TBMC 0.5 Trigonox 145-45pd 1 Aminopropyltriethoxysilane 2 PROPERTIES UTS (MPa) 11 BE (%) 190 HST (200° C./0.2 MPa/15 min) yes Shore A hardness 78
[0088] It can be seen that the thermomechanical properties and the resistance to creep or deformation are good. Shore A hardness is low which is advantageous, particularly for use as a cable insulation or sheath. In addition, this composition possesses good ability to withstand oil (24 hours at 100° C.) in application of ASTM standard No. 2.
[0089] This cross-linked composition is suitable for being subsequently reworked (extruded again) after being stored for at least three months in ambient air, and it conserves mechanical properties similar to those described above.
|
The present invention relates to a composition that is extrudable and cross-linkable in air. The composition that is extrudable and cross-linkable in air comprises a mixture of a copolymer with an ethylenically-unsaturated compound and an unsaturated ester, a hydrolizable silane compound having no ethylenic unsaturation containing functional groups, and a thermoplastic polymer having no functional groups, said functional groups of the ester being selectively reactive with the functional groups of the silane compound. Such a composition is used to fabricate a material for insulating or sheathing a power cable, in particular a medium-voltage cable or a cable for working at a voltage of less than 20 kV. The invention also provides method enabling said composition to be cross-linked and power cables including insulation and/or a sheath containing the composition obtained by the method.
| 2
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to a teaching method and apparatus for teaching a proper golf swing. More particularly the invention concerns a novel method and apparatus for teaching and learning the game of golf by developing a left side to the golfer's swing through the use of a light weight ball and a light weight training club designed to be swung by the use of only the left hand.
2. Discussion of the Prior Art
It has long been suggested, and teaching Golf Professionals agree, that a strong left side is an essential part of the correct golf swing. In fact, those knowledgeable of the game frequently state that golf is primarily a left-handed game played by right-handed persons.
The method of the present invention is largely a self-corrective one and initially makes use of a club which is about one third the weight of a normal club. As the teaching method progresses, incremental weights are added to the blade of a training club until a total of about two-thirds the weight of a normal club is realized.
A golf swing can be characterized to varying degrees of approximation by measuring elements of motion of the club during the swing. For example, the U.S. Pat. to Evans, No. 3,806,131, discloses a system wherein three elements of motion, namely acceleration, torque and shaft flex are measured during the swing. The U.S. Pat. to Hammond, No. 3,945,646, measures acceleration of the club head in three mutually perpendicular directions as well as the torque and flex of the shaft during the swing and thus obtains a closer approximation of the characteristics of a swing. The swing can be characterized to a higher degree of approximation by increasing the number of elements of motion measured during the swing, but this leads to a more complex system of measurement and leaves the problem of interpreting the data and making use of it to produce a proper swing to the learning player.
Important to the present invention is the fact that the characteristics of the swing can also be predicted by the action of the body on the club through the hands for a club of given mechanical properties. Thus, the placement of the elements of the body with respect to the ball and their motion during the swing also determines the characteristics of the swing. Further, the degree of approximation to a proper swing attained depends on the number of elements of body motion required for a proper swing that are considered and the effectiveness with which they are executed.
Instruction in the placement of the elements of the body required for a proper swing and their motion during the swing is the usual method of teaching and learning the game of golf. In the conventional approach to the teaching of the golf swing, the learning player is told that the entire backswing and downswing to about waist high on the off-target side is controlled dominantly by the left side. In the follow through from waist high to finish of the swing on the target side, the right side controls. Thus the sides that dominate the swing change from the left side at the beginning of the swing to the right side at the finish of the swing. From waist high down on the downswing to and through ball impact to waist high on the follow through both sides are joined in the force of the swing.
The difficulty arises in the multitude of elements of the body and their motion that must be executed in proper sequence and in a timely manner and that the elements of the body producing these motions cannot be clearly divided into those related to the left or right side. Thus the learning player is left in a condition where he cannot tell which side is dominant or subservient in controlling his swing at various points of the swing. The learning player is told to take the right side out of the backswing and the beginning of the downswing but the learning player himself cannot tell when he is or when he is not. The difficulty is compounded by the fact that in a right handed person his right side is much stronger than his left side so that there is a tendency for the right side to dominate throughout the swing. The method of the present invention contemplates eliminating in large part the aforementioned difficulties of teaching and learning the game of golf.
SUMMARY OF THE INVENTION
The present invention provides a largely self-corrective method of teaching and learning a proper golf swing by initially reducing the large number and importance of the elements of motion of the body necessary for a proper golf swing. This is done by using a training club designed to be swung by using only the left arm thus eliminating the confusion between left and right side and the tendency for the right side to dominate in the manner earlier described. The number of elements of body motion required to execute a swing is further reduced by using a club with a head weight of about one-third that of a normal club and such that it can be held stationary at any position of a full golf swing without exerting undue strain on the arm as is the case for a normal club using both hands. Thus initially the motion of the body to trace the swing is that of only the left hand, wrist and arm.
A practice swing pad without a ball is used and the light club is swung so as to skim the surface of the pad. As the swing force is increased it is found that there is strain on the arm if appreciable torque is exerted by the arm to increase the swing force. However, if, following conventional instruction, other elements of body motion are introduced into the swing such as a shifting of the weight from right to left just prior to the beginning of the down swing and the turning of the shoulder, it is found that the arm pulls the shaft of the club, and in turn the head of the club, towards and past the surface of the pad and that little torque exerted by the arm is needed to swing the club and thus there is no strain on the arm. Also there is a feeling of increased swing force as the club head approaches the pad and crosses the pad surface. A light practice ball is then used to improve the accuracy and consistency of the swing and to obtain experience in addressing and hitting a ball. In accordance with the method of the invention, one then adds an increment of weight to the club head whereupon it is found that additional elements of body motion must be introduced in order to swing the club without straining the arm and that the swing force can be again increased. It is found that by increasing the weight of the club head incrementally in this way, one gradually, and in a natural way, introduces the elements of motion of the body necessary for a proper golf swing.
The process of adding weights to the club head and practicing the golf swing progresses to a point where the club head weight is about two-thirds that of a normal club. This is found to be the optimum upper weight of the club head, depending upon the physique of the player, that can be used effectively in developing the elements of motion required of the left side for a proper swing. A heavier club results in instability of the club during the swing with corresponding degradation of the swing. This is because the apparatus of the present invention comprises a training club that teaches one to make use of a largely existing left side in developing a proper swing and not an exercise club designed to strengthen the muscles of the left side.
The learning golfer practices with his normal clubs using the conventional two handed grip during the latter part of the learning regime and continues to use the one handed club at its optimum weight but now as a practice club to continue to improve and maintain his swing. Because the left handed club is swung with little torque exerted by the left arm and the right hand is absent, this method of teaching and learning the golf swing produces a smooth swing where the back swing is fully integrated into the down swing and throughout the entire swing.
The apparatus contemplated by the invention for learning the game of golf comprises a training type club with the general lift configuration of a pitching iron whose head is of aluminum or other light material and a head weight measured by having the hand grip on a fulcrum of 5 ounces with provisions so that the weight of the club head can be increased in increments of one ounce to a total of about 9 ounces.
The method according to the present invention also contemplates the use of the one handed club at its optimum upper weight or a club specifically made at this optimum weight in a new game to be played on a pitch and put golf course with a normal putter and a ball that is about three-quarters the weight of a normal golf ball and approximately the same size as a normal golf ball.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a generally perspective view of the light weight golf club of the present invention showing its general configuration and its manner of use with a one handed grip.
FIG. 2 is a fragmentary perspective view of the club showing the front striking surface of the blade and showing a weight segment removably attached to the rear surface of the blade.
FIG. 3 is a fragmentary view showing the rear surface of the blade of the device and illustrating the configuration of the weight segments and the attachment means for the apparatus.
FIG. 4 is a fragmentary view of the club showing the bottom, or sole, portion of the blade.
FIG. 5 is a fragmentary edge view showing the appearance of the front edge of the blade.
FIG. 6 is a side elevational view showing the tapered configuration of a weight segment adapted to be removably affixed to the rear surface of the blade.
DESCRIPTION OF THE INVENTION
Referring now to the drawings and specifically to FIGS. 1, 2 and 3, the numeral 10 generally designates the light weight golf club, or swing learning device, of the present invention. Club 10 includes a tapered shaft 12 of a length and diameter substantially corresponding to the length and diameter of a conventional adult pitching type club, or pitching iron. Shaft 12, which is about 35 inches long, as measured from one extremity of club 10 to the other, has first and second end portions 14 and 16. Provided proximate the first end portion 14 is gripping means shown here as a substantially conventional hand grip 18 of such a length that it can conveniently be grasped by the trainee with one hand 20.
Affixed at the second end portion 16 of the shaft 12 is a blade 22 having a front striking surface, or face, 24 and a spaced apart rear surface 26 (FIG. 5). Blade 22 is attached to the shaft 12 by a hosel 28 which is fixed to the blade. Blade 22 with hosel 28 is preferably fabricated from a metal alloy such as aluminum alloy or from another light, impact resistant material such as plastic or composite material.
The blade end of the club 10 as weighed with the end of the handgrip 18 on a fulcrum, is approximately 5 ounces, or about one third that of a normal pitching iron. The striking face 24 of the blade is oriented at an angle of approximately 45 degrees with respect to the longitudinal axis of shaft 12 as in a standard pitching iron construction.
As best seen by referring to FIG. 5, the rear surface 26 of the blade 22 is recessed so as to define a shoulder, or ridge 30 proximate the lower portion of the blade. In one form of the invention, excess weight means is provided for incrementally supplying increased weight to the blade. The excess weight means is adapted to be affixed to the rear surface of the blade by attachment means generally designated in FIGS. 3, 4 and 5 by the numeral 32. In the embodiment of the invention shown in the drawings, the excess weight means is provided in the form of a plurality of weight segments of predetermined weight. For example, as shown in FIG. 5, one of the weight segments, identified by the numeral 34, has a weight of about one ounce and is in the configuration of a flat or wedge shaped plate. Plate, or segment, 34, which is preferably fabricated from an aluminum alloy and has the outline of the recessed rear face 26, is removably secured to blade 22 by the attachment means of the invention. As best seen in FIGS. 4 and 5, the attachment means here comprises an externally threaded stud 36 which extends outwardly from rear face 26 of the blade and a nut 38 which is threadably received over stud 36. An additional weight segment, made of lead and of a substantially smaller area, is provided in the form of a washer 40. Washer 40, being of a more dense material, also has a weight of about one ounce. Weight segments 34 and 40 are apertured at 35 and 41 respectively and are affixed to blade 22 in the manner shown in FIGS. 3, 4 and 5. Also forming a part of the excess weight means of the present embodiment of the invention is a second weight 34a which is of the same size and shape as weight 34 but is made of a material such as zinc, brass or iron, whose density is approximately three times that of aluminum. Accordingly, the weight of weight segment 34a is approximately 3 ounces. Segment 34a is apertured at 37 and is affixed to blade 22 in the same manner as segment 34.
As essential feature of the arrangement of the weight segments of the excess weight means 32 and their method of attachment to the blade 22 is that they do not interfere with the execution of the swing. Ridge 30 provides a means for positioning the weight segment as well as means whereby the sole 42 of the blade does not expose the weight segment 34 to the pad or ground surface during the swing.
Use of the excess weight means of the invention as thus described and as illustrated in the drawings, permits the weight of the blade 22 to be adjustably varied within a range from 5 ounces with no weight added to the blade, to 6 ounces using weight segment 34, to 7 ounces using both segments 34 and 40. When weight segment 34a is used in lieu of segment 34, a weight of approximately 8 ounces can be achieved. Using both segments 34a and 40, a total weight of approximately 9 ounces can be realized. Thus the total weight of the blade can be incrementally adjusted through a range of five head weights ranging from approximately 5 ounces, which is about one-third of the weight of a standard club head, to 9 ounces, which is about two-thirds of the weight of a normal club head.
In the practice of the method of the invention using the apparatus as described in the preceding paragraphs, the conventional instructions given by golf instructors and as set forth in books such as "Golf" by V. L. Nance and E. C. Davis are substantially followed. More specifically, or after the rudimentary aspects of the golf swing have been practiced, the learning player uses the device of the present invention in a conventional manner to the extent possible in light of the proscribed use of only the left arm. Through the use of the novel light weight club of the present invention, however, it has been demonstrated that the learning player can more easily absorb and understand the conventional instructions. This is because the elements of motion of the body required to execute a proper swing are introduced gradually and in a more natural way as the learning player progresses toward developing a proper swing.
As a first step in the practice of the method of the invention, the trainee, or learning player, positions himself before a practice pad in a normal address stance but without a ball being positioned on the pad. With the device 10 of the invention firmly grasped in his left hand with no weights added to blade 22, the trainee slowly swings the club, periodically pausing at various positions along the arc of a correctly configured swing. The reduced club head weight permits the trainee to easily hold the club at the various positions along the swing arc to obtain the "feel" of the correctly configured swing and to check his position with instructional photographs. Next the trainee swings the club freely and in a manner to closely duplicate the arc of the correct swing. Each swing is executed so that the blade 22 of the club just skims the surface of the pad and the swing arc corresponds to the photographs contained in standard instructional materials.
After numerous repeated swings, the trainee usually discovers that his left arm aches and the muscles have begun to stiffen. This indicates that the trainee is exerting excessive torque with his arm and is not properly using the other elements of the body to correctly produce the swing. This is a common failing in the beginning player as well as in more experienced players. By following conventional instruction to introduce the correct elements of body motion into the swing, including a shifting of the weight from the right to the left just prior to the down swing simultaneously with the correct turning of the shoulder, the trainee soon finds that he can effectively pull the club head toward and across the surface of the pad surface while exerting very little torque with his left arm. He then finds that numerous swings can be made without arm ache and that, in fact, his swing force towards the pad and across the pad is greatly increased.
Continued practice of the method of the invention as described in the preceding paragraphs gradually introduces into the swing the elements of body motion necessary for a proper swing. Next the trainee uses the light practice ball in practicing the swing and thereby gains experience in developing consistency and accuracy in his swing while at the same time gaining experience in addressing and hitting a ball. Since the practice ball of the invention can be of any light weight, but in any event no more than about 75 percent the weight of a standard ball, the light weight club can be effectively used in simulating the correct swing and the correct impact upon the ball.
After the trainee progresses to the point where he can hit the ball consistently with increasing swing force by correctly introducing the various elements of body motion into his swing, he next adds weight 34 to the rear surface of blade 22 and repeats the previously ennumerated steps of the method. With the added weight, the trainee finds that he must introduce still other elements of body motion and improve the coordinated use of these body elements in order to develop a greater swing force without straining his arm. However, he finds that the introduction and coordination of these other body motions comes much more naturally having developed the basic swing with the unweighted club. Once the swing is perfected using weight 34 the trainee can next proceed to practice swings using the added weight segment 40.
In a relatively short period of practice using the heavier weighted club the trainee finds that his swing is being correctly "grooved in". He can then replace weight segment 34 with segment 34a and continue his practice. The ability to swing the device without exerting excessive swing force with the arm, which results in arm strain, and the corresponding feeling of developing greater swing force with the elements of body motion are the positive indicators that the learning player uses to appraise himself of his progress towards a proper golf swing. In this manner, a proper golf swing is developed by successive approximations that converge to a proper golf swing by introducing the elements of body motion required for a proper swing gradually and in a way the learning player can understand.
Experience has shown for average trainees there is an optimum upper club head weight of approximately two thirds the weight of a normal club head, beyond which the trainee is no longer learning to make use of his left side, but rather is involved merely in strengthening the muscles of his left side. Instability of the swing usually appears at this point. The training club at this optimum comfortable weight using weight segments 34a and 40 can now be used as a practice device to continue to improve and maintain his left side.
During the latter part of the training regime, normal clubs and traditional techniques are used and complete swings using both hands are developed for all of the clubs.
The foregoing is considered as illustrative only of the principles 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 shown and described and accordingly all suitable modifications and equivalents may be resorted to falling within the scope of the invention.
|
A method and apparatus for teaching a correct golf swing wherein a light weight golf club of standard length is gripped and swung with only one hand and a light weight ball is used to teach the fundamentals of the correct swing. Once the basics of the swing are mastered, weight can be incrementally added to the club head to gradually increase the club head weight.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of copending application Ser. No. 680,681, filed Apr. 27, 1976, which in turn is a continuation of application Ser. No. 491,318, filed July 24, 1974. Both of the above-identified applications are now abandoned.
BACKGROUND OF THE INVENTION
The invention relates to fluid-jet looms, and more particularly to arrangements in such looms for controlling the introduction of a weft thread from a system of plates of a picking comb into the loom shed.
One typical arrangement of this type is disclosed in German published application No. 2,105,559, having a publication date of Aug. 10, 1972. A control plate is inserted into a system of plates of the loom picking comb. Illustratively, the control plate has a pair of opposed arms that define a picking opening therebetween, and a narrow exit slot communicating with the picking opening for removal of the weft. A light source and a photocell are disposed on respectively opposite sides of a narrow portion of the exit slot of the control plate to define a detecting section, such section being located as close as practicable to the picking space of the control plate. At the location of the aligned light source and photocell, the narrowed exit slot of the control plate is made substantially equal to the diameter of the exiting weft thread. In such design, the confronting ends of both the light source and the photocell terminate flush with, or in recessed relation to, the respective peripheral walls of the exit slot.
SUMMARY OF THE INVENTION
The present invention contemplates an improvement of the weft exit control arrangement of the general type discussed above. In particular, in contrast to the flush or recessed relation of each of the light source and photocell of the detecting section, at least one of the detecting elements projects into the associated narrowed portion of the fixed exit slot, so that during the exit of the weft thread through the fixed slot, the weft will execute an enhanced wiping action on the detecting elements.
Such wiping action has been found to be advantageous in maintaining optimum efficiency of the detecting section, particularly in the normal dusty surroundings of the associated air-jet loom; in particular, the wiping action maintains the effective surfaces of the detecting section free of the ambient dust that would normally collect thereon.
BRIEF DESCRIPTION OF THE DRAWING
Exemplary embodiments of the object of the invention are shown in the attached drawings, wherein:
FIG. 1 is a cross-sectional view of a part of the picking comb;
FIG. 2 is a detailed view of the slot for the removal of the weft thread of a control plate;
FIG. 3 shows an exemplary embodiment of the control section of the picking comb in a partly cross-sectional view;
FIG. 4 is a similar view of another exemplary embodiment; and
FIG. 5 is a front view of the control section shown in FIG. 3.
DETAILED DESCRIPTION
A picking comb 2 with a reed 3 is supported by the slay 1 of a weaving machine, the slay, reed, and comb performing an oscillating movement. The picking comb 2 is composed of a system of plates 4 which at the picking moment are engaged into the shed 6 formed by opened weft threads 5 (FIG. 3). Each plate 4 has a picking opening 7 and a slot 8 for the removal of the weft thread. In the case of pneumatic picking, the picking opening 7 has a profile adapted for causing the stream of the medium taking along the weft thread to flow in a straight path. A control plate 10, controlling the removal of the weft 9 through a slot 8' corresponding to slots 8 of the plates 4, is inserted into the system of plates 4 of the picking comb 2 at a location where this control should be accomplished. In order to ensure a reliable operation thereof, this control plate 10 should be situated at a place on the picking comb 2 where at the picking moment it engages between the warp threads 5 of the shed 6. The shape of the control plate 10 corresponds substantially to the shape of the remaining plates 4 of the picking comb 2 in order to be able to penetrate into the shed 6 by a smooth pushing apart of the warp threads 5.
The control plate 10 comprises in addition to its supporting part 13 two opposed arms 11, 12. The detection means, i.e., a receiver of the detection signal, for instance a photocell 14, is situated on one of these arms 11 of the control plate 10 and a source of the detecting signal, for instance a light guide 15 such as a curved rod or fiber made of acrylic resin such as "Lucite," is situated together with the light source 16 at the incoming edge of the other arm 12 of the control plate 10. The light source 16 is cushioned and supported adjustably with respect to the inlet end of the light guide 15. At least one of the elements 14 and 15 (illustratively the photocell 14) projects into the slot 8' as shown best in FIG. 2, while the other of the elements 14 and 15 may either project into the slot, or, as shown in FIG. 2, terminate flush with it. As indicated below, the position of the detecting section 17 in the slot 8' for removal of the weft thread is important for a reliable indication, and thus also for the control of whether the weft has been correctly introduced into the shed. It is necessary to have the detecting section 17 at least on the borders of the picking space of the control plate 10. The picking spaces can comprise not only the picking opening 7' of the control plate 10, but also a part of the length of the slot 8' for the removal of the weft thread. This is due to the fact that the track of the introduced weft 9 passes not only along the axis of picking openings 7 of the picking comb 2 composed of plates, but through the whole space of picking openings 7 and through a part of their slots 8 for the removal of the weft thread.
The picking openings 7, or the slots 8 for the removal of the weft thread, may be closed by an easily deformable diaphragm 18 (see FIG. 3), the detecting section 17 of the slot 8 of the control plate 10 for the removal of the weft then being situated behind this diaphragm 18. When the slots 8 of the plates 4 of the picking comb 2 for removal of the weft thread are closed by the warp threads 5 of the shed 6, the detecting section 17 is situated behind the plane of these warp threads 5. It is, however, sufficient if the detecting section 17 is situated behind the warp threads 5 closing the slot 8' for removal of the weft of at least the control plate 10.
This is achieved if the warp threads 5 do not close the slots 8 of the plates 4 of the picking comb 2 and if the slot 8' of the control plate 10 for removal of the weft is prolonged. It is equally advantageous to reduce the width of the slot 8' of the control plate 10 for removal of the weft at the detecting section 17 but only to a minimum equal to the diameter of the controlled weft thread 9 in order to enable its removal. Because of the projection of the photocell 14 into the reduced-width portion of the slot 8', the exiting weft thread 9 will exert a positive wiping action of a frictional nature on each of the elements of the detecting section 17. The detecting section 17 thus remains constantly clean without dust or fibers, and consequently does not cause the generation of wrong signals.
Picking combs 2, particularly in looms of larger width may be divided into sections and arranged on the slay 1 of the loom. The plates 4 of each section of the picking comb 2 are fixed on a bar 20, for instance by glueing. The bars 20, with the plates 4 together with the reed 3, are mounted in a groove 19 of the slay and secured thereto by screws 21.
The arrangement for the control of the introduced weft 9 represents advantageously an independent control section of the picking comb 2 (see FIGS. 3 and 4), fixed on the required control place of the introduced weft by means common to that for fixing the sections of the picking comb 2 and of the reed 3, i.e., in the groove 19 of the slay and secured thereto by screws 21.
The arrangement for the control of the introduced weft 9 represents advantageously an independent control section of the picking comb 2 (see FIGS. 3 and 4), fixed on the required control place of the introduced weft by means common to that for fixing the sections of the picking comb 2 and of the reed 3, i.e., in the groove 19 of the slay 1 and secured by screws 21.
The control plate 10 together with other plates 4 is fixed on a body 22 of the control section of the picking comb 2. The body 22 corresponds by its external shape to the shape of the bar 20. It is, however, provided with a recess 23, which can be closed by a removable cover 24. A light source 16 fixed on a bearing plate 25 (FIG. 4), which can be advantageously of resilient material in order to cushion the light source 16 from the shocks of the slay 1, is arranged in this recess 23. The cushioning of the light source 16 substantially increases its operating life.
As shown in FIG. 3, the cushioning of the light source 16 can be also achieved if the control plate 10 is resiliently supported in the body 22 of the control section. In this embodiment, the supporting part 13 of the control plate 10 is supported in the body 22 of the control section by means of an elastic insert 29. The light source 16 is here fixed on the supporting part 13 of the control plate 10. Thus, there is achieved not only the cushioning of the light source 16, but also the cushioning of the detecting means, particularly of the photocell 14. The bearing plate 25 of the light source 16 is fixed to the body 22 of the control section of the picking comb 2 by screws 26. The openings 27 of the bearing plate 25 of the light source, through which the fixing screws 26 pass, are provided with an increased play. That enables a lateral adjustment of the position of the light source 16 with respect to the inlet end of the light guide 15. The adjustment of the height of the light source 16 is accomplished by inserts or shims 28 (FIG. 5).
A simple electronic device for processing the signal from the detecting means can be alternatively also provided in the recess 23 of the body 22. The control section of the picking comb 2 is connected by a cable 31 with an evaluating and operating part, situated on a frame (not shown) of the loom. The cable 31 serves both for the transmission of the control signal for evaluation and for the supplying of electric power to the control section.
The apparatus of the invention operates as follows: In the course of the movement of the slay 1 into the picking position, the plates of the picking comb 2 together with the control section penetrate into the shed 6 and take their position for the introduction of the weft 9. The weft 9 is introduced in a known way through the picking openings 7 of the plates 4 of the picking comb 2 and through the picking opening 7' of the control plate 10. When the slay 1 starts its movement into its beating position, the system of plates 4 and the control plate 10 are removed from the shed 6. Due to the action of the lower warp threads 5 of the shed 6, the introduced weft is forced through the slots 8 for the removal of the weft. The weft 9 introduced through the control plate 10 is forced to pass through the slot 8' of the control plate 10, and in the course of its passage through the detecting section 17, causes a change of the light flux to the photocell 14.
This signal is processed by the electronic device 30 and is transmitted via the cable 31 to the evaluating device. If the weft 9 has not passed through the detecting section 17 of the slot 8' for the removal of the weft of the control plate 10, the loom is stopped.
The arrangement for the control of the introduced weft according to this invention is obviously not limited to the described embodiments, it can be applied at all looms wherein the weft is introduced into the shed by a stream of a fluid take-up medium, by clamps and the like, guided by a picking comb.
Although the invention is illustrated and described with reference to a plurality of preferred embodiments thereof, it is to be expressly understood that it is in no way limited to the disclosure of such a plurality of embodiments, but is capable of numerous modifications within the scope of the appended claims.
|
A novel construction of a control plate inserted within and corresponding to a system of plates of a picking comb of a fluid-jet loom is described. The exit opening of the control plate has a detecting section including a light source and a photocell disposed in aligned spaced relation on opposite sides of the exit slot. The width of the exit slot is narrowed, at the location of the source and photocell, to a dimension substantially equal to the diameter of the weft thread exiting from the picking space of the control plate. At least one of the light source and photocell projects into the narrow exit slot to assure an enhanced wiping action of the weft thread on the detecting elements as the weft thread moves through the exit slot.
| 3
|
CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation of application U.S. Ser. No. 07/542,351 filed Jun. 22, 1990, now abandoned, which is a continuation-in-part of U.S. Ser. No. 279,194 filed Dec. 6, 1988, now U.S. Pat. No. 5,138,069, which is a continuation-in-part of U.S. Ser. No. 142,580 filed Jan. 7, 1988, now abandoned, which is a continuation-in-part of U.S. Ser. No. 373,755 filed on Jun. 30, 1989, now abandoned.
FIELD OF THE INVENTION
This invention relates to a method of treating chronic renal failure and, in particular, to a method which utilizes imidazole angiotensin-II (AII) receptor antagonists to treat chronic renal failure mediated by angiotensin-II.
BACKGROUND OF THE INVENTION
Angiotensin converting enzyme inhibitors may have beneficial effects over other antihypertensive agents in progressive renal disease of various origins including diabetic nephropathy, essential hypertension and other intrinsic renal diseases (See, e.g., Hypertension: Pathophysiology, Diagnosis, and Management, ed. by J. H. Laragh and B. M. Brenner, vol. 1, pp. 1163-1176, Raven Press, Ltd., New York, 1990; Hypertension: Pathophysiology, Diagnosis, and Management, ed. by J. H. Laragh and B. M. Brenner, vol. 2, pp. 1677-1687, Raven Press, Ltd., New York, 1990). For instance, in partially nephrectomized rats, glomerular capillary hypertension in the remnant kidney is associated with progressive proteinuria, focal glomerular sclerosis, and moderate hypertension. Angiotensin converting enzyme inhibitors, which lower systemic arterial pressure and glomerular capillary pressure, limit the progression of glomerular injury.
There are other antihypertensive agents which lower systemic arterial blood pressure to a similar extent, but fail to reduce glomerular capillary pressure. Such agents do not prevent the progression of glomerular injury. It is speculated that in these rats intrarenal generation of angiotensin-II constricts the renal efferent arteriole and causes an increase in glomerular hydraulic pressure. Glomerular hyperfiltration, hyperperfusion and/or hypertension may then initiate and induce glomerular lesions. Thus, blockade of the intrarenal formation of angiotensin-II by angiotensin converting enzyme inhibitors may retard the deterioration of renal failure.
Although the partially nephrectomized rat is associated with moderate hypertension, systemic hypertension does not appear to be necessary for the acceleration of renal disease. In the insulin-treated rat with streptozocin-induced diabetes, systemic arterial pressure is normal but glomerular capillary pressure is high. Similar to the partially nephrectomized rat model, angiotensin converting enzyme inhibitors are beneficial in limiting the glomerular structural lesions, suggesting that glomerular capillary hypertension but not systemic arterial hypertension play a critical role in rats with progressive renal failure.
Nonpeptide angiotensin-II receptor antagonists are believed to be more efficacious than angiotensin converting enzyme inhibitors in treating chronic renal failure because the nonpeptide angiotensin-II receptor antagonists may block the renal effect of angiotensin-II more completely irrespective of the source of angiotensin-II. In contrast, angiotensin converting enzyme inhibitors selectively block kininase II and, thus, may not inhibit totally the local formation of angiotensin-II in the kidney. Other types of peptidyl dipeptidase may also be responsible for the formation of angiotensin-II. (Wong, P. C. and Zimmerman, B. G.: Role of Extrarenal and Intrarenal Converting Enzyme Inhibition in Renal Vasodilator Response to Intravenous Captopril. Life Sci. 27: 1291, 1980; Schmidt M., Giesen-Crouse, E. M., Krieger, J. P., Welsch, C. and Imbs, J. L.: Effect of angiotensin converting enzyme inhibitors on the vasoconstrictor action of angiotensin I on isolated rat kidney. J. Cardiovasc. Pharmacol. 8 (Suppl. 10): S100, 1986)).
In clinical renal artery stenosis, the usefulness of angiotensin converting enzyme inhibitors may be limited by a reversible loss of filtration in the stenotic kidney. It is possible that nonpeptide angiotensin II receptor antagonists may have a similar renal effect in the stenotic kidney.
K. Matsumura, et al., in U.S. Pat. No. 4,207,324 issued Jun. 10, 1980 discloses 1,2-disubstituted-4-haloimidazole-5-acetic acid derivatives of the formula: ##STR1## wherein R 1 is hydrogen, nitro or amino; R 2 is phenyl, furyl or thienyl optionally substituted by halogen, lower alkyl, lower alkoxy or di-lower alkylamino; R 3 is hydrogen or lower alkyl and X is halogen; and their physiologically acceptable salts. These compounds have diuretic and hypotensive actions.
Furukawa, et al., in U.S. Pat. No. 4,355,040 issued Oct. 19, 1982 discloses hypotensive imidazole-5-acetic acid derivatives having the formula: ##STR2## wherein R 1 is lower alkyl, cycloalkyl, or phenyl optionally substituted; X 1 , X 2 , and X 3 are each hydrogen, halogen, nitro, amino, lower alkyl, lower alkoxy, benzyloxy, or hydroxy; Y is halogen and R 2 is hydrogen or lower alkyl; and salts thereof.
Furukawa, et al., in U.S. Pat. No. 4,340,598, issued Jul. 20, 1982, discloses hypotensive imidazole derivatives of the formula: ##STR3## wherein R 1 is lower alkyl or, phenyl C 1-2 alkyl optionally substituted with halogen or nitro; R 2 is lower alkyl, cycloalkyl or phenyl optionally substituted; one of R 3 and R 4 is --(CH 2 ) n COR 5 where R 5 is amino, lower alkoxyl or hydroxyl and n is 0, 1, 2 and the other of R 3 and R 4 is hydrogen or halogen; provided that R 1 is lower alkyl or phenethyl when R 3 is hydrogen, n=1 and R 5 is lower alkoxyl or hydroxyl; and salts thereof.
Furukawa et al., in European Patent Application 103,647 discloses 4-chloro-2-phenylimidazole-5-acetic acid derivatives useful for treating edema and hypertension of the formula: ##STR4## where R represents lower alkyl and salts thereof.
The metabolism and disposition of hypotensive agent 4-chloro-1-(4-methoxy-3-methylbenzyl)-2-phenyl-imidazole-5-acetic acid is discloses by H. Torii in Takeda Kenkyushoho, 41, No 3/4, 180-191 (1982).
Frazee et al., in European Patent Application 125,033-A discloses 1-phenyl(alkyl)-2-(alkyl)-thioimidazole derivatives which are inhibitors of dopamine-β-hydroxylase and are useful as antihypertensives, diuretics and cardiotonics. European Patent Application 146,228 filed Oct. 16, 1984 by S. S. L. Parhi discloses a process for the preparation of 1-substituted-5-hydroxymethyl-2-mercaptoimidazoles.
A number of references disclose 1-benzyl-imidazoles such as U.S. Pat. No. 4,448,781 to Cross and Dickinson (issued May 15, 1984); U.S. Pat. No. 4,226,878 to Ilzuka et al. (issued Oct. 7, 1980); U.S. Pat. No. 3,772,315 to Regel et al. (issued Nov. 13, 1973); U.S. Pat. No. 4,379,927 to Vorbruggen et al. (issued Apr. 12, 1983); amongst others.
Pals et al., Circulation Research, 29, 673 (1971) describe the introduction of a sarcosin residue in position 1 and alanine in position 8 of the endogenous vasoconstrictor hormone AII to yield an (octa)peptide that blocks the effects of AII on the blood pressure of pithed rats. This analog, [Sar 1 , Ala 8 ] AII, initially called "P-113" and subsequently "Saralasin", was found to be one of the most potent competitive antagonists of the actions of AII, although, like most of the so-called peptide-AII-antagonists, it also possesses agonistic actions of its own. Saralasin has been demonstrated to lower arterial pressure in mammals and man when the (elevated) pressure is dependent on circulating AII (Pals et al., Circulation Research, 29, 673 (1971); Streeten and Anderson, Handbook of Hypertension, Vol. 5, Clinical Pharmacology of Antihypertensive Drugs, A. E. Doyle (Editor), Elsevier Science Publishers B. V., p. 246 (1984)). However, due to its agonistic character, saralasin generally elicits pressor effects when the pressure is not sustained by AII. Being a peptide, the pharmacological effects to saralasin are relatively short-lasting and are only manifest after parenteral administration, oral doses being ineffective. Although the therapeutic uses of peptide AII-blockers, like saralasin, are severely limited due to their oral ineffectiveness and short duration of action, their major utility is as a pharmaceutical standard.
SUMMARY OF THE INVENTION
According to the present invention there is provided a method of treating chronic renal failure mediated by AII in a mammal comprising administering to the mammal a therapeutically effective amount of a pharmaceutical composition having the formula (I): ##STR5## wherein
R 1 is 4--CO 2 H; 4--CO 2 R 9 ; ##STR6##
R 2 is H; Cl; Br; I; F; NO 2 ; CN; alkyl of 1 to 4 carbon atoms; acyloxy of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms; CO 2 H; CO 2 R 9 ; NHSO 2 CH 3 ; NHSO 2 CF 3 ; CONHOR 12 ; SO 2 NH 2 ; ##STR7## aryl; or furyl;
R 3 is H; Cl, Br, I or F; alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms;
R 4 is CN, NO 2 or CO 2 R 11 ;
R 5 is H, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, alkenyl or alkynyl of 2 to 4 carbon atoms;
R 6 is alkyl of 2 to 10 carbon atoms, alkenyl or alkynyl of 3 to 10 carbon atoms or the same groups substituted with F or CO 2 R 14 ; cycloalkyl of 3 to 8 carbon atoms, cycloalkylalkyl of 4 to 10 carbon atoms; cycloalkylalkenyl or cycloalkylalkynyl of 5 to 10 carbon atoms; (CH 2 ) s Z(CH 2 ) m R 5 optionally substituted with F or CO 2 R 14 ; benzyl or benzyl substituted on the phenyl ring with 1 or 2 halogens, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms or nitro;
R 7 is H, F, Cl, Br, I, NO 2 , C v F 2v+1 , where v=1-6; C 6 F 5 ; CN; ##STR8## straight or branched alkyl of 1 to 6 carbon atoms; phenyl or phenylalkyl, where alkyl is 1 to 3 carbon atoms; or substituted phenyl or substituted phenylalkyl, where alkyl is 1 to 3 carbon atoms, substituted with one or two substituents selected from alkyl of 1 to 4 carbon atoms, F, Cl, Br, OH, OCH 3 , CF 3 , and COOR, where R is H, alkyl of 1 to 4 carbon atoms, or phenyl; vinyl; alkynyl of 2-10 carbon atoms; phenylalkynyl where the alkynyl portion is 2-6 carbon atoms; heteroaryl selected from 2- and 3-thienyl, 2- and 3-furyl, 2-, 3-, and 4-pyridyl, 2-pyrazinyl, 2-, 4-, and 5-pyrimidinyl, 3- and 4-pyridazinyl, 2-, 4- and 5-thiazolyl, 2-, 4-, and 5-selenazolyl, 2-, 4-, and 5-oxazolyl; 2- or 3-pyrrolyl, 3-, 4- or 5-pyrazolyl, and 2-, 4- or 5-imidazolyl; o-, m- or p-biphenylyl; o-, m- or p-phenoxyphenyl; substituted phenylalkynyl, heteroaryl, biphenyl or phenoxyphenyl as defined above substituted on ring carbon with 1 or 2 substituents selected from halogen, alkoxy of 1-5 carbon atoms, alkyl of 1-5 carbon atoms, --NO 2 , --CN, --CF 3 , --COR 16 , --CH 2 OR 17 , --NHCOR 17 , CONR 18 R 19 , S(O) r R 17 , and SO 2 NR 18 R 19 ; pyrrolyl, pyrazolyl or imidazolyl as defined above substituted on ring nitrogen with alkyl of 1-5 carbon atoms or benzyl; or substituted alkyl, alkenyl, or alkynyl of 1 to 10 carbon atoms substituted with a substituted or unsubstituted heteroaryl, biphenylyl or phenoxyphenyl group as defined above; any of the foregoing polycyclic aryl groups substituted with 1 or 2 substituents selected from halogen, alkoxy of 1-5 carbon atoms, alkyl of 1-5 carbon atoms, --NO 2 , --CN, --CF 3 , --COR 16 , --CH 2 OR 17 , --NHCOR 17 , CONR 18 R 19 , S(O) r R 17 , and SO 2 NR 18 R 19 ; the anhydride of 4,5-dicarboxyl-1- or 2-naphthyl; or substituted alkyl of 1 to 10 carbon atoms, alkenyl or alkynyl of 2 to 10 carbon atoms substituted with a substituted or unsubstituted polycyclic aryl group as defined above;
R 8 is H, CN, alkyl of 1 to 10 carbon atoms, alkenyl of 3 to 10 carbon atoms, or the same groups substituted with F; phenylalkenyl wherein the aliphatic portion is 2 to 6 carbon atoms; --(CH 2 ) m -imidazol-1-yl; --(CH 2 ) m -1,2,3-triazolyl optionally substituted with one or two groups selected from CO 2 CH 3 or alkyl of 1 to 4 carbon atoms; --(CH 2 ) s -tetrazolyl; ##STR9##
R 9 is ##STR10##
R 10 is alkyl of 1 to 6 carbon atoms or perfluoroalkyl of 1 to 6 carbon atoms, 1-adamantyl, 1-naphthyl, 1-(1-naphthyl)ethyl, or (CH 2 ) p C 6 H 5 ;
R 11 is H, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl or benzyl;
R 12 is H, methyl or benzyl;
R 13 is --CO 2 H; --CO 2 R 9 ; --CH 2 CO 2 H, --CH 2 CO 2 R 9 ; ##STR11##
R 14 is H, alkyl or perfluoroalkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl or benzyl;
R 15 is H, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl, benzyl, acyl of 1 to 4 carbon atoms, phenacyl;
R 16 is H, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, (CH 2 ) p C 6 H 5 , OR 17 , or NR 18 R 19 ;
R 17 is H, alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, phenyl or benzyl;
R 18 and R 19 independently are H, alkyl of 1 to 4 carbon atoms, phenyl, benzyl, α-methylbenzyl, or taken together with the nitrogen form a ring of the formula ##STR12##
Q is NR 20 , O or CH 2 ;
R 20 is H, alkyl of 1-4 carbon atoms, or phenyl;
R 21 is alkyl of 1 to 6 carbon atoms, --NR 22 R 23 , or ##STR13##
R 22 and R 23 independently are H, alkyl of 1 to 6 carbon atoms, benzyl, or are taken together as (CH 2 ) u where u is 3-6;
R 24 is H, CH 3 or --C 6 H 5 ;
R 25 is NR 27 R 28 , OR 28 , NHCONH 2 , NHCSNH 2 , ##STR14##
R 26 is hydrogen, alkyl with from 1 to 6 carbon atoms, benzyl, or allyl;
R 27 and R 28 are independently hydrogen, alkyl with from 1 to 5 carbon atoms, or phenyl;
R 29 and R 30 are independently alkyl of 1-4 carbon atoms or taken together are --(CH 2 ) q --;
R 31 is H, alkyl of 1 to 4 carbon atoms, --CH 2 CH═CH 2 or --CH 2 C 6 H 4 R 32 ;
R 32 is H, NO 2 , NH 2 , OH or OCH 3 ;
X is a carbon-carbon single bond, --CO--, --CH 2 --, --O--, --S--, --NH--, ##STR15## --OCH 2 --, --CH 2 O--, --SCH 2 --, --CH 2 S--, --NHC(R 27 )(R 28 )--, --NR 23 SO 2 --, --SO 2 NR 23 --, --C(R 27 )(R 28 )NH--, --CH═CH--, --CF═CF--, --CH═CF--, --CF═CH--, --CH 2 CH 2 --, --CF 2 CF 2 --, ##STR16##
Y is O or S;
Z is O, NR 11 , or S;
m is 1 to 5;
n is 1 to 10;
p is 0 to 3;
q is 2 to 3;
r is 0 to 2;
s is 0 to 5;
t is 0 or 1;
or a pharmaceutically acceptable salt thereof; provided that:
(1) the R 1 group is not in the ortho position;
(2) when R 1 is ##STR17##
X is a single bond, and R 13 is CO 2 H, or ##STR18## then R 13 must be in the ortho or meta position; or when R 1 and X are as above and R 13 is NHSO 2 CF 3 or NHSO 2 CH 3 , R 13 must be ortho;
(3) when R 1 is ##STR19## and X is other than a single bond, then R 13 must be ortho except when X=NR 23 CO and R 13 is NHSO 2 CF 3 or NHSO 2 CH 3 , then R 13 must be ortho or meta;
(4) when R 1 is 4--CO 2 H or a salt thereof, R 6 cannot be S-alkyl;
(5) when R 1 is 4--CO 2 H or a salt thereof, the substituent on the 4-position of the imidazole cannot be CH 2 OH, CH 2 OCOCH 3 , or CH 2 CO 2 H;
(6) when R 1 is ##STR20## X is --OCH 2 --, and R 13 is 2--CO 2 H, and R 7 is H then R 6 is not C 2 H 5 S;
(7) when R 1 is ##STR21## and R 6 is n-hexyl, then R 7 and R 8 are not both hydrogen;
(8) when R 1 is ##STR22## R 6 is not methoxybenzyl;
(9) the R 6 group is not --CHFCH 2 CH 2 CH 3 or CH 2 OH;
(10) when r=0, R 1 is ##STR23## X is --NH--CO--, R 13 is 2--NHSO 2 CF 3 , and R 6 is n-propyl, then R 7 and R 8 are not --CO 2 CH 3 ;
(11) when r=0, R 1 is ##STR24## X is --NH--CO--, R 13 is 2--COOH, and R 6 is n-propyl, then R 7 and R 8 are not --CO 2 CH 3 ;
(12) when r=1, R 1 = ##STR25## X is a single bond, R 7 is Cl, and R 8 is --CHO, then R 13 is not 3-(tetrazol-5-yl);
(13) when r=1, R 1 = ##STR26## X is a single bond, R 7 is Cl, and R 8 is --CHO, then R 13 is not 4-(tetrazol-5-yl).
Preferred in the method of this invention are compounds having the formula (II): ##STR27## wherein
R 1 is --CO 2 H; --NHSO 2 CF 3 ; ##STR28##
R 6 is alkyl of 3 to 10 carbon atoms, alkenyl of 3 to 10 carbon atoms, alkynyl of 3 to 10 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, benzyl substituted on the phenyl ring with up to two groups selected from alkoxy of 1 to 4 carbon atoms, halogen, alkyl of 1 to 4 carbon atoms, and nitro;
R 8 is ##STR29## phenylalkenyl wherein the aliphatic portion is 2 to 4 carbon atoms; --(CH 2 ) m -imidazol-1-yl; or --(CH 2 ) m -1,2,3-triazolyl optionally substituted with one two groups selected from --CO 2 CH 3 or alkyl or 1 to 4 carbon atoms;
R 13 is --CO 2 H, --CO 2 R 9 , NHSO 2 CF 3 ; SO 3 H; or ##STR30##
R 16 is H, alkyl or 1 to 5 carbon atoms, OR 17 , or NR 18 R 19 ;
X is carbon-carbon single bond, --CO--, --CH 2 CH 2 --, ##STR31## --OCH 2 --, --CH 2 O--, --O--, --SCH 2 --, --CH 2 S--, --NH--CH 2 --, --CH 2 NH-- or --CH═CH--; and pharmaceutically acceptable salts of these compounds.
More preferred in the process of the invention are compounds of the preferred scope where:
R 2 is H, alkyl of 1 to 4 carbon atoms, halogen, or alkoxy or 1 to 4 carbon atoms;
R 6 is alkyl, alkenyl or alkynyl of 3 to 7 carbon atoms;
R 7 is heteroaryl selected from 2- and 3-thienyl, 2- and 3-furyl, 2-, 3-, and 4-pyridyl, p-biphenylyl; H, Cl, Br, I; C v F 2v+1 , where v=1-3; ##STR32## straight or branched chain alkyl of 1 to 6 carbon atoms; or phenyl;
R 8 is ##STR33##
R 10 is CF 3 , alkyl or 1 to 6 carbon atoms or phenyl;
R 11 is H, or alkyl or 1 to 4 carbon atoms;
R 13 is CO 2 H; CO 2 CH 2 OCOC(CH 3 ) 3 ; NHSO 2 CF 3 ; ##STR34##
R 14 is H, or alkyl of 1 to 4 carbon atoms;
R 15 is H, alkyl or 1 to 4 carbon atoms, or acyl or 1 to 4 carbon atoms;
R 16 is H, alkyl or 1 to 5 carbon atoms; OR 17 ; or ##STR35##
m is 1 to 5;
X=single bond, --O--; --CO--; --NHCO--; or --OCH 2 --; and
pharmaceutically acceptable salts.
More preferred in the method of the invention are compounds of Formula II, wherein R 1 is ##STR36## and X is a single bond; and pharmaceutically suitable salts thereof.
Most preferred in the method of the invention are compounds of formula II selected from the following, and pharmaceutically acceptable salts thereof:
2-Butyl-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]-5-(hydroxymethyl)imidazole
2-Butyl-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]-5-(hydroxymethyl)imidazole
2-Butyl-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]-5-[(methoxycarbonyl)aminomethyl] imidazole
2-Butyl-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]-5-[(propoxycarbonyl)aminomethyl] imidazole
2-Butyl-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-Butyl-1-[(2'-carboxybiphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-(1E-Butenyl)-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]-5-(hydroxymethyl)imidazole
2-(1E-Butenyl)-4-chloro-1-[(2'-carboxybiphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-Propyl-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]-5-(hydroxymethyl)imidazole
2-Propyl-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-Butyl-4-chloro-1-[2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-(1E-Butenyl)-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]-5-hydroxymethyl)imidazole
2-(1E-Butenyl)-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-Butyl-4-chloro-1-[(2'-(1H-tetrazol-5-yl)-biphenyl-4-yl)methyl]imidazole-5-carboxylic acid
2-Propyl-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxylic acid
2-Propyl-4-trifluoromethyl-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxylic acid
2-Propyl-4-trifluoromethyl-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]-5-(hydroxylmethyl)imidazole
2-Butyl-4-trifluoromethyl-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboyxlic acid
2-Propyl-4-trifluoromethyl-1-[(2'-(carboxybiphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
2-Propyl-4-pentafluoroethyl-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]-5-(hydroxymethyl)-imidazole
2-Propyl-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-4,5-dicarboxylic acid
2-Propyl-4-pentafluoroethyl-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxylic acid
2-Propyl-4-pentafluoroethyl-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]imidazole-5-carboxaldehyde
1-[(2'-(1H-Tetrazol-5-yl)biphenyl-4-yl)methyl]-4-phenyl-2-propylimidazole-5-carboxaldehyde
1-[(2'-Carboxybiphenyl-4-yl)methyl]-4-phenyl-2-propylimidazole-5-carboxaldehyde
Note that throughout the text when an alkyl substituent is mentioned, the normal alkyl structure is meant (i.e., butyl is n-butyl) unless otherwise specified.
Pharmaceutically suitable salts include both the metallic (inorganic) salts and organic salts; a list of which is given in Remington's Pharmaceutical Sciences, 17th Edition, pg. 1418 (1985). It is well known to one skilled in the art that an appropriate salt form is chosen based on physical and chemical stability, flowability, hydroscopicity and solubility. Preferred salts of this invention for the reasons cited above include potassium, sodium, calcium and ammonium salts.
Also within the scope of this invention are methods of using pharmaceutical compositions comprising a suitable pharmaceutical carrier and a compound of Formula (I), to treat chronic renal failure. The pharmaceutical compositions can optionally contain one or more other therapeutic agents. It should be noted in the foregoing structural formula, when a radical can be a substituent in more than one previously defined radical, that first radical can be selected independently in each previously defined radical. For example, R 1 , R 2 and R 3 can each be CONHOR 12 . R 12 need not be the same substituent in each of R 1 , R 2 and R 3 but can be selected independently for each of them.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of Formula (I) useful in this invention are described in and prepared by methods set forth in European Patent Application EPA 0 324 377, published Jul. 19, 1989, (page 17, line 5 through page 212, line 32), European Patent Application EPA 0 253,310, published Jan. 20, 1988 (page 15, line 26, through page 276) and copending commonly-assigned U.S. patent application U.S. Ser. No. 07/373,755, filed Jun. 30, 1989, (page 16, line 21 through page 153, line 15), the disclosures of which are hereby incorporated by reference.
It is believed that the compounds described herein are efficacious in the treatment of most chronic renal failure cases mediated by AII. While it is not clear, there is a possibility that the efficacy of these compounds may be limited in the treatment of renal artery stenosis due to a reversible loss of filtration in the stenotic kidney.
The following illustrate the use of nonpeptide AII receptor antagonists to treat chronic renal failure mediated by angiotensin-II:
PARTIALLY NEPHRECTOMIZED RATS
Rats are subjected to five-sixths renal ablation by surgically removing the right kidney and infarction of about two-thirds of the left kidney by ligation of two or three branches of the left renal artery as described by Anderson et al. in J. Clin. Invest., Vol. 76, pages 612-619 (August 1985). Rats are fed standard rat chow containing about 24% protein by weight and are separated into two groups. The rats in Group I are not treated. The rats in Group II are treated over a period of four weeks using one of the compounds described above. Renal hemodynamics and glomerular injury are monitored in both groups of rats after four weeks.
It is expected that the rats in Group I (no treatment) would have high blood pressure, protein urea and glomerular structural lesions whereas the rats in Group II (treatment with the test compound) would have normal blood pressure, less protein urea and fewer glomerular lesions.
STREPTOZOTOCIN-INDUCED DIABETIC RATS
This procedure is described by Zatz et al. in Proc. Natl. Acad. Sci. USA 82: 5963-5967 (September 1985). Rats are studied two to ten weeks after being injected once with streptozotocin (60 mg/kg i.v.). In addition, ultralente insulin is given to maintain the blood glucose level between 200-400 mg/dl. Rats are maintained on diet containing about 50% protein by weight. The rats are then separated into two groups. The rats in Group I are not treated. The Group II rats are treated for about four to five weeks after streptozotocin injection using one of the compounds described above. Renal hemodynamics and glomerular injury are monitored in both groups of rats.
It is expected that the rats in Group I (no treatment) would have normal blood pressure, protein urea, and glomerular structural lesions whereas the rats in Group II (treatment with the test compound) would have slightly lower blood pressure, less protein urea and fewer glomerular lesions.
DOSAGE FORMS
The compounds of this invention can be administered for the treatment of AII-mediated chronic renal failure according to the invention by any means that effects contact of the active ingredient compound with the site of action. For example, administration can be parenteral, i.e., subcutaneous, intravenous, intramuscular, or intraperitoneal. Alternatively, or concurrently, in some cases administration can be by the oral route.
The compounds can be administered by any conventional means available for use in conjunction with pharmaceuticals, either as individual therapeutic agents or in a combination of therapeutic agents. They can be administered alone, but are generally administered with a pharmaceutical carrier selected on the basis of the chosen route of administration and standard pharmaceutical practice.
For the purpose of this disclosure, a warm-blooded animal is a member of the animal kingdom possessed of a homeostatic mechanism and includes mammals and birds.
The dosage administered will be dependent on the age, health and weight of the recipient, the extent of disease, kind of concurrent treatment, if any, frequency of treatment and the nature of the effect desired. Usually, a daily dosage of active ingredient compound will be from about 1-500 milligrams per day. Ordinarily, from 10 to 100 milligrams per day in one or more applications is effective to obtain desired results.
The active ingredient can be administered orally in solid dosage forms, such as capsules, tablets, and powders, or in liquid dosage forms, such as elixirs syrups, and suspensions. It can also be administered parenterally, in sterile liquid dosage forms.
Gelatin capsules contain the active ingredient and powdered carriers, such as lactose, starch, cellulose derivatives, magnesium stearate, stearic acid, and the like. Similar diluents can be used to make compressed tablets. Both tablets and capsules can be manufactured as sustained release products to provide for continuous release of medication over a period of hours. Compressed tablets can be sugar coated or film coated to mask any unpleasant taste and protect the tablet from the atmosphere, or enteric coated for selective disintegration in the gastrointestinal tract.
Liquid dosage forms for oral administration can contain coloring and flavoring to increase patient acceptance.
In general, water, a suitable oil, saline, aqueous dextrose (glucose), and related sugar solutions and glycols such as propylene glycol or polyethylene glycols are suitable carriers for parenteral solutions. Solutions for parenteral administration preferably contain a water soluble salt of the active ingredient, suitable stabilizing agents, and if necessary, buffer substances. Antioxidizing agents such as sodium bisulfite, sodium sulfite, or ascorbic acid, either alone or combined, are suitable stabilizing agents. Also used are citric acid and its salts and sodium EDTA. In addition, parenteral solutions can contain preservatives, such as benzalkonium chloride, methyl- or propylparaben, and chlorobutanol.
Suitable pharmaceutical carriers are described in Remington's Pharmaceutical Sciences, A. Osol, a standard reference text in this field.
Useful pharmaceutical dosage-forms for administration of the compounds of this invention can be illustrated as follows:
Capsules:
A large number of unit capsules are prepared by filling standard two-piece hard gelatin capsules each with 100 milligrams of powdered active ingredient, 150 milligrams of lactose, 50 milligrams of cellulose, and 6 milligrams magnesium stearate.
Soft Gelatin Capsules:
A mixture of active ingredient in a digestible oil such as soybean oil, cottonseed oil or olive oil is prepared and injected by means of a positive displacement pump into gelatin to form soft gelatin capsules containing 100 milligrams of the active ingredient. The capsules are washed and dried.
Tablets:
A large number of tablets are prepared by conventional procedures so that the dosage unit is 100 milligrams of active ingredient, 0.2 milligrams of colloidal silicon dioxide, 5 milligrams of magnesium stearate, 275 milligrams of microcrystalline cellulose, 11 milligrams of starch and 98.8 milligrams of lactose. Appropriate coatings may be applied to increase palatability or delay absorption.
Injectable:
A parenteral composition suitable for administration by injection is prepared by stirring 1.5% by weight of active ingredient in 10% by volume propylene glycol. The solution is made to volume with water for injection and sterilized.
Suspension:
An aqueous suspension is prepared for oral administration so that each 5 milliliters contain 100 milligrams of finely divided active ingredient, 100 milligrams of sodium carboxymethyl cellulose, 5 milligrams of sodium benzoate, 1.0 grams of sorbitol solution, U.S.P., and 0.025 milliliters of vanillin.
The same dosage forms can generally be used when the compounds of this invention are administered stepwise in conjunction with another therapeutic agent. When the drugs are administered in physical combination, the dosage form and administration route should be selected for compatibility with both drugs.
|
Substituted imidazoles such as 2-butyl-4-chloro-1-[(2'-(1H-tetrazol-5-yl)biphenyl-4-yl)methyl]-5-(hydroxymethyl)imidazole and 2-butyl-4-chloro-1-[(2'-carboxybiphenyl-4-yl)-methyl]-5-(hydroxymethyl)imidazole and pharmaceutically acceptable salts thereof are useful for treating chronic renal failure, mediated by angiotensin-II.
| 2
|
BACKGROUND OF THE INVENTION
[0001] (a) Technical Field of the Invention
[0002] The present invention relates to firefly-container, and in particular to a firefly container for use in observing and feeding fireflies, which comprises transparent walls and an observer is able to observe metamorphosis of fireflies through the transparent walls.
[0003] (b) Brief Description of the Prior Art
[0004] Children as well as the adults are fascinated by fireflies as they fluorescence. If fireflies are used as teaching material for the subject of biology, the degree of acceptance in rearing insects will increase and the public will understand the life cycle of insects. However, fireflies are forced to be reared in an ordinary aquarium or insect container because there was no container specifically designed for feeding and observing fireflies available in the market nowadays. These aquariums and insect containers are usually huge and heavy that they can only be displayed at a fixed position. People can merely watch the insects at a specific position, and these boxes are not conveniently to be moved, or the aquariums and insect boxes cannot be carried along. In addition, the shapes of these feeding containers available in the market are mostly cuboid and cubic shape, which are not attracted to consumers.
[0005] In order to improve the designs of aquariums and insect boxes available in the market, the present invention integrates the fluorescent characteristic of fireflies into the design of insect container, so as to enhance the will of the public to contact and rear fireflies.
SUMMARY OF THE INVENTION
[0006] The present invention provides a firefly-container for observing and feeding of fireflies, which comprises transparent walls having at least one hole for ventilation and providing a habitat for fireflies by supplying nutrients and water, covering object and a feeding base, to allow the fireflies to live. The container is provided with a component for hand-carrying such that the container is used as a firefly-lantern, and this provides teaching and funs to children.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows the structure of a firefly-container in accordance with the present invention.
[0008] FIG. 2 shows the actual usage of the firefly-container in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0009] The present invention provides a firefly-container for observing and feeding of fireflies, which comprises transparent walls having at least one hole for ventilation and providing a habitat for fireflies by supplying nutrients, water, covers and the feeding bases, to allow the fireflies to live. The container is provided with a component for hand-carrying such that the container is used as a firefly-lantern, and this provides teaching and funs to children.
[0010] The walls of the firefly-container of present invention are made from transparent materials, such as glass and plastic et al. to allow users to observe the metamorphosis of fireflies conveniently and to allow fluorescence emitted by fireflies be seen easily.
[0011] The firefly-container of the present invention also provides air-hole for ventilation between inside and outside of the container to avoid fireflies from suffocating within the container. The air-hole can be openings on the walls or nets which are used to replace one of the walls, such as the top end of the container. The air-holes are so small that fireflies in the firefly-container will not escape to the outside.
[0012] A feeding base placed in the firefly-container will discharge water and to maintain humidity in the firefly-container, so as to provide an inhabitation for fireflies. Furthermore, if plants are grown in the firefly-container, the feeding base acts as a ground for plants growing. The feeding base composed of inorganic soil, organic soil or artificial substrates. The definition of inorganic soil is products effloresced from rocks and mines in nature, such as earth, gravel and sand; the definition of organic soil is products which are rotten and decomposed from organism, such as dead woods, dead leaves and rotten woods; and the artificial substrates include paper-products, plastics, sponge or other artificial pad material for insect-feeding.
[0013] The covering objects within the container are used to shelter fireflies from lights, and the covering objects also provide a place of crawling and resting. For this reason, any object which can block lights is used as a covering object, such as plants, laminated board, and miniature structure and housing models.
[0014] A damp environment is required for the growth of fireflies and the environment is maintained by placing a water pool in the firefly-container or sprinkling water regularly. The firefly-container of the present invention further comprises water treatment equipment or a water conditioner to keep the pool water quality constant.
[0015] The firefly-container of the present invention further comprises a handle for convenient moving of the firefly-container. All decorative components in the firefly-container are firmly secured so as to avoid the living environment of fireflies from being destroyed when the firefly-container is being moved from place to place.
[0016] The firefly-container of the present invention provides a living environment for each developmental stage of fireflies, which include egg, larva, pupa and imago. Therefore, it is easier to feed fireflies and observe the life cycle of firefly using the firefly-container of the present invention.
[0017] The firefly-container of the present invention provides fun and teaching to children and the knowledge of life cycle of fireflies. In addition, the firefly-container is being shown as a work of art because of its aesthetic appearance of various shapes. When a hand-carrying component is attached, the container is turned into a “firefly-lantern”.
EXAMPLES
[0018] The structure of a firefly-container of the present invention was shown in FIG. 1 . A major part of the present firefly-container included transparent walls, having air-holes for ventilation. The transparent walls of the firefly-container were made of hyaline glass, hyaline plastics or other transparent materials. The air-holes of the present firefly-container were displayed in form of openings around the peripheral walls or a nets structure.
[0019] To furnish ornamental or decorative objects inside the firefly-container conveniently, the present invention comprised a movable sliding door or a lid. Detachable walls for the firefly-container were also designed for the same purpose. Besides, the walls could be detached for cleaning and feeding the fireflies in the container. In one embodiment, the air-hole and detachable walls of firefly-container were designed to be an integer. There was a handle attached to the container and the size and weight of the container allowed it to be easy carried in one hand.
[0020] FIG. 2 was a schematic view showing the feeding of fireflies in the firefly-container of the present invention. The present invention of firefly-container, which comprises a pool, soil and plants et al., can provide a favorable environment for the development of fireflies. Additionally, the fluorescence of fireflies was easily emitted to outside because of the transparent walls of the firefly-container, which made the present firefly-container to be a firefly-lantern.
[0021] While the invention has been described with respect to preferred embodiment, it will be clear to those skilled in the art that modifications and improvements may be made to the invention without departing from the spirit and scope of the invention. Therefore, the invention is not to be limited by the specific illustrative embodiment, but only by the scope of the appended claims.
|
The present invention provides a firefly container, comprising transparent outer walls and air holes. After putting nutrients, water, shelters, and matrixes into the viewer, fireflies can be allowed to live in it. Moreover, if a handling device is installed on the present invention, it can be used as a “firefly lantern” and provides edutainmental functions.
| 1
|
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority and all other benefits under
[0002] [0002] 35 U.S.C. §119 of prior filed co-pending British patent application No. 00 022274.9, filed Feb. 1, 2000, entitled, ELECTRO-OPTICAL POLARIZATION CONTROLLER and is incorporated herein by reference thereto.
FIELD OF THE INVENTION
[0003] The present invention relates to an electro-optical polarization controller and methods of using such a polarization controller as well as an optical system employing such a controller, such as an optical telecommunication system.
BACKGROUND OF THE INVENTION
[0004] There are several problems associated with the transmission of data at high data rates over long-distances using optical signals which are propagated along optical fibers. Regimes for the compensation of loss and dispersion are well known, but a remaining obstacle to high-data rate long-distance data transmission is polarization mode dispersion (PMD), where the polarization of the transmitted signal varies in a random manner, caused primarily by fibre birefringence.
[0005] In an attempt to address the problem of PMD, it is known to deploy in a receiver a polarization controller that is able to control dynamically the polarization state of a received optical signal. See, for example, Nigel G. Walker et al., Journal of Lightwave Technology, Vol. 8(3), pp. 438-457, 1990 and U.S. Pat. No. 5,212,743. In the embodiment of such a controller, the polarization state of a received optical signal is monitored and the polarization controller is appropriately driven to restore the polarization state of the received signal to a required state downstream of the controller.
[0006] A known form of such a polarization controller has an optical waveguide formed in a lithium niobate substrate. Suitable electrode structures or sets of electrodes are provided on the surface of the substrate in the vicinity of the waveguide so that driving the electrodes with suitable electrical control signals adjusts the optical birefringence of the waveguide. In this way, the polarization state of the optical signal may be restored dynamically to a required state. Notionally, such a controller having a single control section with three electrodes can function to transfer any state of polarization to any other state of polarization. However, if periodic resetting of the controller is to be eliminated (so-called endless control), then it has been established that two or three control sections are required, arranged serially or in cascade along the length of the optical waveguide.
[0007] In one known form of polarization controller of the kind described above, two separate control sections, each having individual electrodes, are provided in cascade along the length of the waveguide, and each is driven separately. In an alternative configuration, three such sections are provided serially along the length of the waveguide and again each section can be driven separately. In the case of a three section controller, the first and third sections may each be substantially a one quarter waveplate (QWP) element (at the intended frequency of operation) and the intermediate second section is substantially a one half waveplate (HWP) element. Then, the first and third sections can be driven synchronously and the second section is driven independently to obtain the required functionality. See, for example, the article of F. Heisman et al., Electronics Letters, Vol. 27(4), pp. 377-379, Feb. 14, 1991 as well as the above mentioned U.S. patent.
[0008] Although both of the above designs are able to operate very effectively, neither design has clear advantages over the other, for all circumstances of operation. Sometimes it may be better to use one of the designs or types, whereas in other circumstances it may be better to use the other controller design or type. However, once a receiver has been constructed to implement one type of polarization controller, it is very difficult to change the controller configuration to implement another type of polarization controller.
[0009] Thus, it is an object of this invention to provide a polarization controller that is more universal in its application.
[0010] It is a further object of this invention to provide a single polarization controller that can be re-configured into different wave plate geometries to perform different polarization modes of operation on a propagating optical signal.
SUMMARY OF THE INVENTION
[0011] According to one aspect of this invention, there is provided a versatile electro-optical polarization controller to restore or otherwise change the polarization state of an optical signal comprises a lithium niobate substrate having an optical waveguide for propagation of an optical signal with separate first, second, third and fourth control sections sequentially formed in cascaded fashion along the length of the waveguide. Each control section is provided with driver electrodes arranged to be driven with suitable electrical control signals to induce electro-optical birefringence in the waveguide along its respective control section length of the optical waveguide. More than four sections can be utilized in cascade along the waveguide to achieve better birefringence control of the optical signal. Thus, the more the control sections, the better the control performance with an upper limit as a compromise of device cost versus the additional performance realized.
[0012] A package is provided to contain a chip comprising a polarization device that includes the lithium niobate substrate and respective individual electrical connections for the driver electrodes of each section to extend separately out of the package. Alternatively, a wafer may be employed that includes a plurality of polarization devices on the same substrate to preform multiple signal corrections. The plurality of polarization control sections can be independently operated and/or interconnected externally of the package to give a required control characteristic to the polarization state of the waveguide through varying the orientation of the linear birefringence of the waveguide. The polarization state can be varied among the several control sections in a predetermined manner such that each section is substantially a one quarter wave plate element at the intended operational frequency of the controller.
[0013] Advantageously, embodiments of this invention permit reconfiguring of a polarization controller constructed as a single, integrated optical device, so that the controller may be used either as a two section polarization controller or as a three section polarization controller.
[0014] It will be appreciated that the polarization controller of this invention has four sections arranged serially or in cascaded fashion along the length of the optical waveguide. Each section may be substantially of one quarter waveplate design, at the intended frequency of operation. The control electrodes of each section are led out of the package so as to be externally accessible. In this manner, once manufacture of the controller has been completed, it can be used as a four section controller, with appropriate drive signals supplied to each control section. Alternatively, by appropriate interconnection of the external terminals of the electrodes or matching the drive signals of selected electrodes, the controller may serve as a two section device or as a three section device as previously indicated.
[0015] The electro-optical polarization controller if this invention is utilized in optical systems for signal correction. For example, the present invention has utility in optical telecommunication systems for controlling the polarization state of optical data signals received in such systems. Such controllers can be employed in other optical systems to change the polarization state of an optical signal.
[0016] One embodiment can be realized in which the offset angle between the waveguide and the z-axis of the LiNbO 3 can be arranged, preferably optimized, to achieve a nominal tuning voltage, V tune , of zero. Further embodiments can be realized that have a positive offset angle which reduces the drive voltage for mode conversion and increases the drive voltage for phase shift and, visa versa, for a negative offset angle.
[0017] One method of controlling the operation of the polarization controller of this invention is to provide a change in polarization state of an optical signal propagating along the length of the optical waveguide. The problems associated with polarization mode dispersion (PMD) in an optical fiber for high data rates in optical telecommunication systems are well known in the art. Polarization controllers are employed to restore the polarization state of an optical signal received in a receiver in such systems. A method of this invention comprises the first and fourth control sections of the device separately driven by first and second suitable control signals or synchronously driven by a single, suitable control signal, and the corresponding electrodes of the second and third control sections are linked together externally of the package and are driven by a third common drive signal.
[0018] Another method of controlling the operation of the polarization controller of this invention comprises the corresponding electrodes of the first and second control sections being linked together externally of the package and driven by a first common drive signal, and the corresponding electrodes of the third and fourth control sections being linked together externally of the package and driven by a second common drive signal.
[0019] Preferably, each control section of the polarization controller has two associated driver electrodes and a ground electrode. Each of these electrodes extend along the waveguide for a length sufficient to form a one-quarter waveplate element at the intended operating frequency of the controller. Such electrodes should be configured with a central ground electrode and the pair of driver electrodes arranged, one to each side of the central ground electrode. In this case, the central ground electrode of each section may extend along the waveguide.
[0020] The connections to the driver electrodes of each section are separately brought out of the package to give external access to those electrodes to permit the configuration or driving of the controller as described above. The ground electrode of each section may also be terminated externally of the package to provide separate access to each ground electrode. In an alternative embodiment, the ground electrodes of each section may be connected internally of the package to avoid the need for separate terminations for each ground electrode external of the package. In a further embodiment a single ground electrode may be provided, extending along the length of the waveguide and through each of the four control sections.
[0021] The various features of the present invention and its preferred embodiments may be better understood by referring to the following discussion and the accompanying drawings in which like reference numerals refer to like elements in the several figures. The contents of the following discussion and the drawings are set forth as examples only and should not be understood to represent limitations upon the scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] [0022]FIG. 1 diagrammatically illustrates a first embodiment of a polarization controller comprising this invention.
[0023] [0023]FIG. 2 shows the polarization controller connected in a first configuration of the invention.
[0024] [0024]FIG. 3 shows the polarization controller connected in a second configuration of the invention.
[0025] [0025]FIGS. 4A, 4B and 4 C are graphic illustrations of polarization Poincare sphere coverage to illustrate the improved coverage in the case of the multi-control sectioned polarization controller of this invention.
DETAILED DESCRIPTION OF THE INVENTION
[0026] [0026]FIG. 1 diagrammatically illustrates an integrated optical device comprising a polarization controller 10 of this invention. The device comprises a lithium niobate substrate 10 A which is mounted within a metallic package 11 . Subsequent to manufacture, the package may be hermetically sealed to protect substrate 10 A from the ambient environment. An optical waveguide 12 extends linearly through the substrate 10 A, the waveguide being formed in a well known manner, by doping the lithium niobate, for example, with titanium. Pigtails 13 and 14 , each comprising a short length of optical fiber, are secured to the end faces of substrate 10 A in optical alignment with waveguide 12 and are led out of the package. Each pigtail terminates in a respective connector 15 . Pigtails 13 , 14 permit light, in the form of an optical signal, to be fed into waveguide 12 at the input end of the device and to exit from waveguide 12 from the output end of the device.
[0027] Electrode structures are formed on the upper surface of the substrate. It can be seen in FIG. 1 that there are four separate sets of electrodes 31 , 32 , 33 , 34 arranged serially or in cascade along the length of waveguide 12 formed in substrate 10 A. Each of these electrode sets comprises a separate and independently control section of polarization controller 10 . Each electrode set 31 - 34 comprises a central ground electrode 16 positioned immediately above or overlying a portion of the waveguide 12 , and to each side of that central ground electrode, there is a pair of driver electrodes 17 , 18 . The three electrodes 16 , 17 , 18 of each electrode set 31 - 34 extend substantially parallel to one another along the length of waveguide 12 . A buffer layer (not shown) typically is provided between each electrode and the surface of the substrate to isolate the electrodes 16 - 18 from waveguide 12 .
[0028] On the surface of substrate 10 A, each electrode is connected to a respective termination pad 19 , which is connected by means of a flying connect wire 25 to a respective pin 20 projecting from the package 11 . Thus, an electrical connection may be made externally of the package to each individual electrode 16 , 17 or 18 formed on substrate 10 A.
[0029] Each set of electrodes 16 , 17 or 18 forms one control section 21 , 22 , 23 or 24 of the device and can independently function as a one quarter waveplate (QWP) element. By applying a suitable drive signal to electrode set 16 - 18 of any one control section, that section serves to vary the orientation of linear birefringence of waveguide 12 in that section to change the state of polarization of the optical signal propagating through that section along waveguide 12 , which phenomena and function is known in the art.
[0030] [0030]FIG. 2 shows one possible electrical-connect configuration for the plurality of control sections 31 - 34 of polarization controller 10 in FIG. 1. In the case here, the two central control sections 32 , 33 have their respective electrodes 16 - 18 linked externally by conductors 21 between the respective pins 20 of the two control sections. Thus the two central control sections 32 , 33 together form a one half waveplate (HWP) element at the intended frequency of operation while the two outer sections 31 , 34 function as separate quarter waveplate (HWP) elements. In this manner, the entire polarization controller may serve as a QWP+HWP+QWP device, with the QWP first and fourth control sections 31 , 34 being driven synchronously by first driver signals and the second and third control sections 32 , 33 being driven simultaneously by the same, second driver signals.
[0031] [0031]FIG. 3 shows another electrical-connect configuration for the plurality of control sections 31 - 34 of polarization controller 10 in FIG. 1. In FIG. 3, the first and second control sections 31 , 32 have their electrodes 16 - 18 linked together by means of external conductors 22 connected to respective pins 20 of these two sections. Similarly, the third and fourth control sections 33 , 34 have their electrodes linked together by means of external conductors 23 connected to respective pins 20 of those two sections. In this manner, the overall polarization controller may serve as a two section device, with the first and second control sections 31 , 32 being driven simultaneously by a first driver signal and the third and fourth control sections 33 , 34 being driven simultaneously by a second driver signal.
[0032] It will be appreciated that at the time of manufacture, the embodiments are not committed to being a two section device, three section device or a four section device. Rather subsequent to manufacture of the device and only at the time the device is to be incorporated into a receiver is the device committed to being functionally of one kind of operation or another, thereby leading to considerable economies, and removing the need to separately manufacture different devices dependent upon the kind of polarization control that is desired to be deployed.
[0033] A further advantage arising from the polarization controller arranged as a series of four sections, such as compared to the known constructions of having either two sections in series or three sections in series, is that an improvement in performance can be expected. Due to the limits on processing tolerances, an integrated device cannot be ideal. For example, the alignment between the waveguide and the electrodes will be less than perfect due to these tolerances. This can be compensated to some extent by adjusting various parameters, such as, for examples, the compensation voltage to compensate for offset angle variation and electrode-waveguide misalignment. It will be appreciated that compensation for offset angle variation involves increasing the compensation voltage as the offset angle increases and visa versa. Furthermore, dividing the electrodes into increasingly smaller sections allows the compensation voltage to be more closely matched to a respective section of waveguide misalignment which will improve the operation of the device. Since the non-ideal real configuration may vary along the length of a section, ideally one should apply a varying compensation voltage along the length of that section, to ensure it operates with the improved performance. Unfortunately, this is not possible, and in practice one must apply a constant correction to the whole length of the section. The probability is that for much of the length of the section, the wrong correction is applied.
[0034] By dividing the length of a control section into several smaller sub-sections, and applying the appropriate correction individually to each sub-section, a greater part of the combined whole section can be operated nearer to an ideal condition. Consequently, the division of a section into several smaller sub-sections and simultaneously applying optimal correcting parameters for each sub-section should lead to an improved overall performance. Ideally, a device should be divided into a number of control sections such that each section is small enough so that waveguide misalignment can be easily compensated. However, while the addition of smaller control sections along the waveguide will improve overall performance, it adds complexity to its operation and control. Thus, the dividing a half wave plate into two quarter waveplates adds one more section with improved performance. The dividing of all four half wave plates into eight smaller one-eight wave plates would provided even more improved performance, but it may not be as practical from a cost standpoint. However, depending upon the application, it may be still desired where demands for higher performance are required.
[0035] Referring to FIG. 4A, there is shown a 2-dimensional plot of the Poincare sphere coverage for an ideal polarization controller. The results were obtained by modeling such that a known and fixed polarization state of an optical signal was input to the device and the drive voltage was varied to produce all possible, or at least a subset of all possible, output polarization states. It can be appreciated from the plot of FIG. 4A that the ideal polarization controller can convert any input polarization state to any of the possible output states.
[0036] However, it can also be appreciated that the same cannot be said for a non-ideal half-wavelength polarization controller as can be seen from FIG. 4B. FIG. 4B illustrates a Poincare sphere plot for a non-ideal half wavelength plate having a fixed degree of skew and a half-wavelength plate. It can be seen that the non-ideal half-wavelength plate polarization controller there is region 404 representing polarization states to which the controller cannot convert the input optical signal. It can be appreciated from FIG. 4C, which shows a Poincare sphere plot 406 for a non-ideal quarter-wavelength plate, which has the same degree of skew as for FIG. 4B, that region 408 of non-coverage is reduced in size relative to that of region 404 of the half-wavelength plate shown in the plot of FIG. 4B. Therefore, it can be appreciated that the smaller the length of the electrodes used in a polarization controller, the greater the degree of control that can be exerted over the output signal polarization states. However, this greater degree of control requires more complex management of the drive signals that are applied to the signal electrode sets of the various cascaded control sections of the controller.
[0037] As a consequence, a single manufactured device can serve as either known form of polarization controller with greater economies being possible in view of the need to make only one device in larger quantities. Further, it is easier to manufacture the device to closer tolerances in order to give improved performances during its operation.
[0038] To deploy the device of this invention in a receiver, it is preferable to provide a monitor for determining the polarization of the received or transmitted optical signal. Such monitoring is preferably performed downstream of the device and is dynamically compared with the required polarization state. Drive signal amplifiers, connected to the various electrodes of the device, are then controlled to dynamically control the polarization state of the optical signal exiting the device, based upon the monitored state, so as to set that state to the required polarization mode. The monitoring of the polarization state and the controlling of drive signal amplifiers will not be described in further detail here.
[0039] Although the invention has been described in conjunction with one or more preferred embodiments, it will be apparent to those skilled in the art that other alternatives, variations and modifications will be apparent in light of the foregoing description as being within the spirit and scope of the invention. Although the above embodiments have been described in terms of realizing a λ/4,λ/2,λ/4, and a λ/2,λ/2 wavelength plates, it will be appreciated that the embodiments can also be realized in which any combination of the four λ/4 wavelength plates is used to control the polarization. For example, the first and third electrode sets may be driven separately from the second and fourth electrode sets. Furthermore, it can be appreciated that the drive voltages applied to the electrode sets may be arranged in any combination, for example, the first electrode set may be driven synchronously with the second, third, fourth electrode sets or any combination thereof. The same applies to the remaining electrodes. Thus, the invention described herein is intended to embrace all such alternatives, variations and modifications as that are within the spirit and scope of the following claims.
|
A polarization device is disclosed that provides versatility in achieving a desired polarization state of an optical signal. Current polarization controllers are provided with two or three control sections to induce λ/4 or λ/2 changes in the received optical signal. However, once designed, those controller have a fixed polarization mode of operation. The electro-optical polarization controller disclosed comprises a lithium niobate substrate having an optical waveguide for propagation of an optical signal with separate first, second, third and fourth control sections sequentially formed in cascaded fashion along the length of the waveguide. Each control section is provided with driver electrodes arranged to be driven with suitable electrical control signals to induce electro-optical birefringence in the waveguide along its respective control section length of the optical waveguide. More than four sections can be utilized in cascade along the waveguide to achieve better birefringence control of the optical signal.
| 6
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to post-layout circuit simulation. In particular, the present invention relates to techniques that reduce the size of a post-layout circuit simulation output waveform database, without loss of essential information and accuracy.
[0003] 2. Discussion of the Related Art
[0004] As the feature sizes of an integrated circuit (IC) decrease, and as circuit density and performance increase, circuit simulation has become a critical aspect of ensuring that the IC meets requirements. However, as IC technology continues to advance, circuit simulation continues to require greater computing resources and time. Consequently, circuit verification and debugging based on circuit simulation results have become the bottleneck in the design process of ICs.
[0005] In the IC design flow, a pre-layout circuit simulation primarily verifies circuit functionality and performs a first-pass circuit optimization. Because pre-layout circuit simulations are performed prior to layout, a pre-layout circuit description (“netlist”) contains only the design circuit elements. A pre-layout netlist is typically extracted from a schematic capture design environment, where the circuit designers draw the schematic circuits. As the ICs incorporate ever smaller features, layout-related effects have become increasingly important. These layout effects result from, for example, such parameters as capacitance, resistance, inductance, cross-talk, or resistive voltage drop in the realized circuit elements. A post-layout netlist may have many times the number of circuit elements than the corresponding pre-layout netlist. Thus, a post-layout circuit simulation is typically significantly slower than the corresponding pre-layout circuit simulation. A post-layout circuit simulation not only ensures that circuit functionality is maintained during the layout process, it also ensures that the circuit elements to be fabricated meet timing and power requirements.
[0006] There are three netlist formats that are widely used in the industry to represent a post-layout netlist; namely, the SPICE, SPEF and DSPF netlists. The SPICE netlist is the most commonly used netlist format for circuit simulation. SPICE—which stands for Simulation Program with Integrated Circuit Emphasis—is a circuit simulator originally developed at the University of California, Berkeley. The latest version of SPICE is referred to as “SPICE3.” SPICE is typically used for general circuit simulation, including DC analysis, AC analysis, operating point analysis, transient analysis and many other circuit analyses using such circuit elements as voltage or current sources, resistors, capacitors, inductors, metal-oxide-semiconductor field effect transistors (MOSFETs), bipolar junction transistors (BJTs), diodes and other circuit elements. Many commercial circuit simulators are based on the original SPICE program. Thus, the SPICE netlist format is considered an industry standard and is supported by most circuit simulators. Although subsequent circuit simulators have extended the SPICE format to support additional features, the basic SPICE netlist format remains unchanged over the years.
[0007] The SPEF netlist is not SPICE-compatible, in that it cannot be read directly by most circuit simulators. The SPEF netlist may be used to provide back-annotation to the original pre-layout netlist that is used for digital logic simulation. As the SPEF netlist is not suitable for analog circuit simulation, the SPEF netlist is not further considered here.
[0008] DSPF—which stands for “Detailed Standard Parasitic Format”—is a post-layout netlist format that provides in a SPICE file format parasitic resistors and capacitors for each pre-layout net. An exemplary DSPF file may read:
[0000]
*|DSPF 1.0
*|DESIGN “BUF”
*|DIVIDER/
*|DELIMITER :
.subckt BUF A Z VSS VDD
*|GROUND_NET 0
*
* Net Section
*
*|NET A 4.0e−14
*|I (M2:g M2 g I)
*|I (M3:g M3 g I)
*|P (A X 0.0)
*|S (A:1)
c0 A:1 0 10f
c1 A 0 10f
c2 M3:g 0 10f
c3 M2:g 0 10f
r0 A A:1 1000
r1 A:1 M3:g 100
r2 A:1 M2:g 100
*|NET INT 6.0e−14
*|I (M0:g M0 g I)
*|I (M1:g M1 g I)
*|I (M2:s M2 s B)
*|I (M3:s M3 s B)
*|S (INT:1)
*|S (INT:2)
c4 INT:1 0 10f
c5 M2:s 0 10f
c6 M3:s 0 10f
c7 INT:2 0 10f
c8 M1:g 0 10f
c9 M0:g 0 10f
r3 M3:s INT:2 100
r4 M2:s INT:2 100
r5 INT:2 INT:1 1000
r6 INT:1 M1:g 100
r7 INT:1 M0:g 100
*|NET VSS 1e−13
*|NET VDD 1e−13
*|NET Z 4.0e−14
*|I (M0:d M0 d B)
*|P (Z X 0.0)
*|I (M1:d M1 d B)
*|S (Z:1)
c10 M1:d 0 10f
c11 Z 0 10f
c12 M0:d 0 10f
c13 Z:1 0 10f
r8 Z:1 M1:d 100
r9 M0:d Z:1 100
r10 Z:1 Z 1000
*
* Instance Section
*
M2 M2:s M2:g VSS VSS NMOS L=6e−08 W=3.5e−07
M0 M0:d M0:g VSS VSS NMOS L=6e−08 W=7e−07
M3 M3:s M3:g VDD VDD PMOS L=6e−08 W=5e−07
M1 M1:d M1:g VDD VDD PMOS L=6e−08 W=10e−07
*
.ends
[0009] A DSPF netlist embeds non-standard SPICE format statements in comment lines that begin with ‘*|’, such as:
*|I(InstancePinName InstanceName PinName PinType PinCap X Y)
*|P(PinName PinType PinCap X Y)
*|NET NetName NetCap
*|S(Sub-nodeName X Y)
*|GROUND_NET NetName
[0010] The following DSPF directives are relevant to understanding the following detailed description: “NET”, “P”, “I”, and “S.” The “NET” directive begins a new net description, and is associated with a “NetName” parameter and a “NetCap” parameter. The “NetName” parameter provides a unique name for the net, which normally corresponds to a pre-layout node name. The “NetCap” parameter provides a total capacitance for the net identified by the NetName. The “P” directive denotes a pin of a net, and is associated with a “PinName” parameter and a “PinType” parameter. The “PinName” parameter provides a name for the pin, and the “PinType” provides the pin type, which may be “I” (for input), “O” (for output) or another identifier for an approved pin type. The “I” directive denotes an instance pin of a net, and is associated with (a) the “InstancePinName” parameter, which provides a name for the instance pin; (b) the “InstanceName” parameter, which provides a name for an element instance to which the instance pin identified by the “InstancePinName” parameter is connected to; (c) the “PinName” parameter provides a name for the pin in the element instance identified by the “InstanceName” parameter that connects to the instance pin identified by the “InstancePinName” parameter, and (d) the “PinType” parameter, which can be “D” (for drain), “S” (for source), and “G” (for gate) when used with an MOS transistor, but may receive other values, when used with any of numerous other types for circuit elements. The “S” directive denotes a sub-node of a net, and is associated with the “Sub-nodeName” parameter, which provides a name for the sub-node. A sub-node is neither a pin nor an instance pin.
[0011] The DSPF netlist format can be used to back-annotate a pre-layout netlist to allow post-layout circuit simulations. However, the back-annotation approach may be too error-prone for many applications, as back-annotation does not handle cross-talk capacitance or device back-annotation efficiently and correctly, especially for custom-designed circuits that have high simulation accuracy requirements. For a custom-designed circuit, a DSPF or a SPICE netlist that is not a back-annotation of a pre-layout netlist is preferred.
[0012] Post-layout simulations can take up to hours, days or even weeks to complete. Numerous methods have been invented to speed up the simulation. Most methods are based on reducing the parasitic circuit elements (“parasitic reduction”) or the number of circuit elements, either during circuit simulation or during a pre-processing step for the circuit simulation. Parasitic reduction methods use either an ad hoc method (e.g., parallel, series reduction or filters), or a mathematical method (e.g., model order reduction (“MOR”)). Methods aimed at reducing the number of circuit elements are often used for simulating memory circuits, since the post-layout netlists may contain arrays of memory cells that are not exercised during the simulation. These methods all suffer some accuracy loss, as the reduction ratio is always traded-off with error minimization. In a method where the reduction technique is applied outside the simulator, the errors may be quantified by comparing the results before and after application of the reduction technique. However, in a method where the reduction technique is applied within the circuit simulator, the errors are more difficult to quantify, as how the reduction algorithm affect the results cannot not be readily ascertained. Most designers prefer a circuit reduction algorithm that achieves better circuit simulation performance within certain accuracy limits.
[0013] In the prior art, a post-layout circuit simulation is performed using a flattened netlist. The flattened netlist uses either index numbers or flattened hierarchical names to represent the circuit elements and the nodes. Such forms of identification are very tedious to specify, especially when one needs to use node or circuit element names to map the post-layout nodes or circuit elements to the corresponding pre-layout nodes or circuit elements for examination or verification. The problem is exacerbated when the post-layout netlist is not in a “proper” DSPF netlist, uses index nodes or element names, or is a SPICE netlist. Manual matching is practical only when there are only a few nodes required to be selected for examination. When there are more nodes required to be selected or when the whole circuit is required, such an approach is not practical. During circuit verification and debugging, a designer often prefers to select every node in the circuit for examination. To facilitate specifying a large number of nodes, the “wild card matching” method allows a wild card character (e.g., “*”) to be used in a name. For example, the name “*ABC*” is interpreted to mean a selection of all names containing the character string “ABC”. Most circuit simulators support wild card matching. However, wild card matching is not useful when the names are index numbers. Using wild card matching also tends to select for examination far more data than is necessary.
[0014] Furthermore, since the post-layout netlist is flat (i.e., not hierarchical), the circuit simulation result database is also flat. Most waveform display tools that operate from such a database typically cannot resolve flattened hierarchical names. Thus, a user may be presented with far too many node names at once to select nodes for display. In that situation, a user often resorts to a filter function in the waveform tool that is able to process the hierarchical names to find the matching nodes. Such a filter function can be very slow when the output database is large. In addition, a hierarchical name may be matched by hundreds of nodes in the database. At that point, the user may have to manually trace in the post-layout netlist to identify the intended node to examine. The entire process from specifying the hierarchical name to successfully reaching the intended node to examine is very time consuming. When the element or node name is an index number, the matching process may be even more difficult. Due to the inefficiency in this process, many hours, even days, may be spent reviewing just one set of circuit simulation results.
[0015] The post-layout netlists are often significantly larger than the pre-layout netlist, resulting in a post-layout circuit simulation output database that may be tens or hundreds of times larger than the corresponding pre-layout circuit simulation output database, even when circuit reduction techniques are used. Because a designer may need to access any node within the circuit during the verification and debugging phases, most designers will select all the nodes for output. Post-layout circuit simulation output file sizes are often in the Gigabyte range (i.e., one billion bytes or more). Outputting such large output file in simulation is very slow, the time to output the waveform may be comparable or even longer than the time required for carrying out the circuit simulation itself. Displaying such large file in waveform viewer is also very slow. As a result, designer productivity suffers.
[0016] As mentioned above, the efforts to improve post-layout circuit simulation performance have mainly focused on reducing parasitic circuit elements or circuit size. For example, U.S. Patent Application Publication No. 2003/0126575, entitled “RC netlist reduction for timing and noise analysis,” discloses a RC parasitic reduction method to improve circuit analysis speed while maintaining good accuracy. U.S. Pat. No. 6,874,132, entitled “Efficient extractor for post-layout simulation on memories,” discloses a post-layout circuit size reduction method that extracts only the active rows and columns of a memory array. U.S. Patent Application Publication No. 2009/0113356, entitled “Optimization of Post-Layout Arrays of Cells for Accelerated Transistor Level Simulation,” discloses an approach for reducing post-layout array in memory circuits to accelerate transistor level simulation. However, the present inventor is not aware of any solution developed to address inefficiency in usage of post-layout circuit simulation data. Therefore, what is needed is a new method on how to create and access post-layout circuit simulation results for examination. Such a method would reduce output file size—hence storage requirements—significantly, while also improving circuit simulation speed. There is also a need to reduce the number of nodes displayed, without loss of information essential for debugging and verification. The flattened circuit simulation results also need to be converted to a hierarchical format to allow the waveforms in the simulated nodes to be easily accessed and displayed.
SUMMARY
[0017] The present invention provides a method for creating and accessing post-layout circuit simulation results for examination. A method of the present invention reduces output file size—hence storage requirements—significantly, while improving circuit simulation speed. In addition, a method of the present invention reduces the number of nodes displayed, without loss of information essential for debugging and verification. The flattened circuit simulation results are also converted to refer to hierarchical names, so as to allow the waveforms of the simulated nodes to be easily accessed and displayed. Therefore, the present invention significantly improves designer productivity during circuit verification and debugging phases.
[0018] According to one embodiment of the present invention, a method identifies subnets that are instance pin nodes and sub-nodes, and identifies whether an instance pin node is a driver node or a receiver node, and provides output statements referring to the identified subnets in post-layout netlist formats, e.g., the proper DSPF format, a simplified DSPF format, or a SPICE netlist format. A path-tracing program may be used to find parasitic circuit elements and subnets, and to identify whether a subnet is an instance pin node or a sub-node and whether an instance pin node is a driver node or a receiver node. The method may be implemented in a circuit simulator, as a pre-processor to a circuit simulator, or a post-processor to a circuit simulator. When implemented in a circuit simulator, the method reduces the number of post-layout nodes to be output, based on user preference. When implemented in a preprocessor to a circuit simulator, the method receives both a pre-layout netlist that includes output commands and a post-layout netlist, and generates output statements to be included in the post-layout netlist, according to user specification. The output statements output a reduced number of nodes than a conventional post-layout circuit simulation would normally output. When implemented in a post-processor to a circuit simulator, the method receives a pre-layout netlist that includes output statements, a post-layout simulation netlist, a circuit simulation result waveform database, and provides, based on user preference, a reduced circuit simulation result waveform database.
[0019] According to one embodiment of the present invention, a method addresses how output waveforms are displayed in a waveform display program. The method not only converts a flattened waveform database into a hierarchical waveform database, but also improves readability and intuitiveness of assigned hierarchical node names in a waveform display tool to facilitate navigation and node selection.
[0020] According to one embodiment of the present invention, a path-tracing program finds all the nodes within a net and determines whether they are instance pin nodes or sub-nodes. To represent a flattened signal in a hierarchical output database (e.g., a subnet node name that is an index number or device terminal, which may be named differently from its associated net), a method of the present invention uses a SPICE output statement to assign a hierarchical name to the output signal.
[0021] The present invention has at least two advantages over conventional post-layout circuit simulations. First, the number of nodes output in a post-layout circuit simulation based on the output statements of the present invention is significantly reduced, so that storage requirements for the post-layout circuit simulation results are in the same order of magnitude as the corresponding pre-layout circuit simulation results. Second, the unfamiliar flattened signal names are renamed as hierarchical names similar to those used in a pre-layout circuit simulation. The output database is also organized hierarchically. Thus, navigating the post-layout circuit simulation results within a waveform tool is thus made much easier and may, in fact, be similar to navigating results of a pre-layout circuit simulation. In addition, essential information is preserved. For example, the signal timings for the leading, trailing edges and the interconnect delays are all preserved. The present invention also reduces the time required to carry out a post-layout circuit simulation.
[0022] The present invention is better understood upon consideration of the detailed description below in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 is a block diagram showing a method in a preprocessor of a circuit simulator for reducing the size of a post-layout circuit simulation output database, according to one embodiment of the present invention;
[0024] FIG. 2 is a block diagram showing a method in a post-processor for reducing a post-layout circuit simulation output database, according to one embodiment of the present invention;
[0025] FIG. 3A illustrates a SPICE netlist of a 3-inverter circuit;
[0026] FIG. 3B shows the schematic of an inverter of the 3-inverter circuit of FIG. 3A ;
[0027] FIG. 3C illustrates, on the left drawing and the right drawing, respectively, a flattened view and a hierarchical view of the three serially connected inverters of FIG. 3A .
[0028] FIG. 3D shows a pre-layout SPICE netlist of a buffer circuit “BUF”;
[0029] FIG. 3E shows the schematic of buffer circuit “BUF” of FIG. 3D ;
[0030] FIG. 4 is a proper post-layout DSPF netlist for buffer circuit “BUF” of FIG. 3E , using flattened hierarchical names;
[0031] FIG. 5 is a post-layout DSPF netlist for buffer circuit “BUF” of FIG. 3E , in which index numbers are used for the node names;
[0032] FIG. 6A is a post-layout SPICE netlist, in which each net of buffer circuit “BUF” of FIG. 3E is provided in a sub-circuit (.subckt) definition;
[0033] FIG. 6B is a post-layout SPICE netlist for the buffer circuit “BUF” in which the post-layout nets are not separately set forth in sub-circuit (.subckt) definitions;
[0034] FIG. 7A shows all the subnet voltage waveforms of a simulation of post-layout net INT in the buffer circuit “BUF” of FIG. 3E ;
[0035] FIG. 7B shows a leading edge of a waveform of a subnet (specifically, instance pin driver node M 3 :s) in net INT (See, FIG. 9 for subnet locations);
[0036] FIG. 7C shows a trailing edge of a waveform of a subnet (specifically, instance pin receiver node M 0 :g) in net INT (See, FIG. 9 for subnet location);
[0037] FIG. 7D shows a waveform envelope for net INT, including the leading edge of a waveform at instance pin driver node M 3 :s and the trailing edge of a waveform for instance pin receiver nodes M 0 :g, respectively (See, FIG. 9 for subnet locations);
[0038] FIG. 7E shows leading edges of the waveforms for instance pin driver nodes M 2 :s and M 3 :s in net INT. (See, FIG. 9 for subnet locations);
[0039] FIG. 7F shows trailing edges of the waveforms of instance pin receiver nodes M 0 :g and M 1 :g in net INT. (See, FIG. 9 for subnet locations);
[0040] FIG. 7G shows a waveform envelope of net INT, including the leading edges of the waveforms at instance pin driver nodes M 2 :s and M 3 :s and the trailing edges of the waveforms for instance pin receiver nodes M 0 :g and M 1 :g, respectively;
[0041] FIG. 8A shows a simulation deck used in a post-layout circuit simulation for buffer circuit “BUF”;
[0042] FIG. 8B shows a generated simulation deck for a post-layout circuit simulation of buffer circuit “BUF”, when the user output preference is set to “pin”, according to one embodiment of the present invention;
[0043] FIG. 8C shows generated output statements for a post-layout circuit simulation of buffer circuit “BUF”, when the user output preference is set to “driver”, according to one embodiment of the present invention;
[0044] FIG. 8D shows generated output statements for a post-layout circuit simulation of buffer circuit “BUF”, when the user output preference is set to a single receiver node, according to one embodiment of the present invention;
[0045] FIG. 8E shows the generated output statements for a post-layout circuit simulation of circuit buffer “BUF”, when the user output preference is set to “envelope”, according to one embodiment of the present invention;
[0046] FIG. 9 is a schematic circuit of post-layout buffer circuit “BUF”, which illustrates using a path-tracing program to identify subnets of post-layout nets, according to one embodiment of the present invention; and
[0047] FIG. 10 is a schematic circuit of post-layout buffer circuit “BUF”, which illustrates node-matching using element names to identify subnets of post-layout nets, according to one embodiment of the present invention.
DETAILED DESCRIPTION
[0048] Reference is now made in detail to one or more embodiments of the present invention. While the present invention is described in conjunction with these embodiments, such embodiments are not intended to be limiting the present invention. On the contrary, the present invention is intended to cover alternatives, variations, modifications and equivalents within the scope of the present invention, as defined in the accompanying claims.
[0049] Hierarchical and flattened pre-layout and post-layout circuit descriptions or netlists are illustrated by way of examples in FIGS. 3A-3E , FIGS. 4-5 , and FIGS. 6A-6B .
[0050] FIG. 3A shows a typical SPICE-compatible netlist of a 3-inverter circuit. The netlist describes a circuit that includes MOS transistors, resistors, and capacitors; the netlist contains a sub-circuit definition of an inverter provided in the .subckt directive, and serially connected instances X 0 , X 1 and X 2 of the inverter sub-circuit, each of which contains two MOS transistors, a resistor and a capacitor. As shown in FIG. 3A , in the sub-circuit definition, an inverter cell is defined which includes four ports—“VDD”, “vss”, “in” and “out”. The inverter sub-circuit is shown schematically in FIG. 3B , including NMOS transistor M 1 , PMOS transistor M 2 , resistor R 1 , and capacitor C 1 . The top level circuit description in the netlist of FIG. 3A also defines VDD and VIN as supply and input voltage sources, respectively. The right drawing of FIG. 3C illustrates schematically the serially connected inverters of FIG. 3A . As each inverter instance is represented by an inverter symbol, rather than the basic circuit elements (e.g., transistors, resistors, and capacitors), the view illustrated in the right drawing of FIG. 3C is considered “hierarchical.” The netlist also includes a reference to another file “bsim4_models” which contains the device models for the NMOS and PMOS transistors. The netlist also includes “.print” output statements which output the voltages of nodes “in”, “out”, “n 1 ” and “n 2 ”.
[0051] The left drawing of FIG. 3C illustrates, respectively, a flattened view of the three serially connected inverters of FIG. 3A . The flattened view shows that, when the circuit elements of instances X 0 , X 1 and X 2 are drawn with express details, the circuit of FIG. 3A has six MOS transistors (M 0 , M 1 , M 2 , M 3 , M 4 , M 5 ), three resistors (R 1 , R 2 , R 3 ), and three capacitors (C 1 , C 2 , C 3 ).
[0052] FIG. 3D shows a pre-layout SPICE netlist for buffer circuit “BUF”. As shown in FIG. 3D , the netlist for buffer circuit “BUF” includes four MOS transistors—M 0 , M 1 , M 2 and M 3 , and four ports—A, Z, VSS and VDD. FIG. 3E shows schematically buffer circuit “BUF” of FIG. 3D .
[0053] A post-layout netlist includes both the circuit elements of the pre-layout netlist and parasitic resistor and capacitor elements. This is best illustrated by a DSPF format netlist, which lists in a “net section” the parasitic circuit elements associated with nets. A net in a post-layout DSPF netlist typically includes parasitic circuit elements and subnets. Subnets may be further divided into nodes that are pins, instance pins and sub-nodes. A subnet that is a pin represents a pin that is connected to the pre-layout net. A pin with a PinType of “IN” is considered a driver node to the net. A subnet that is an instance pin represents a pin of a pre-layout circuit element connected to the pre-layout net. Some instance pins are driver nodes, while other instance pins are receiver nodes. For example, an instance pin connected to a drain or source terminal of a MOSFET is a driver node, while an instance pin connected to a gate terminal of a MOS is a receiver node. (Drain and source terminals of a MOSFET are typically interchangeable.) A subnet that is a sub-node is not connected to either a pre-layout net or a pre-layout circuit element. The subnets in a DSPF netlist are treated as discrete nodes in a circuit simulation. Typically in a post-layout circuit simulation, node voltages are output for all nodes or for nodes that are specified using pattern-matching. Thus, when a net is selected for output, most or all of its subnets are selected for output. However, as shown in FIG. 7A , the voltage waveforms of the subnets in a post-layout net closely resemble each other, such that the waveforms can be enclosed by a single envelope. Furthermore, as shown in FIG. 7D , for each net, the waveforms of internal sub-nodes in the subnets can also be enclosed by the waveforms for the pins and instance pins.
[0054] Ideally, a fully compliant DSPF netlist (in a “proper” DSPF netlist format) provides all information required to determine whether a subnet is a pin, an instance pin or a sub-node. However, not all DSPF netlists provide complete information. To reduce file size, some simplified DSPF netlists may only provide NET information, which specifies only the post-layout net without specifying the subnets. Also, a post-layout SPICE netlist does not follow the net-by-net format of a DSPF netlist, as circuit elements and nodes are randomly arranged. Some post-layout SPICE netlists group all the subnets of a net together in a subcircuit (“.subckt”) definition, so that every net has a subcircuit which defines the post-layout subnets.
[0055] FIG. 4 is a proper post-layout DSPF netlist for buffer circuit “BUF” of FIG. 3E , using flattened hierarchical names. As shown in FIG. 4 , the netlist includes nets listed in a “Net Section.” Information regarding the subnets within each net is provided following the |NET directive: pin (the |P directive), instance pin (the |I directive) and sub-node (the |S directive). This information allows the net to be directly mapped to one or more pre-layout nodes, and facilitates user selection of pins or instance pins (which may be driver nodes or receiver nodes) or sub-nodes for output. The waveforms associated with these nodes are often displayed to allow examination of leading edges, trailing edges, or envelopes of signals in circuit simulation results or waveforms. In FIG. 4 , the node names used are flattened hierarchical names. For example, net INT includes:
[0000] *|NET INT 6 e - 14
*|I(M 0 :g M 0 g I)
*|I(M 1 :g M 1 g I)
*|I(M 2 :s M 2 s B)
*|I(M 3 :s M 3 s B)
[0056] *|S(INT: 1 )
*|S(INT: 2 )
[0057] Therefore, subnets M 0 :g, M 1 :g, M 2 :s, M 3 :s are identified as instance pins that connect to the gate terminals of MOS transistors M 0 and M 1 , and source terminals of MOS transistors M 2 and M 3 , respectively. Subnets INT: 1 and INT: 2 are identified as sub-nodes that are neither connected to pins nor instance pins. No subnet that is identified as a pin is listed for net INT. (In contrast, a pin is listed as a subnet in each of nets A and Z.)
[0058] Parasitic circuit elements within a net are then listed after the pin, instance pin and sub-node specifications for the net. In FIG. 4 , parasitic resistors r 0 -r 10 , parasitic capacitors c 0 -c 13 and their nodes are listed for nets A, INT, VSS, VDD and Z (no parasitic resistors or capacitors are specifically listed for nets VSS and VDD). For example, the post-layout parasitic circuit elements of net INT are:
[0000] c 4 INT: 1 0 10 f
c 5 M 2 :s 0 10 f
c 6 M 3 :s 0 10 f
c 7 INT: 2 0 10 f
c 8 M 1 :g 0 10 f
c 9 M 0 :g 0 10 f
r 3 M 3 :s INT: 2 100
r 4 M 2 :s 1 NT: 2 100
r 5 INT: 2 INT: 1 1000
r 6 INT: 1 M 1 :g 100
r 7 INT: 1 M 0 :g 100
[0059] Parasitic capacitors c 4 -c 9 are subnet-to-ground capacitors for the subnet INT: 1 , INT: 2 , M 2 :s, M 3 :s, M 0 :g, and M 1 :g. Parasitic resistors r 4 -r 7 connect all the subnets within net INT.
[0060] The netlist of FIG. 4 also includes an “Instance Section” in which the pre-layout circuit elements M 0 , M 1 , M 2 and M 3 are listed in its flattened form. The post-layout circuit of FIG. 4 is shown schematically in FIG. 9 .
[0061] FIG. 5 is a post-layout DSPF netlist for buffer circuit “BUF” of FIG. 3E , in which index numbers are used as node names. As in FIG. 4 , the netlist includes a “Net Section” which lists parasitic resistors and capacitors for each of nets A, INT, VSS, VDD, Z. The netlist also includes an “Instance Section” in which pre-layout circuit elements M 0 , M 1 , M 2 and M 3 are listed. In FIG. 5 , the node names used are index numbers, and the element names in the Instance Section match the pre-layout names. In contrast to the DSPF netlist of FIG. 4 , in the DSPF netlist of FIG. 5 , no identification of a subnet as a pin, an instance pin, or a sub-node is provided. Thus, the present invention uses a path-tracing program to determine whether each subnet is a pin, an instance pin, or a sub-node. In the case of an instance pin, the path-tracing program also identifies if the instance pin is a driver node or a receiver node. The post-layout buffer circuit “BUF” of FIG. 5 is shown schematically in FIG. 10 .
[0062] FIG. 6A is a post-layout SPICE netlist, in which each net of buffer circuit “BUF” of FIG. 3E is provided in a subcircuit (.subckt) definition. This format is similar to the DSPF net-by-net approach illustrated in FIG. 5 . As shown in FIG. 6A , each subcircuit definition for a net includes both the subnet post-layout circuit elements and its nodes. The name of each subcircuit definition matches a pre-layout node name to facilitate cross-reference. For example, the subcircuits N_A, N_INT and N_Z correspond to pre-layout nets A, INT and Z, respectively, although this netlist format is not a recognized post-layout SPICE netlist. If the subcircuit names cannot be matched to pre-layout node names, a path-tracing program may be used to match element names and connectivity to resolve the pre-layout and post-layout node names, as element names are typically preserved between pre-layout and post-layout circuit netlists. In addition, the path-tracing program may also identify if a node is a pin, an instance pin driver node, an instance pin receiver node, or a sub-node.
[0063] FIG. 6B is a post-layout SPICE netlist for buffer circuit “BUF” in which the post-layout nets are not separately set forth in subcircuit (.subckt) definitions. A path-tracing program may be used to identify the post-layout parasitic circuit elements and nodes within each net and to determine whether a subnet is a pin, an instance pin driver node, an instance pin receiver node, or a sub-node. The path-tracing program may perform this determination by matching element names and connectivity, as pre-layout element names are preserved between pre-layout and post-layout netlists.
[0064] The present invention exploits certain characteristics of the post-layout waveforms that allow a significant reduction in the size of the output database, as well as improving the time required for carrying out a post-layout circuit simulation. FIG. 7A shows all the subnet voltage waveforms of a simulation of post-layout net INT in buffer circuit “BUF” of FIG. 3E . The waveforms of FIG. 7A include waveforms of all subnets of net INT, including all driver nodes, receiver nodes and sub-nodes. FIG. 7A confirms that the voltage waveforms of all subnets within a post-layout net, such as INT, are similar. Each waveform differs from another due to their respective timing delays within the post-layout net.
[0065] FIG. 7B shows a leading edge of a waveform of a subnet (specifically, instance pin driver node M 3 :s) in net INT. (See, FIG. 9 for subnet location).
[0066] FIG. 7C shows a trailing edge of a waveform of a subnet (specifically, instance pin receiver node M 0 :g) in net INT. (See, FIG. 9 for subnet location).
[0067] FIG. 7D shows a waveform envelope of net INT, including the leading edge of a waveform at instance pin driver node M 3 :s and the trailing edge of a waveform for instance pin receiver nodes M 0 :g, respectively.
[0068] FIG. 7E shows leading edges of the waveforms for instance pin driver nodes M 2 :s and M 3 :s in net INT. (See, FIG. 9 for subnet locations).
[0069] FIG. 7F shows trailing edges of the waveforms of instance pin receiver nodes M 0 :g and M 1 :g in net INT. (See, FIG. 9 for subnet locations).
[0070] FIG. 7G shows a waveform envelope of net INT, including the leading edges of the waveforms at instance pin driver nodes M 2 :s and M 3 :s and the trailing edges of the waveforms for instance pin receiver nodes M 0 :g and M 1 :g, respectively.
[0071] From these figures, it is observed that:
1. Approximate timing in the waveforms of a net may be obtained from the waveforms of any sub-node, pin or instance pin in the net. 2. The leading edges in the waveforms of a net may be obtained from the waveforms of a subnet of a driver node in the net (e.g., an input pin node or an instance pin node connected to a drain or source terminal of a MOSFET). 3. The trailing edges in the waveforms of a net may be obtained from the waveforms of an output pin or subnet that is a receiver node of the net (e.g., an instance pin node connected to a gate terminal of a MOSFET). When there is no receiver node in the net, then a driver node of the net can be used. 4. The leading and trailing edges or the envelope of the waveforms of a net may be obtained from the waveforms of a pin or an instance pin of the net, or from the waveforms of a driver node and a receiver node of the net.
[0076] A user may select any suitable waveform from among the driver nodes, the receiver nodes, or the envelopes of a net.
[0077] According to one embodiment of the present invention, a method identifies subnets that are instance pins and sub-nodes, identifies whether an instance pin is a driver node or a receiver node, and generates output statements in post-layout netlist formats, e.g., the proper DSPF format, a simplified DSPF format, or a SPICE netlist format. A path-tracing program may be used to find parasitic circuit elements and subnets and identifies whether a subnet is an instance pin or a sub-node and whether an instance pin is a driver node or a receiver node. The method may be implemented in a circuit simulator, as a pre-processor to a circuit simulator, or a post-processor to a circuit simulator. When implemented in a circuit simulator, the method reduces the number of post-layout nodes to be output, based on user specification. When implemented in a preprocessor to a circuit simulator, the method receives both a pre-layout netlist that includes output statements and a post-layout netlist, and generates output statements for inclusion in the post-layout netlist, according to user specification. Typically, the generated output statements output a reduced number of nodes. When implemented in a post-processor to a circuit simulator, the method receives a pre-layout netlist that includes output statements, a post-layout simulation netlist, and a post-layout simulation result output waveform database, and provides, based on user specification, a reduced simulation result output waveform database.
[0078] According to one embodiment of the present invention, a method addresses how output waveforms are displayed in a waveform display program. The method not only converts a flattened waveform database into a waveform database accessible by hierarchical names, but also improves readability and intuitiveness of assigned hierarchical node names in a waveform display tool to facilitate navigation and node selection.
[0079] In the proper DSPF netlist format, the “DIVIDER” and “DELIMITER” directives support hierarchy. The header of a DSPF file may contain the following statements:
*DSPF 1 . 0
*DIVIDER /
*DELIMITER:
*BUS_DELIMITER [ ]
[0080] The DIVIDER directive defines a character to be used for separating instant names in a hierarchical name and the DELIMITER directive defines a character to be used for introducing a subnet node name. For example, the hierarchical node names may be:
/X 1 /X 2 /A: 3
/I 1 / 12 /A: 3
/XI 1 /XI 2 /A: 3
[0081] In the first example, /X 1 /X 2 /A: 3 specifies a node in subnet A: 3 of net A in instance X 2 , which is within instance X 1 . The two other examples illustrate that different layout parasitic extractor programs may use slightly different naming convention for hierarchical node names. In these examples, X 1 , I 1 , and XI 1 are names generated under different naming conventions for the same instance. Once the hierarchy of a node name is identified, the name can be used in a hierarchical database accordingly.
[0082] An instance pin presents a different issue. An instance pin in net /X 1 /X 2 /A may be named /X 1 /X 2 /X 3 /M 1 :d. Although this node is an instance pin within net /X 1 /X 2 /A, by observing the names alone, there is no clear connection between the two names, /X 1 /X 2 /A and /X 1 /X 2 /X 3 /M 1 :d. In the proper DSPF netlist format, the node /X 1 /X 2 /X 3 /M 1 :d is identified as an instance pin within net /X 1 /X 2 /A in the net section as shown by:
*|NET /X 1 /X 2 /A
[0083] . . .
*|I(/X 1 /X 2 /X 3 /M 1 :d /X 1 /X 2 /X 3 /M 1 . . . )
[0084] However, if the netlist is not presented in a proper DSPF netlist or as a SPICE netlist, the information connecting the names /X 1 /X 2 /A and /X 1 /X 2 /X 3 /M 1 :d is not available. The path-tracing program of the present invention finds all the nodes within each net and determines whether they are instance pins or sub-nodes. To represent a flattened signal in a hierarchical output database (e.g., a subnet node name that is an index number or a device terminal, which may be named differently from its associated net), a method of the present invention uses a SPICE output statement to assign a hierarchical name to the signal to be output. (This output statement may be used with practically all commercial circuit simulation programs.) For example, a pre-layout simulation may have the output statement:
[0000] .print tran v(X 1 .X 2 .A) v(X 2 .X 3 .B) i(X 1 .X 2 .M 1 )
[0085] The symbol “.” in the net name is the default hierarchy divider used by most circuit simulators. The following output statements using corresponding hierarchical names may be generated for a post-layout simulation of the circuit:
[0000] .print tran X 1 .X 2 .A=v(/X 1 /X 2 /A)
.print tran X 1 .X 2 .A:DDD: 1 =v(/X 1 /X 2 /X 3 /M 1 :d)
.print tran X 1 .X 2 .A:RRR: 1 =v(/X 1 /X 2 /X 4 /M 2 :g)
.print tran X 1 .X 2 .A:SSS: 1 =v(/X 1 /X 2 /A: 3 )
.print tran X 2 .X 3 .B:RRR: 1 =v(F 1234 )
.print tran X 1 .X 2 .M 1 :III: 1 =i(/X 1 /X 2 /M 1 )
[0086] The name “DDD” is a predefined postfix for a driver node; the name “RRR” is a predefined postfix for a receiver node; the name “SSS” is a predefined postfix for a sub-node, and the name “III” is a predefined postfix for node current. A designer may choose to output either a pin, a driver node, a receiver node or a sub-node.
[0087] The statement “.print tran X 1 .X 2 .A=v(/X 1 /X 2 /A)” outputs the voltage of a hierarchical node “X 1 .X 2 .A” which corresponds to the net name “/X 1 /X 2 /A” in the DSPF netlist format. In this instance, the subnet /X 1 /X 2 /A is identified as a pin of net /X 1 /X 2 /A. By this statement, the voltage v(/X 1 /X 2 /A) is to be output and represented as “X 1 .X 2 .A”. The name “X 1 .X 2 .A” is a hierarchical name which can be stored in the hierarchical output database.
[0088] The statement “.print tran X 1 .X 2 .A:DDD: 1 =v(/X 1 /X 2 /X 3 /M 1 :d)” outputs a voltage of a driver node of net X 1 .X 2 .A where the subnet /X 1 /X 2 /X 3 /M 1 :d is identified as a driver node. X 1 .X 2 .A:DDD: 1 is interpreted to refer to the first driver node of hierarchical node X 1 .X 2 .A. Similarly, the statement “.print tran X 1 .X 2 .A:RRR: 1 =v(/X 1 /X 2 /X 4 /M 2 :g)” outputs a receiver node of net X 1 .X 2 .A, where the subnet /X 1 /X 2 /X 4 /M 2 :g is identified as a receiver node. X 1 .X 2 .A:RRR: 1 is interpreted to refer to the first receiver node of hierarchical node X 1 .X 2 .A.
[0089] The statement “.print tran X 1 .X 2 .A:SSS: 1 =v(/X 1 /X 2 /A: 3 )” outputs a voltage of a sub-node of net X 1 .X 2 .A, where the subnet /X 1 /X 2 /A: 3 is identified as a sub-node. X 1 .X 2 .A:SSS: 1 is interpreted to refer to the first sub-node of hierarchical node X 1 .X 2 .A.
[0090] The statement “.print tran X 2 .X 3 .B:RRR: 1 =v(F 1234 )” outputs a voltage of a subnet which has index number F 1234 as its name. This statement associates index number F 1234 to the hierarchical name X 2 .X 3 .B, and allows the subnets belonging to net X 2 .X 3 .B to be identified. When a designer desires to output a receiver node, from this association, the path-tracing program would identify subnet F 1234 as a receiver node of net X 2 .X 3 .B. X 2 .X 3 .B:RRR: 1 is interpreted to refer to the first receiver node of net X 2 .X 3 .B.
[0091] The statement “.print tran X 1 .X 2 .M 1 :III: 1 =WX 1 /X 2 /M 1 )” outputs a current through node X 1 .X 2 .M 1 (or node /X 1 /X 2 /M 1 , hierarchically). X 1 .X 2 .M 1 :III: 1 is interpreted to refer to the first current output of hierarchical element X 1 .X 2 .M 1 .
[0092] The same technique may be used in other output statements than “.print” (e.g., “.plot”, “.probe”, “.measure”, and others). The “.measure” or “.meas” statement outputs a waveform measurement between signals. Conventionally, a designer painstakingly identifies an exact node name in the post-layout netlist to specify in the “.measure” statement, as an exact name, rather than a name-matching wild card, must be used. The path-tracing program avoids the tedious search of an exact name. For example, consider the following pre-layout statement and its corresponding post-layout statement:
[0000] .meas delay_AB . . . v(x 1 .A) . . . v(x 1 .B) . . .
.meas delay_AB . . . v(/x 1 /x 2 /m 1 :d) . . . v(/x 1 /x 3 /m 2 :d) . . .
[0093] The pre-layout statement measures a delay between signals x 1 .A and x 1 .B. The corresponding post-layout statement also measures that delay, but the designer has to specify using exact subnet signal names /x 1 /x 2 /m 1 :d and /x 1 /x 3 /m 2 :d.
[0094] According to one embodiment of the invention, the path-tracing program identifies the required signal names from a post-layout netlist and associates them with the pre-layout nets X 1 .A and X 1 .B. The .meas statement may then use the identified subnet names in the .meas statements. The following output statement is therefore generated:
[0000] .meas delay_AB . . . v(/x 1 /x 2 /m 2 :d) . . . v(/x 1 /x 3 /m 1 :d) . . .
[0095] The subnet nodes /x 1 /x 2 /m 2 :d and /x 1 /x 3 /m 1 :d selected by the path-tracing program may be different from what the designer may manually choose. In practice, however, the choice discrepancy is not significant, as the difference in delay between the manually selected nodes and the path-tracing program selection is typically insignificant. Also, a designer often picks nodes randomly, without any apparent preference for the driver nodes, the receiver nodes, or any other subnets. If the post-layout netlist is a proper DSPF netlist, the path-tracing program may identify the post-layout subnets from the net section. If the post-layout netlist is a SPICE netlist, the net-by-net format of the DSPF file format would not be available. In that case, a post-layout net name for each group of subnets is required and may be obtained by either node name matching with pre-layout names, or element name matching with pre-layout names. In either case, the post-layout SPICE netlist needs to contain pre-layout name information in a particular format. Most layout parasitic extraction programs preserve pre-layout net name information in the post-layout SPICE netlists, if requested. The pre-layout node name may directly appear in the post-layout netlist, or be embedded in the post-layout net names as a prefix or a postfix, or the pre-layout name may appear with a different hierarchy divider. For example, the pre-layout net name X 1 .X 2 .N 3 may be used to provide post-layout net names such as X 1 _X 2 _N 3 and ABC_X 1 _X 2 _N 3 _ 21 _DEF. In this case of X 1 _X 2 _N 3 , the post-layout name uses a different hierarchy divider from the pre-layout name. In the case of ABC_X 1 _X 2 _N 3 _ 21 _DEF, prefix ABC and postfix DEF are used to generate the post-layout net name, together with character string “21”, which is the subnet index.
[0096] Since different parasitic extraction programs use different prefixes, postfixes and hierarchy dividers, element name matching may be more reliable than node name matching for identifying post-layout net names. Typically, element names are exactly matched between a pre-layout netlist and its corresponding post-layout netlist, although different hierarchy dividers, or device finger designations under simple device naming rules are possible. For example, consider the pre-layout element name X 1 .X 2 .M 1 and the matching post-layout elements MX 1 /X 2 /M 1 and MX 1 /X 2 /M 1 @1. Under the SPICE naming convention, a MOSFET is assigned a name that has “M” as the first letter. MX 1 /X 2 /M 1 , using a different hierarchy divider “/”, maps to the same element X 1 .X 2 .M 1 . In MX 1 /X 2 /M 1 @1, the “@1” portion represents a device finger in the device X 1 .X 2 .M 1 . (A large transistor may be realized in the layout as a large number of device fingers, each device finger being a separate transistor that may be extracted separately in the post-layout netlist.) Once a device or circuit element is matched between the pre-layout and post-layout netlists, net matching between the pre-layout and post-layout netlists can be performed through tracing the associated nets.
[0097] The user can also choose to output waveform envelopes from a net which includes driver and receiver nodes. Although outputting one driver node and one receiver node is the default option, post-layout circuit simulation may also output more driver and receiver nodes. If there is no receiver node in a net, then a driver node may also be considered a receiver node. The waveform envelope, including the leading and trailing edges and the interconnect wire delays, typically contains all the information necessary for circuit analysis. By outputting either just one subnet or the waveform envelope of a net, the number of nodes to be output is significantly reduced. For example, the following statements output just one driver node and one receiver node of net X 1 .X 2 .A:
[0000] .print tran X 1 .X 2 .A:DDD: 1 =v(/X 1 /X 2 /X 3 /M 1 :d)
.print tran X 1 .X 2 .A:RRR: 1 =v(/X 1 /X 2 /X 4 /M 2 :g)
[0098] In contrast, the following example outputs all driver and receiver nodes of net X 1 .X 2 .A, which includes 2 driver and 2 receiver nodes:
[0000] .print tran X 1 .X 2 .A:DDD: 1 =v(/X 1 /X 2 /X 3 /M 1 :d)
.print tran X 1 .X 2 .A:DDD: 2 =v(/X 1 /X 2 /X 3 /M 2 :d)
.print tran X 1 .X 2 .A:RRR: 1 =v(/X 1 /X 2 /X 4 /M 2 :g)
.print tran X 1 .X 2 .A:RRR: 2 =v(/X 1 /X 2 /X 4 /M 1 :g)
[0099] FIG. 8A shows a simulation deck that is used in a pre-layout circuit simulation for buffer circuit “BUF”. As shown in FIG. 8A , the simulation deck refers to a DSPF netlist file, a device model file, a statement for voltage supply VDD, a piece-wise linear specification of input stimulus “vin” that is applied to node “in”, and instance X 0 of buffer circuit BUF, which provides an output signal at node “out”. FIG. 8A includes the following output statements for the simulation results:
[0000] .print tran v(in) v(out) v(x 0 .INT)
.meas tran fall trig v(out) val=0.7 fall=last targ v(out) val=0.3 fall=last
[0100] The .print statement outputs transient waveforms for nodes “in”, “out”, and internal node “X 0 .INT”. The .meas statement outputs a measurement of a signal transition time—from 0.7 volt to 0.3 volt—of the last falling edge of the net “out”.
[0101] FIG. 8B shows a generated simulation deck for a post-layout circuit simulation of buffer circuit “BUF”, when the user output preference is set to “pin”, according to one embodiment of the present invention. For this post-layout circuit simulation, an appropriate netlist may be, for example, the DSPF netlist of FIG. 4 . In this embodiment, the following output statements are generated for this post-layout circuit simulation deck in place of the output statements of FIG. 8A :
[0000] .print tran in=v(in)
.print tran out=v(out)
.print tran x 0 .INT=v(x 0 .M 0 :g)
.meas tran fall trig v(out) fall=last targ v(out) val=0.3 fall=last
[0102] To generate these output statements, a method of the present invention first maps the post-layout nets to the pre-layout nets. For example, the pre-layout net “in” may be mapped to post-layout net “A” of instance X 0 of buffer circuit “BUF”. Similarly, the pre-layout net “out” is mapped to post-layout net “Z”. The pre-layout net “X 0 .INT” is mapped to post-layout net “INT”. (See, e.g., in FIG. 4 , the DSPF file for nets A, Z, and INT, and their associated circuit elements). Furthermore, in this example, as user output preference is set to “pin,” the method locates the pin-type subnets of each net and their corresponding post-layout hierarchical names. The post-layout names for the pin-type subnets are mapped to the pre-layout hierarchical names for output. For example, as shown in FIG. 4 , the pin-type subnet for net “A” is node “A” (see the subnet corresponding to the IP directive). Node “A” is mapped to node “in” at the top level test bench. Thus, in the .print output statement, the method maps the pin node name to “in”. In FIG. 4 , the pin-type subnet for net “Z” is node “Z” (see the subnet corresponding to the IP directive). Thus, node Z is assigned to “out” at the top level test bench. As mentioned above, the corresponding post-layout net for “X 0 .INT” is net “INT”. As there is no pin-type subnet in post-layout net INT, a subnet within the post-layout net “INT” is selected. The method of the present invention selects receiver node “M 0 :g”, which is an instance pin. In the output statement, the selected node “X 0 .M 0 :g” is assigned to hierarchical name “X 0 .INT”. For the measurement statement, the node voltage “v(out)” of the simulation deck of the pre-layout simulation of FIG. 8A is now replaced with the output pin “v(out)”, which is identical to the original node name.
[0103] FIG. 8C shows generated output statements for a post-layout circuit simulation of buffer circuit “BUF”, when the user output preference is set to “driver”, according to one embodiment of the present invention. Again, the DSPF netlist of FIG. 4 is used to illustrate this post-layout circuit simulation. The generated output statements replace the output statements of FIG. 8A . The generated output statements are:
[0000] .print tran in:DDD: 1 =v(in)
.print tran out:DDD: 1 =v(X 0 .M 0 :d)
.print tran x 0 .INT:DDD: 1 =v(x 0 .M 2 :s)
.meas tran fall trig v(X 0 .M 0 :s) val=0.7 fall=last targ v(X 0 .M 0 :s) val=0.3 fall=last
[0104] The mapping between the post-layout nets and the pre-layout nets has already been discussed above with respect to FIG. 8B . A method of the present invention determines a driver node of each post-layout net, as the user output preference specifies a single “driver” node. Therefore, as a driver node of post-layout net “X 0 .A” is pin “A”, that node A is assigned to the pre-layout name “in” at the top level test bench. In the output .print statement, the voltage “v(in)” is assigned to the voltage of node “in:DDD: 1 ”, which specifies the first driver node of pre-layout node “in”. As one of the driver nodes of post-layout net “X 0 .Z” is “X 0 .M 0 :d”, which is an instance pin, the generated output statement assigns the voltage “v(X 0 .M 0 :d)” to the voltage of the node with the hierarchical name “out:DDD: 1 ”, which specifies the first driver node of pre-layout node “out”. In other embodiments, the other driver node “X 0 .M 1 :d” of post-layout net “X 0 .Z” may be selected and used in the output statement. As there are two driver nodes in post-layout net “X 0 .INT”, “X 0 .M 2 :s” and “X 0 .M 3 :s”, which are instance pins, a method of the present invention may select “X 0 .M 2 :s” as the driver node for the output statement, although the choice of “X 0 .M 3 :s” for the output statement is equally valid. In the output statements, the voltage output “v(X 0 .M 2 :s) is assigned to the voltage of node “X 0 .INT:DDD: 1 ”, which specifies the first driver node of pre-layout node “X 0 .INT”. For the measurement statement, the node voltage “v(out)” of the simulation deck of the pre-layout simulation of FIG. 8A is now replaced with the driver node voltage “v(X 0 .M 0 :d)”.
[0105] FIG. 8D shows generated output statements for a post-layout circuit simulation of buffer circuit “BUF”, when the user output preference is set to a single receiver node, according to one embodiment of the present invention. Again, the DSPF netlist of FIG. 4 is used to illustrate this post-layout circuit simulation. The generated output statements replace the output statements of FIG. 8A . The generated output statements are:
[0000] .print tran in:RRR: 1 =v(X 0 .M 2 :g)
.print tran out:RRR:1=v(out)
.print tran x 0 .INT:RRR: 1 =v(x 0 .M 0 :g)
.meas tran fall trig v(out) val=0.7 fall=last targ v(out) val=0.3 fall=last
[0106] The mapping between the post-layout nets and the pre-layout nets has already been discussed above with respect to FIG. 8B . A method of the present invention determines a receiver node of each post-layout net, as the user output preference is set to a single receiver node. Therefore, as a receiver node of post-layout net “X 0 .A” is pin “X 0 .M 2 :g”, the output statement assigns voltage node v(X 0 .M 2 :g) to the voltage of node “in.RRR: 1 ,” which specifies the first receiver node of pre-layout node “in”. The other receiver node “X 0 .M 3 :g” of post-layout net “X 0 .A” is also a suitable choice. The pin subnet “Z” in the post-layout net “XO.Z” is a receiver node, and thus is mapped to node “out” at the top level test bench. In the output statements, the voltage “v(out)” is assigned to the voltage of node “out:RRR: 1 ”, which specifies the first receiver node of pre-layout node “out”. As one of the receiver nodes in post-layout net “X 0 .INT” is “X 0 .M 0 :g”, which is an instance pin, the output statement assigns the voltage node “v(X 0 .M 0 :g) to the voltage of node “X 0 .INT:RRR: 1 ”, which specifies the first receiver node of pre-layout node “X 0 .INT”. Receiver node “X 0 .M 1 :g” of post-layout net “X 0 .INT” is also a valid selection. For the measurement statement, the node voltage “v(out)” of the simulation deck of the pre-layout simulation of FIG. 8A is now replaced with the output pin “v(out)”, which is identical to the original node name.
[0107] FIG. 8E shows the generated output statements for a post-layout circuit simulation of circuit buffer “BUF”, when the user preference is set to “envelope”, according to one embodiment of the present invention. Again, the DSPF netlist of FIG. 4 is used to illustrate this post-layout circuit simulation. The generated output statements replace the output statements of FIG. 8A . The generated output statements are:
[0000] .print tran in:DDD:1=v(in)
.print tran in:RRR:1=v(X 0 .M 2 :g)
.print tran out:DDD:1=v(X 0 .M 0 :d)
.print tran out:RRR:1=v(out)
.print tran x 0 .INT:DDD:1=v(x 0 .M 2 :s)
.print tran x 0 .INT:RRR:1=v(x 0 .M 0 :g)
.meas tran fall trig v(out) val=0.7 fall=last targ v(out) val=0.3 fall=last
[0108] The mapping between the post-layout nets and the pre-layout nets has already been discussed above with respect to FIG. 8B . In addition, a method of the present invention providing output statements for the “envelope” user preference determines a driver node and a receiver node using the methods already described above for determining pins, driver nodes and receiver nodes of each post-layout net in conjunction with FIGS. 8B , 8 C, and 8 D, respectively. For net “in”, the driver node voltage “v(in)” is assigned to the voltage of node “in:DDD: 1 ” and the receiver node voltage “v(X 0 .M 2 :g)” is assigned to the voltage of node “in:RRR: 1 ” in the output statements. (The receiver node voltage “v(X 0 .M 3 :g)” may also be assigned to the voltage of node “in:RRR: 1 ”.) For net “out”, the driver node voltage “v(X 0 .M 0 :d)” is assigned to the voltage for node “out:DDD: 1 ” and the receiver node voltage “v(out)” is assigned to the voltage of node “out:RRR: 1 ”. (The driver voltage “v(X 0 .M 1 :d)” may be assigned to the voltage of the node “out:DDD: 1 ”.) For net “X 0 .INT”, the driver node voltage “v(X 0 .M 2 :s)” is assigned to the voltage of node “X 0 .INT:DDD: 1 ” and the receiver node voltage “v(X 0 .M 0 :g)” is assigned to the voltage of node “X 0 .INT:RRR: 1 ”. (The driver node voltage v(X 0 .M 3 :s) may also be assigned to the voltage of node “X 0 .INT:DDD: 1 ” and the receiver node voltage “v(X 0 .M 1 :g)” may also be assigned to the voltage of node “X 0 .INT:RRR: 1 ”). For the measurement statement, the node voltage “v(out)” of the simulation deck of the pre-layout circuit simulation of FIG. 8A is now replaced with the output pin “v(out)”, which is identical to the original node name.
[0109] FIG. 9 is a schematic circuit of the post-layout buffer circuit BUF, which illustrates using a path-tracing program to identify subnets of post-layout nets, according to one embodiment of the present invention. The netlist for the schematic circuit of FIG. 9 is set forth in the post-layout DSPF netlist of FIG. 4 . The post-layout schematic circuit of FIG. 9 includes both the pre-layout circuit elements and post-layout parasitic circuit elements. According to one embodiment of the present invention, for each post-layout net, a path-tracing program selects a resistor element in the net and then identifies and records all resistors in the net that are connected to the selected resistor. The path-tracing program records the resistors and their associated subnets. The procedure is repeated for all post-layout nets until all resistors are identified and recorded. In like manner, the path-tracing program identifies and records all capacitors in each net and their associated subnets. For buffer circuit “BUF”, the path-tracing program searches three post-layout nets A, INT and Z. Post-layout net A includes resistors R 0 , R 1 , R 2 and subnets A, A: 1 , M 2 :g, and M 3 :g. Post-layout net INT includes resistors R 3 , R 4 , R 5 , R 6 , R 7 and subnets M 2 :s, M 3 :s, INT: 1 , INT: 2 , M 0 :g and M 1 :g. Post-layout net Z includes resistors R 8 , R 9 , R 10 and subnets M 0 :d, M 1 :d, Z: 1 and Z. The path-tracing program further determines whether each subnet identified is a pin, an instance pin, or a sub-node. For each pin, the subnet may be further determined as a driver node or a receiver node. Subnets A and Z are pins and have the same names as their respective post-layout nets. Subnet A is a driver node and subnet Z is a receiver node. Subnets M 0 :g, M 1 :g, M 2 :g and M 3 :g are instance pins that are receiver nodes. Subnets M 0 :d, M 1 :d, M 2 :s and M 3 :s are instance pins that are driver nodes. Subnets A: 1 , INT: 1 , INT: 2 and Z: 1 are each a sub-node that is neither a pin or an instance pin.
[0110] FIG. 10 is a schematic circuit of the post-layout buffer circuit BUF, which illustrates node-matching using element names to identify subnets of post-layout nets, according to one embodiment of the present invention. The netlist for buffer circuit “BUF” is set forth in the post-layout DSPF netlist of FIG. 5 . Unlike the post-layout schematic circuit of FIG. 9 , which uses pre-layout node names in some nets, the post-layout schematic circuit of FIG. 10 uses index numbers which are independent of pre-layout node names. As the element names are preserved between the pre-layout and post-layout netlists, pre-layout node names and post-layout node names may be mapped through element names and node connectivity. According to one embodiment of the present invention, a method uses a path-tracing program to first identify each post-layout net. Post-layout net A includes subnets A, F 1 , F 2 , and F 3 and is connected to gate terminals of transistors M 2 and M 3 . Post-layout net INT includes subnets F 4 , F 5 , F 6 , F 7 , F 8 , and F 9 and is connected to the gate terminals of transistors M 0 and M 1 and drain terminals of transistors M 2 and M 3 . Post-layout net Z includes subnets F 10 , F 11 , F 12 , and Z and is connected to the drain terminals of transistors M 0 and M 1 . As pre-layout net IN is connected to the gate terminals of M 2 and M 3 , pre-layout net IN matches post-layout net A. Similarly, as pre-layout net INT connects to the gate terminals of transistors M 0 and M 1 and the drain terminals of transistors M 2 and M 3 , pre-layout net INT matches post-layout net INT. As pre-layout net OUT is connected to the drain terminals of transistors M 0 and M 1 , pre-layout net OUT matches post-layout net Z.
[0111] Therefore, to achieve the advantages stated above, one method carries out the following steps in a preprocessor to a circuit simulator, in a post-processor to a circuit simulator, or as part of a circuit simulator:
(a) providing a post-layout netlist for circuit simulation; (b) providing a pre-layout netlist corresponding to the post-layout netlist, the pre-layout netlist including output statements; (c) receiving user preference regarding data output for a post-layout circuit simulation; (d) searching the post-layout netlist for all the parasitic circuit elements and subnets associated with each net in the pre-layout netlist; (e) matching net names between the post-layout netlist and the pre-layout netlist, using either post-layout node names or post-layout element names; and (f) when carrying out the method in the preprocessor, generating hierarchical output statements for the post-layout circuit simulation based on user preference and the pre-layout output statements, thereby producing a reduced output simulation result database based on the user preference;
(ii) when carrying out the method in the post-processor, generating a reduced hierarchical output database based on the user preference and a post-layout simulation result database; and (iii) when carrying out the method in the circuit simulator, generating output statements for the circuit simulation based on the user preference and the pre-layout output statements, thereby causing generation of a reduced circuit simulation result database.
[0120] FIG. 1 is a block diagram showing a method in a preprocessor of a circuit simulator for reducing the size of a post-layout simulation output database, according to one embodiment of the present invention. In FIG. 1 , post-layout netlist 100 contains pre-layout circuit elements and post-layout parasitic circuit elements. Simulation deck or test bench 101 contains simulation input stimuli and output statements for the circuit simulator. The output statements may specify nodes using pre-layout net names. Preference file 102 includes user specified output data preference. For example, in preference file 102 , a user may specify output of leading driver nodes, trailing receiver nodes, and envelope signals based on the leading driver nodes and the trailing receiver nodes. Post-layout circuit simulation results reduction program 103 receives post-layout netlist 100 , simulation deck 101 and user preference file 102 to generate simulation deck 104 , which includes generated output statements that may specify nodes using post-layout net names. Simulation deck 104 and post-layout netlist 100 are read into the circuit simulator as input files for a post-layout simulation 105 . The circuit simulator then produces reduced simulation output database 106 , which may be hierarchical.
[0121] FIG. 2 is a block diagram showing a method in a post-processor for reducing a post-layout simulation output database, according to one embodiment of the present invention. In FIG. 2 , post-layout netlist 200 contains pre-layout circuit elements and post-layout parasitic circuit elements. Simulation deck or test bench 201 contains simulation input stimuli and output statements for the circuit simulator. The output statements may specify nodes using post-layout net names. Preference file 202 includes user specified output data preference. For example, in preference file 202 , a user may specify output of leading driver nodes, trailing receiver nodes, and envelope signals based on the leading driver nodes and the trailing receiver nodes. Circuit simulator output database 203 contains a post-layout circuit simulation result database. Post-layout circuit simulation result reduction program 204 receives post-layout netlist 200 , simulation deck 201 , preference file 202 , and circuit simulation result database 203 to generate reduced circuit simulation results database 205 , which may have a reduced size, relative to circuit simulation output database 203 , and may also be hierarchical.
[0122] The detailed description herein is provided to illustrate specific embodiments of the present invention and is not intended to be limiting. Numerous modifications and variations within the scope of the invention are possible. The present invention is set forth in the following claims.
|
A method for reducing the size of post-layout circuit simulation output waveform database without a loss of essential information and accuracy. The reduced waveform database requires significantly less storage than the typical waveform database for post-layout simulation, thereby improving the time required for a waveform tool to access, and for a user to navigate, the post-layout simulation results. The method therefore greatly improves designer productivity during circuit verification and debugging phases. The method can be carried out in a preprocessor to a circuit simulator, in a post-processor to a circuit simulator, or may be directly built into a circuit simulator. The method is applicable to any post-layout netlists with schematic node names or circuit element names.
| 6
|
BACKGROUND
[0001] There is a significant need for structurally sound and aesthetically attractive retaining walls made from manufactured blocks. In the past, natural stone boulders, cinder blocks, and other inferior blocks have been used with limited success.
SUMMARY
[0002] A retaining block wall, retaining blocks and a related manufacturing method have been invented.
[0003] The retaining wall block itself may include a combination of one or more of the following features:
(a) a hollow core to facilitate water migration within the interior of a wall made of the blocks, from top to bottom, via gravity flow;, and which makes the block lighter and uses less concrete to manufacture than a solid block, (b) a water trough at the bottom of the blocks so that any wall constructed using the blocks has incorporated within it a water trough to move water away from the retaining wall, thus mitigating the effects of hydraulic pressure and erosion, allowing water to go into a drainage device if desires, such as a gravel field, perforated pipe, etc., (c) an integral top nub and bottom receptacle on the blocks so that blocks, once stacked into a retaining wall, are mechanically interlocked by the block material itself and without the need for separate connecting mechanisms such as rebar, etc., (d) location of the nub on the top of each block and the receptacle on the bottom of each block so that no special blocks are needed for construction of the bottom of a retaining wall, (e) the receptacle (for an interconnecting nub) being formed on the blocks as a lateral groove across the block so that workers can assemble the blocks with any desired offset, (f) the nub and receptacle being formed with a predetermined batter, such as 5 degrees (about 9 percent) to facilitate the blocks being used to form a high wall with ample structural integrity, (g) an integral core on a wall formed by the blocks, the wall having sloped walls, the walls sloping from narrow to wide from top to bottom so that gravel will completely fill the block cores if gravel is used, thereby creating a mechanical interlock by way of gravel interference between vertically adjacent blocks, (h) angular side walls on the blocks so that they can readily be used for constructing retaining walls with non-planar shapes, and (i) an outer wall aesthetic pattern in order to present an attractive view in a finished retaining wall.
[0013] A retaining block wall made using the blocks will have these and other features that distinguish them from the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 depicts a top view of a top retaining wall block without nubs.
[0015] FIG. 2 depicts a top view of a retaining wall block with nubs.
[0016] FIG. 3 depicts a side view of a top retaining wall block of FIG. 1 .
[0017] FIG. 4 depicts a side view of the retaining wall block of FIG. 2 .
[0018] FIG. 5 depicts a side view of a retaining wall made with retaining wall blocks.
[0019] FIG. 6 depicts a top view of a curved retaining wall made with retaining wall blocks, showing a tight convex curve made as a result of angled blocks (such as a 16 ft. radius).
[0020] FIG. 7 depicts a frontwise perspective view of a mold for making retaining wall blocks.
[0021] FIG. 8 depicts a rearwise perspective view of a mold for making retaining wall blocks.
[0022] FIG. 9 depicts a rear view of a mold for making retaining wall blocks.
[0023] FIG. 10 depicts a side view of a mold for making retaining wall blocks.
[0024] FIG. 11 depicts a top view of a mold for making retaining wall blocks.
[0025] FIG. 12 depicts a front view of a mold for making retaining wall blocks.
[0026] FIG. 13 depicts a side sectional view of a mold for making retaining wall blocks after a block has been cast with the mold core being disengaged or removed.
[0027] FIG. 14 depicts a side sectional view of a mold for making retaining wall blocks after a block has been cast with the mold core (such as a tapered barrel) disengaged and mold sides opened so that the block can be lifted from the mold and put into inventory or taken to a construction site.
DETAILED DESCRIPTION
[0028] Referring to FIGS. 1- 4 , both a retaining wall block 102 ( FIGS. 2 and 4 ) and a special top retaining wall block 101 ( FIGS. 1 and 3 ) are depicted. Each block has an outer periphery wall 101 b and 102 b surrounding a hollow inner core 101 a and 102 a. Each block has a top 101 c and 102 c, and a bottom 101 d and 102 d. On its top, each block that is not a top block, such as 102 , has a nub 102 e for insertion into block bottom receptacle or channel 101 f or 102 f. Insertion of the nub into the receptacle forms a mechanical interlock between the blocks. Block sides 101 h, 101 i, 102 h, and 102 i may be angled as desired, such as being angled toward the front as shown, to facilitate placement of concrete of the blocks in a configuration that creates a non-planar retaining wall. The top block may include a lip 101 j for further retention and aesthetic purposes. The lip allows the material being retained, such as earth, to be brought over the top of the block and against the angled portion shown in the figure, if desired, to conceal the top of the block. Optionally the blocks may have a pickup joint 101 k and 102 k.
[0029] Referring to FIGS. 5 and 6 , a retaining wall 501 constructed of the invented retaining wall block is depicted. The example wall has a top row of top retaining wall blocks 101 without nubs. The example wall also has three mechanically interlocked retaining wall blocks 102 stacked with a positive batter for structural stability, however a wall of the user's design could be as high or low as desired. Each block with a nub 102 e has the nub inserted into a receptacle (easily seen at 102 f ) to create the mechanical interlock which creates a stable wall. A mechanical interlock between two blocks, one on top of the other, is created by the block material itself (such as concrete) rather than by a separate device such as rebar or a bolt. Further, the block bottom receptacle from a series of blocks forms a channel that accommodates water flow along the bottom of any row of blocks and along the bottom of a retaining wall made from blocks to facilitate runoff and avoid erosion. Viewing the wall from the top such as in FIG. 6 , the voids in the interiors of the blocks create generally vertical hollow columns which can be filled with gravel or other filler material for creating of a unified interlocked block retaining wall. Those generally vertical columns also permit water to flow vertically down through the blocks to the channel mentioned above. This permits water to be drained off from the retaining wall to avoid hydraulic pressure buildup, ground softening, freezing and erosion.
[0030] As desired, the front face of the blocks may include an aesthetic design 101 g and 102 g to create an attractive retaining wall when construction is complete.
[0031] The retaining wall blocks are stackable to create a structurally sound retaining wall. Location of the nub and receptacle features for a predetermined batter, such as 5 degrees, facilitate the blocks being used to form a high wall with structural integrity. The blocks may have an internal core that has sloped walls if desired, the walls sloping from narrow to wide from top to bottom so that the vertical columns created by those voids will fill completely with gravel or other fill material, thereby creating a second mechanical interlock mechanism by way of gravel or fill interference between vertically adjacent blocks. The blocks may be manufactured with angled sides so that they can readily be used to build retaining walls with non-planar shapes.
[0032] An example of dimensions of the blocks is 2′×4′×3′ (height×length×depth). This has been found to provide excellent structural integrity. Use of a ration of block depth to height, where the block depth is at least 125% of block height, or at least about 150% of block height, contributes to stability, as do the mechanical interlock of the nub and receptacle as well as the second mechanical interlock of the fill material such as gravel.
[0033] Use of blocks with hollow cores permits installation of fencing directly on top of a wall made from the blocks. With prior art devices, fences were often offset from the retaining wall, resulting in loss of usable real estate, difficulties with lawn mowing and upkeep, and aesthetic impairment.
[0034] Referring to FIG. 7-14 , a mold 701 for making the invented retaining wall blocks is depicted. The mold 701 includes a mold body 702 and a core 703 . The mold core projects into the mold body in order to take up space so that completed block has a hollow inner core of the dimensions and geometry desired. The inner core forms one side of the mold. The mold has two sides 707 and 708 which can fold into place for block formation and fold away from the formed block for block removal. The mold core 703 may be drawn into the mold and pushed back out of the mold by use of a hand crank, rotatable screw or bolt 710 projecting through bore 706 . The hand crank is a dual thrust stripping assembly. Cranked one way, the hand crank draws the mold core in tight, and turned the other way it pushes the core from the interior of the mold. A fixed opposing nut 780 or other opposing device may be used to push or pull against. Also, if desired, a secondary mold stripping mechanism 798 may be employed. In this case the secondary mold stripping mechanism is merely a bolt which when turned presses against the mold body to provide additional tension withdrawing the mold core from the mold. By use of a dual stripping assembly such as crank 710 and a secondary mold stripping mechanism, removal of a mold core from a formed concrete block is possible, easy and convenient. Since the sides of the core 703 are sloped in a positive fashion with respect to the direction in which the core is withdrawn from the mold, the mold core easily breaks free from a molded concrete block. The mold core 703 also has the ability to pivot with respect to a lower pivot point 720 by use of pivot frame 721 to which the mold core 703 is attached. Movement of the mold core into and out of the mold may be facilitated by use of a mold core track 750 and wheels or bearings in that track 760 to cause the mold core to move more easily. The front of the mold body 702 can pivot away from the molded block at a pivot point 770 if desired. The mold may have a bottom 729 to hold concrete when the block is forming. As an example, a polyurethane form liner may be used to form a texture on the block. Use of this mold assembly results in a formed concrete block 799 ready to use.
[0035] As depicted, the mold may be used to form a block in face-down fashion. This facilitates formation of an aesthetic pattern with deep relief on the block and allows air bubbles to rise away from the block face.
[0036] The mold may be made from any desired material, such as metal, wood, plastic, composites or other materials. The mold geometry can be adjusted to create the desired tapers, channels, nubs and receptacles on the finished retaining wall blocks.
[0037] When in use, the mound forms a block by a particular method which can be altered per the user's requirements. Example steps in the method include obtaining a suitable mold, placing the mold core into the mold, placing concrete into the mold, allowing the concrete to cure into a retaining wall block, removing the mold core from the mold, pivoting the mold sides away from the block, and removing the block from the mold. The mold core may be moved into place in the mold interior with a pivot and pivot frame, with a track and rollers and bearings, or by use of both. The mold core may be tightened into place and may be forced out of place, as needed.
[0038] While the present invention has been described and illustrated in conjunction with a specific embodiment, those skilled in the art will appreciate that variations and modifications may be made without departing from the principles of the invention as herein illustrated, described, and claimed. The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiment is to be considered in all respects as only illustrative, and not restrictive. The scope of the invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
|
A retaining block wall, retaining blocks, and a retaining block manufacturing method result in a structural wall with two mechanical interlocks and water management systems.
| 4
|
This application is a division of application Ser. No. 725,226, filed 4-19-85.
BACKGROUND AND PRIOR ART
This invention relates to flight instruments and more particularly to flight instruments based on light interference phenomena for sensing acceleration forces.
There are, in most aircraft, a group of flight instruments that are based on the principle of detecting pressure changes, especially the atmospheric air pressure. The instruments are: (a) the airspeed indicator which senses the difference between the air pressure on the inlet of a pitot tube placed at the front of the aircraft and the reference pressure at some pressure-neutral point of the aircraft fuselage, and (b): the altimeter which measures the aircraft altitude as a function of the barometric pressure at the altitude of the aircraft and (c): the rate-of-climb indicator which measures the rate-of-climb or descent of the aircraft by measuring the difference between the air pressure in a plenum containing a volume of air and connected through a restriction to the point of reference pressure and the unrestricted reference air pressure. In other words, the rate-of-climb indicator performs a differentiation of the air pressure as a function of the aircraft's changing altitude.
The three instruments listed hereinabove all contain an air pressure sensing device which is typically a diaphragm exposed on one or both sides to the air pressure to be measured. The diaphragm is, in conventional flight instruments, connected through a sensitive mechanical linkage to a rotating pointer in front of a dial which displays the visual indication provided by the instrument, such as air speed in nautical miles per hour, altitude in feet and thousands of feet and rate-of-climb in feet per second.
Another flight instrument which depends on sensing of pressures is the accelerometer, which is part of the inertial guidance system used in some large aircraft for navigation. The accelerometer senses the pressure changes as a force exerted on a mass in the accelerometer as the aircraft undergoes changes in velocity. This force is usually sensed by means of suitable electronic sensors that are part of the accelerometer.
The instant application discloses methods for the use of light interference phenomena, which are created by a beam of coherent monochromatic light, for sensing of pressures in flight instruments with a high degree of precision.
Flight instruments of conventional construction based on bellows action or mechanical linkages are subject to corrosion, mechanical wear and intrusion of dust which all contribute to loss of dependability and accuracy.
PRIOR ART
Inventors have in the past sought ways to produce pressure transducers that are highly dependable and avoid the use of complex mechanical linkages.
U.S. Pat. No. 4,160,600 discloses a pressure responsive apparatus using interference rings for reading the deflection of a diaphragm exposed to pressure.
U.S. Pat. No. 3,842,353 discloses a photoelectric transducer which detects optically the position of a diaphragm and translates the position into an electric signal with a feedback circuit for balance.
U.S. Pat. No. 3,590,640 discloses a halographic pressure sensor having a flexible diaphragm exposed on one side to pressure to be measured and on the other side to a light beam which is reflected and halographically reconstructed.
U.S. Pat. No. 3,387,494 discloses a tensioned membrane for use in pressure sensing apparatus. The membrane has a unique construction providing high stability.
U.S. Pat. No. 3,040,583 discloses an optical pressure transducer for sensing small transient pressures by means of a reflected light beam.
SUMMARY OF THE INVENTION
The invention is directed to a flight instrument which uses a beam of coherent monochromatic laser light which is reflected from a pressure responsive diaphragm exposed to the pressure differentials to be sensed and which is coupled to a light reflective element for reflecting the beam of light onto an electroptical target which translates an interference pattern, created by the reflected light, into electrical translation of the sensed pressure.
By the use of such a pressure sensing apparatus for a flight instrument, the drawbacks of mechanical linkage to a visual display can be eliminated and replaced by an all electronic solid-state display.
Furthermore, the translation of the pressure into electronic signals affords the advantage of an electrical connection between the pressure sensing apparatus and the visual display apparatus, thereby alleviating overcrowding of the space available on and behind the aircraft instrument panels.
Further still, the translations of the pressure into electronic signals affords the advantage that the signals can be electronically modified and translated for a better visual presentation to the pilot.
The instant specification also discloses an accelerometer for air navigation based on the same pressure sensing apparatus described hereinabove.
As part of the disclosed invention an embodiment is described which uses a negative feedback arrangement consisting of an electromechanical transducer coupled to the reflectory element which resists, by means of an opposing mechanical force, the deflection of the reflecting element. The transducer may be a linear motor traversed by a current produced by the opto-electronic circuit. The amplitude of the negative feedback current is a measure of the pressure exerted on the pressure responsive diaphragm.
Detection of pressure in the present invention is based on sensing the position and movement of lightwave interference fringes caused by the optical interference caused by pressure changes which cause deflection of the reflecting element.
Further objects and advantges of this invention will be apparent from the following detailed description of presently preferred embodiment which are illustrated schematically in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective diagrammatic, part-cross-sectional view of an altimeter according to the teachings of the invention, showing a housing containing a pressure responsive light reflecting apparatus connected to a bellows communicating with the outside air pressure, a laser light source and an optoelectric sensor;
FIG. 2 is a cross-sectional view of an alternate version of the altimeter based on deflection of a light beam as differentiated from light interference detection showing details of the internal components, shown in FIG. 1, showing details of the internal components;
FIG. 3 is a cross-sectional view of the interior of an embodiment of the invention configured as an airspeed indicator showing the fluid connection with a pitot tube;
FIG. 4a, & 4b is a schematic circuit diagram of the electronic diagram, and the photo sensor.
FIG. 5 is an elevational diagrammatic view of the invention configured as an inertia indicator using a reflective air wedge;
FIG. 6a & 6b is a grammatic detailed view of a photodiode pattern-sensing arrangement using masked photodiodes;
FIG. 7 is a sensitive air pressure indicator having a separate vacuum chamber. The indicator is contemplated as a ground-based barometer.
FIG. 8 is a vent plug for closing the air vent of the instrument according to FIG. 7.
FIG. 9a, 9b, 9c and 9d is a schematic circuit diagram of the circuit for translating the motion of the interference pattern into an electronic digital signal;
FIG. 10 is a diagrammatic view of the invention configured as an accelerometer;
FIG. 11 is a fragmentary detail view of the mass arm pivot point shown in FIG. 10;
FIG. 12 is three axis accelerometer.
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 arrangements shown, since the invention is capable of other embodiments. Also, the terminology used herein is for the purpose of description and not of limitation.
FIG. 1 is an embodiment of the invention configured as a flight altimeter, showing an instrument housing divided into three chambers, namely the laser chamber 11, a lever chamber 12 and a bellows chamber 13.
The laser chamber 11 contains a laser interferometer constructed generally along the lines of a Michelson interferometer, which is well known and described in detail in publications such as Cenco Instrument Corp., Selective Experiments in Physics, No. 71990-548 and others.
The interferometer generally at 10, consists of a laser light emitter 14 with a lens 14a projecting a first diverging beam 15 of laser light onto a first mirror 16 that is tilted such that the beam 15 is projected downward onto a convex lens 17 with such a curvature that the exiting light beam 24 emerging downward from the lens 17 consists of parallel rays. The downward projecting beam 24 meets a half-silvered tilted second mirror 18 that operates as a beam-splitting mirror, so that half of the incident beam 24 is reflected to the left onto a third mirror 19 as a partial beam of light 26. The partial beam is reflected back as the reflected partial beam 27 and travels through the half-silvered mirror 18 until it meets a concave lens 21, disposed at the right hand side of the mirror 18, and emerges from the lens 21 as a second diverging beam 29. The beam 29 meets a convex lens 22 that has such a curvature that a second parallel beam 30 is formed. The vertical parallel beam 24, described hereinabove, was divided by the half-silvered mirror 18, and part of the light of the beam 24 continues down through the half-silvered mirror 18 as a partial vertical beam 31, which is again reflected upward as a second partial reflected beam 32 by the horizontal adjustable mirror 23. The partial second reflected beam 32 impinges on the half silver reflective coating of the tilted mirror 18 and is reflected to the right and merges with the first reflected partial beam 27, and the two merged beams, having the same wavelength and almost identical length of travel path from the laser 14, therefore produce an interference pattern on the surface of the motion sensing photo detector 38.
If the length of travel of the two interfering beams 23 and 27 have a travel difference of exactly 1/2 wavelength of the laser light ,the interference pattern created on the photo detector 38 will be a dark circular pattern on the surface of the photodetector 38. This pattern can be changed, however, by an adjustment of the horizontal mirror 23, which for that purpose is supported by two micrometer screws 33 and 34 so that the mirror 23 can be adjusted to a pattern closer to or farther from the mirror 18 in the direction of the incident light beam 31 and it also can be adjusted to a small angle to the normal of the light beam 31.
As a result of the adjustment of the mirror 23, the interference pattern on the photo detector can be modified from a dark circular pattern to a series of adjustment, alternating dark and bright horizontal parallel interference lines across the surface of the photo detector 38.
If the two mirrors 19 and 23 are accurately perpendicular to each other, the interference fringes will consist of concentric circles. Moving to the mirror 23 about 50 mm from the center of the beam splitter, quite a large number of circular fringes will be seen on the photo sensor 38 and the fringes will be closely spaced. If mirror 23 is moved inward towards the beam splitter, gradually the fringe system will contract and fringes will disappear one at a time at the center of the pattern. As the mirror 23 passes through the position of path equality the central fringe will fill the entire field of view and no fringe will show on the screen. As mirror 23 is moved past the position of path equality (still moving toward the beam splitter) the fringes will begin to re-appear at the center and move outwards. Thus, the motion of the fringes is reversed, more and more fringes will become visible as the path difference is increased.
When the mirror 23 is moved a distance d, n fringes will either appear or disappear at the center of the pattern, or pass a given point near the center, when n times l is equal to 2d, where l is the wavelength of the laser light. If the mirror 23 is tilted a small angle alpha, the fringe interference pattern will assume the appearance of an extended circle sector with a plurality of adjacent circle segments, that are alternately bright and dark. The dark segments (interference) are sharper and have better definition than the light segments.
The photodetector 38 is a motion sensing photo device constructed of two photo diodes 46 and 47 disposed one above the other as shown in FIGS. 6a and 6b; the two photo diodes 46,47 are connected by leads 41, 42, 43 and 44 to amplifying apparatus shown in more detail in FIG. 4a.
The motion sensing photo detector 38 is shown in more detail in FIG. 6a which is a face view showing in phantom line circles two photo diodes 46 and 47 partially covered by two opposing equilateral triangular openings 39 and 40, respectively, cut in a mask 38a in front of the faces of the photo diodes 46 and 47.
Each photo diode 46 and 47 has two leads 41,42 and 43,44 respectively connected to an amplifying circuit shown in FIG. 4a.
In FIG. 4a, the two leads 42 and 44 are in common connected to ground while leads 41 and 43 are connected to two amplifiers 36 and 37 respectively. The outputs of the two amplifiers 36 and 37 are in turn connected to the two opposing field windings F1 and F2 respectively of a reversible linear motor 48 having an axial sliding shaft 49. The two opposing field windings F1 and F2 are commonly connected at the center and in turn connected plus voltage. If the two inputs to the two amplifiers 36 and 37 are of equal magnitude, the combined field from the two field windings F1 and F2 will be zero, but if one is higher than the other, the combined field will assume a certain strength that will cause the sliding shaft 39 to move axially in one direction or the other.
Returning now to FIG. 1, the linear motor 48 is shown at the bottom wall of the laser chamber 11, with its axially slidable shaft 49 coupled by means of a linkage consisting of a lever 51 pivotally attached at its distal end at pivot point 52 to the slidable shaft 49 and at its proximal end pivotally attached at pivot point 53 to the upper wall of the laser chamber 11.
The lever 51 is, at an intermediate pivot point 54, pivotally attached to a horizontally slidable fork element 56 having two outer slidable legs 58, slidably received in loosely fitting sleeves 59, rigidly inserted into the interferometer suporting frame 61. A center leg 62 of the fork element 56 supports the vertical mirror 19 and has a horizontal fork handle 57 that is at its distal end pivotally attached at pivot point 62 to a lever arm 63, which is, in turn, at its distal point pivotally attached at pivot point 64 through a sliding arm 65 to a disc 66, which is coupled on the right hand side to a bellows 67 and on its left hand side to a helical compression spring 68, exerting a force indicated by arrow 69 against the disc 66.
The lever arm 63 is, at its proximal end, at pivot 60 attached to the upper wall of the lever chamber 12.
The three chambers housing the device, namely the laser chamber 11, the lever chamber 12 and the bellows chamber 13 are completely evacuated of air. The interior of the bellows 67 is connected to atmospheric air through an airfilter 71 filled with a filter medium 72 through an air opening 73.
It follows that the laser beam, the entire laser interference arrangement, the photo detector 38, with the amplifier 36-37 and the linear motor 48 together constitute a very sensitive feedback servo system that "locks" onto the dark interference fringe 78.
The voltage across the field windings F1, F2 is further connected to the two inputs of a balanced amplifier 74 which produces an output voltage on its output lead 82 which accordingly is proportional to the airpressure in the bellows 67. Such a sensitive airpressure indicator has applications as a flight instrument for indicating altitude and also for indicating rate of climb ("ROC") by introduction of suitable means for translating the output voltage at lead 82, as described in more detail hereinbelow, in connection with FIG. 4a.
It also has the potential to be used as an aircraft speed indicator when connected with a Pitot tube or as an accelerometer when connected with a defined mass through suitable linkage.
It should be understood that mechanical linkages that interconnect the bellows 67 with the mirror 19 and the linear motor 48, and wherein the ambient atmospheric pressure is balanced against the pressure of a strong spring 68 and a lienar motor 48 by means of an interference fringe created on a motionsensing photo detector, can be realized in many other ways than shown and described hereinabove. In particular, since the mechanical movements are extremely small, the entire mechanical linkage can be constructed with that in mind and flexible frictionless joints can be used throughout, instead of pivot joints.
The fork element 56 may be provided with limit screws 101 and 102 that can be adjusted so that the lateral travel of the fork element 56 is confined within a certain axial range so that the instrument, when initially powered up is always started on the same interference fringe.
The air pressure indicator described hereinabove is well suited as a flight altimeter for an aircraft combined with rate-of-climb indicator by means of a suitable electrical circuit for reading the indicator output as it appears across the field windings F1 and F2 of the linear motor 48.
The basic circuit is shown in FIG. 4a and 4b.
In FIG. 4a, the output from the airpressure indicator taken from the field windings F1 and F2 are connected through leads 75 and 76 to the differential amplifier 74 with the output lead 82, having a potential that at all times represents the airpressure in the bellows 67.
The potential at 82 is connected through a resistor R4 to a voltage indicator ALT, 75, which, using a proper scale indicates altitude in chosen units, e.g. feet, or feet multiplied by 100, 1000's or 10000's as selected by the pilot. A scale selector 85 with a dial enables the pilot to select the most suitable scale factor. A potentiometer P1 serves to selectively provide an off-set corresponding to the barometric pressure at the ground level, which the pilot uses to calibrate his altimeter in a manner well known to pilots of aircraft.
A temperature sensing circuit consisting of a thermal sensor 84 is connected through an amplifier 83 and a resistor R5 to the input to the altitude indicator 75. A temperature correction may be necessary in order to overcome temperature dependency of the mechanical linkages of the airpressure indicator shown in FIG. 1.
The resistors R4, R5 and R7 together form a summing circuit that linearly combines the outputs of the amplifier 74, potentiometer P1 and the temperature compensator 83.
The temperature sensor 84 may be any suitable temperature sensing device such as a thermistor, a diode, a thermocouple or any other suitable element. If it is a thermistor or a diode, a resistor R6 connected to plus potential may be required to provide current bias.
FIG. 2 shows an embodiment of the air pressure indicator that is quite similar to that shown in FIG. 1 and wherein similar elements are shown with the same reference numerals.
The difference resides in a different arrangement for indicating lateral movement of the fork element 56. Instead of using a moving interference fringe the laser beam 15 is projected onto the plane mirror 16, and from there as a slanted light beam 88 onto a cylindrical convex curved mirror 87. As the fork element moves laterally a short distance under control of the changing air-pressure in the bellows 67, the slanted light beam 88 will impinge on different points of the curved mirror 87, which will in turn cause the again reflected light beam 89 to be deflected up or down, as shown by the upper dashed line 89' or the lower dashed line 89", indicating movement of the curved mirror 87 to the right or the left, respectively. The very thin laser beam 15 is shaped by a rectangular horizontal slit 14a at the light emitting aperture of the laser 14, so that the beam has a horizontal rectangular cross-section having a small vertical dimension and will, after being reflected by the curved mirror 87, be dispersed slightly, as shown exaggerated in the Figure and appear on the light sensor 38 as a thin horizontal line of light. The position sensing detector 38 responds to the up-and-down movement of the beam 89 in a manner similar to that described by the interference fringe 78 shown in FIG. 4b, except in this case the sensor responds to a bright line, instead of a dark fringe line. The light sensor 38 is coupled through a circuit similar to that shown in FIG. 4a and "locks" onto the light line of the beam 85 through the linear motor 48. In all other respects the apparatus of FIG. 2 is similar to that of FIG. 1.
FIG. 3 shows another embodiment of the pressure sensing apparatus shown in FIG. 1 except the bellows 67 is connected directly to the fork element 56, instead of through the sliding arm 65 and the lever arm 63, as in FIG. 1.
This embodiment of the pressure indicator is especially useful as an airspeed indicator which responds to air pressure at the point 111 of a pitot tube 112 which is connected through a tube 113 and through an opening 114 to the interior of the bellows 67, located in a bellows chamber 117. The bellows chamber in this case is not evacuated but is filled with atmospheric air through an air filter 71 connected to a reference air pressure point on the aircraft fuselage through a tube 116. In this configuration, the bellows responds to the difference in air pressure between the pressure at the point 111 of the Pitot tube 112 and the pressure at the reference point. This difference indicates the speed of the aircraft relative to the air.
In this case the voltage between the leads F1 and F2 of the linear motor 48 is an indication of the airspeed and can be read by the pilot of a properly calibrated voltage indicator connected to leads F1 and F2 in similarity with the altitude indicator 75 shown on FIG. 4a. A similar temperature correcting arrangement may also be provided.
FIG. 5 shows a pressure indicator that is based on the vertical movement of light interference fringes created by an airwedge consisting of two glass plates 121 and 122 disposed at a small variable angle beta between the glass plates, so that they form an airspace between them, forming a vertical air wedge assembly 130 with its apex 134 at the bottom horizontal line where the adjoining surfaces of the glass plates 121 and 122 meet. The front mirror 122 is rigidly attached, while the rear mirror 121 is pivotable about the horizontal pivot axis 134a, so that it can pivot in response to the movement of the push rod 132, pivotally attached at pivot point 130a to the mirror 121. The front glass plate 122 may advantageously be half-silvered on the inner surface, facing the other glass plate 121. light beam is projected onto such an air wedge, the reflected light beam between the lines 125 and 126 forms a raster of alternating horizontal dark interference lines and bright bands known as Fizeau fringes. If the mirror 121 is moved a small angle about the pivot axis 134a, the raster of Fizeau fringes moves up or down in direct proportion to the distance of transposition of the air wedge 130. The fringes are projected onto a motion-sensing photo detector 38 that is identical to the photo detector 38 described hereinabove in connection with FIGS. 1 and 2.
For best results, the laser beam 123 is made slightly diverging, as shown somewhat exaggerated in the figure by being transmitted through a narrow horizontal slit (not shown) in the light emitter 14 or by means of a suitable lens. The reflected diverging interference pattern defined by the lines 125 and 126 may advantageously be further expanded in the concave lens 136.
The air wedge mirror 121 is attached to a horizontal pushrod 132, which is in turn attached to the center of a circular elastic diaphragm 124 that encloses a vacuum chamber 127, connected to the left hand side of the diaphragm through a channel 129. The push rod 132 is mechanically linked by a lever 51 and a sliding shaft 49 to a linear motor 48 which includes a solenoid F1, F2 seen in FIG. 4a, and the photo detector is coupled to an amplifier circuit as shown in FIG. 4a, which is also connected in a feedback coupling to the linear motor 48. The chamber 120 surrounds the vacuum chamber 127 and the air pressure in the chamber 120 also impinges upon the right hand side of the elastic diaphragm 124, which therefore in yielding to the air pressure bends inward toward the vacuum chamber a small distance that is proportional to the air pressure in the chamber 120. The diaphragm 124, bending inward, and being coupled by the pushrod 132 to the air wedge assembly causes the air wedge mirror 121 to be moved a small angle that is proportional to the movement of the center of the diaphragm 124. The angular movement ofthe mirror 121 causes the horizontal interference lines on the photo detector 38 to move up or down in unison with the movement of the center of the diaphragm 124, which is, in turn, responsive to the changes in air pressure in the chamber 120.
In operation, the entire instrument, using the same feedback mechanism described in connection with the embodiments shown in FIGS. 1, 2 and 3 is capable of "locking onto" one off the fringes, and when such locked, translates the air pressure on the elastic diaphragm 124 into a proportional voltage at the output 82 of the differential amplifier 74 of FIG. 4a, which in turn may be presented as altitude on the instrument ALT 75, and which may be translated into rate-of-climb by differentiation as described hereinabove.
FIG. 7 shows an altimeter using a beam of laser light in a construction that is somewhat similar to that shown in FIG. 5, the main difference being that it does not have the feedback from the linear motor 48 to the mirror 19 and the air wedge assembly 130. In this arrangement of the laser interferometer it is similar to the arrangement of FIG. 1 with a laser 5 projecting a diverging beam 15 onto a mirror 16, and from there downward through the lens 17 onto the half-silvered mirror 18 projecting half of the light onto the mirror 19 and the other half downward onto the adjustable mirror 23 which again reflects the light upward unto the mirror 18 and from there to the right, mixed with the light reflected from the mirror 19 through the two lenses 21, 22 onto a photo detector 140, advantageously intended as ground based air pressure indicator.
In the embodiment shown in FIG. 7, the adjustable mirror 23 is adjusted such that a raster of parallel horizontal interference fringes are created across the face of the photo detector 140. As the air pressure in the chamber 120 changes, the diaphragm 124, which encloses the evacuated chamber 127, flexes and displaces the mirror 19 attached by the pushrod 132 to the diaphragm 124. As the mirror moves back and forth in response to the changing air pressure, the interference fringes across the photo detector 140 move up or down. A certain displacement delta of the mirror 19 causes a certain number of parallel interference fringes 147 shown on FIG. 9a, which shows the photo detector 140 seen from the face side. Two photo diodes 148 and 149 are placed side-by-side instead of one above the other as in FIG. 6a and b. The face of the two photo diodes 148 and 149 are masked such that a bright band travelling downward across the face of the photo detector 148 creates decreasing ramp output signal across terminals 141 and 142 seen in FIG. 9b, trace b, while an increasing ramp output is created by the photo diode 149 seen in FIG. 9b, trace d. Conversely, if the fringe pattern moves upward photo diode 148 produces a rising ramp signal seen in FIG. 9b, trace a, and photo diode 149 produces a falling ramp signal, seen in FIG. 9b, trace c. Using these output signals and electronic circuit as shown in FIGS. 9a-9d, the circuit counts the moving fringes and stores the count in an up-down counter 151, the output of which Q1-Q10 provides a binary digital representation of the displacement delta of the mirror 19 which in turn represents the pressure on the diaphragm 124 and in this way a digital representation of the air pressure in the chamber.
The circuit of FIG. 9d operates as follows:
Viewing first FIG. 9a, alternating dark fringes 147 and bright bands 14 are projected across the face of the photo detector 140 which has the two photo diodes 148 and 149 attached thereto, the diodes having pairs of output leads 141, 142 and 143, 144 respectively. The photo diode 148 has its circular active face masked by a mask having an opening consisting of an equilateral triangle pointing downward therein, while the photo diode 149 has a similar mask, but with an upward pointing triangular opening.
It follows that if a bright band 145 moves downward across the face of the photo detector 140, the diode 148 produces an output signal as shown in FIG. 9b, trace b, while the diode 149 produces a signal shown as trace d.
Conversely, if the bands move upward, the signals will be as shown by traces a and c respectively.
Two differentiating circuits are shown in FIG. 9d each consisting of an input amplifier 156, a differentiating capacitor 157, a diode 158, a resistor 159 and an output threshold amplifier 161. The upper amplifier 161 operates to produce a pulse for each bright band moving downward across the photo detectors at the output of the upper amplifier 161 and at the output of the lower amplifier produces pulses 161 when the fringes are moving upward. The outputs from the amplifiers 161 are shown in the traces a'-d' of which trace b' shows the pulses from the upper amplifier 161 when the fringes are moving downward and trace c' shows the pulses of the lower amplifier 161 when the fringes move upward.
An up-down counter 151 is a conventional well known counting device made by several manufacturers, such as Motorola and Texas Instruments Corporation. The up-down counter 151 contains a number, e.g. ten, counting flip-flops 152 and can be preset to any desired count from an external circuit not shown via preset leads P1-P10. The up-down counter maintains a continuous count of all up and down pulses received. The instant count can be displayed on a visual digital readout 154 via a display driver circuit 153.
Instead of an electronic circuit, the output could be displayed by an electromechanical arrangement wherein the updown pulse drives a small stepping motor of well known construction, which, in turn, via a suitable gear train presents the count total on a dial with hands, in well known manner.
FIG. 10 is another application, namely an accelerometer, of the laser interferometer described in connection with FIG. 1, in particular, as the laser chamber 11 and having all the same components of which some of the major components are shown with the same reference numerals.
The accelerometer has a mass m, 171, disposed at the distal end of mass arm 172 that is pivotable in a single plane about the pivot pin 176 received in a proximal L-piece 174, best seen in FIG. 11.
The mass-arm 172 is connected, at pivot point 177 to the push rod 57 which engages the interferometer 11 as described in detail hereinabove. If the accelerometer is moving to the right as shown by the arrow 178 in the direction x at a constant velocity v which is equal to
v=dx/dt (5)
there will be no force acting on the mass m. If, however, the velocity v is changing, there will be a force f acting on the mass m according to the equation
f=m(dv/dt) (6)
which combined with equation (5) above gives
f=m(d.sup.2 x/dt.sup.2) (7)
The force f is translated to a proportional voltage appearing across the terminals F1 and F2 of the linear motor as also described in detail hereinabove.
FIG. 12 shows a three-axis accelerometer having masses 171 pivoting about orthogonal axes 176, in accordance with the coordinates x, y and z.
|
Aircraft instrument for indicating accelerations of the aircraft movement based on the use of an optical laser interferometer. A mass is connected to one of several mirrors in the interferometer which causes the interference pattern to move up or down in response to the change in acceleration. The interferometer uses a laser beam projected onto on optical detector that senses the motion of the interference pattern and produces a corresponding electrical signal which is connected to a linear motor which in turn is linked to the same mirror but in a negative feed-back arrangement that seeks to restore the position of the interference pattern. The amplifier output is an electrical analog of the acceleration.
| 6
|
In FIG. 3 of U.S. patent application Ser. No. 321,761, a dryer section is disclosed comprising the features (a) to (e) of the enclosed claim 1. The purpose of such a dryer section is to dry a fiber web, in particular within a paper-making machine having a very high operating speed. The maximum operating speed may be about 1,500 m/min or even higher.
Critical points of such a dryer section are:
1. The area where the fiber web is transferred from one dryer group to the next dryer group.
2. The so-called departure points where the fiber web and the support belt depart from the drying cylinders.
In the above-mentioned FIG. 3, for transferring the web from a first to a second dryer group, a first suction roll of the second dryer group has the function of a pick-up roll (75). The support belt (70) of the first dryer group travels around a last suction roll (74) and then tangentially to the periphery of the pick-up roll (75) around which the support belt of the second dryer group travels Upstream of pick-up roll (75), the two support belts (70 and 80) are forming a so-called convergence angle which may be, e.g. between 3 and 30°.
This configuration disclosed in FIG. 3 is preferred to that of FIG. 1 of the same U.S. application. In FIG. 1, the pick-up roll is designated (24a) upstream of which the two support belts are traveling parallel (from roll 24 to roll 24a). In this configuration the fiber web may be subjected to stress, if the two support belts must travel at a certain differential speed.
The high operating speed mentioned above is obtainable, among others, due to the suction rolls since the fiber web is held by suction against the support belt when it travels over the suction rolls, against the centrifugal force exerted on the fiber web. In the area, where the fiber web and the support belt are traveling from the periphery of the so-called delivering drying cylinder onto the periphery of the following suction roll, the fiber web should also be safely held against the support belt. To accomplish this goal, it is known from international publication WO 83/00514, FIG. 2, to provide a very short distance between the periphery of the suction roll and the peripheries of the adjacent drying cylinders. However, a problem may arise from the fact that the suction roll is positioned symmetrically with respect to the two adjacent drying cylinders: in some cases, an air blow box may be arranged on the periphery of the suction roll, preferably covering only the second half of the zone looped by the support belt (as disclosed in FIG. 3 of the above-mentioned U.S. application). This may result in an unfavorable small distance between the air blow box and the periphery of the adjacent drying cylinder.
It is a general object of the invention to improve the runability of the dryer section (allowing an extremely high operating speed and avoiding web breaks) while maintaining a high drying efficiency.
It is a further object of the invention to improve the function of the pick-up roll such that the fiber web is safely transferred from one dryer group to the next, permitting a very high operating speed and avoiding any stress subjected to the fiber web. To accomplish this, according to a first aspect of the invention, the second support belt comes into contact with the first support belt only within a small portion of the periphery of the pick-up roll. In other words, a small portion of the periphery of the pick-up roll is wrapped by the support belt of the first dryer group (see claim 1). Preferably, the angle of this periphery portion is selectable during operation of the machine.
It is a further object of the invention to provide a configuration which guarantees holding the fiber web against the support belt when it travels from one of the drying cylinders to the following suction roll while an air blow box may be arranged on the periphery of the suction roll, preferably in the second half of the zone wrapped by the support belt and/or while a certain space should be maintained where vapor escapes from the web before the web comes into contact with the next cylinder. This is accomplished, according to a second aspect of the invention, by the features mentioned in claim 5.
BRIEF DESCRIPTION OF THE DRAWINGS
The Figure is a schematic side elevation of a drying apparatus or "dryer section" of which three drying groups are shown.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The drying apparatus illustrated is part of a paper making machine. The paper web 9 to be dried (partly shown in a dotted line), in the illustrated embodiment, runs through the drying apparatus from left to right. A first drying group comprises four upper, heatable drying cylinders 11 through 14 and four lower felt rolls designed as suction rolls 21 through 24.
A paper support roll 8 transfers the paper web 9 from a press section 7 to a first endless backing belt 10 or "support belt", which preferably is fashioned as a porous wire belt ("dryer fabric") and which travels over a first belt roll 19b; this may be a suction roll if required. Together with the backing belt 10, the paper web 9 meanders through the drying group, i.e., alternately over the drying cylinders 11 through 14 and over the suction rolls 21 through 24. From the last suction roll 24, the backing belt 10 runs over several normal belt rolls 19 and 19a back to the first belt roll 19b. At the departure point from each drying cylinder 11-14, there is a very short distance A (about 30 to 100 mm) between the peripheries of the cylinder and the adjacent suction guide roll. This prevents the web 9 from sticking at the cylinder surface; the web rather follows the support belt 10, under the influence of the suction gland (e.g. 21') of the suction roll. The latter may have a conventional stationary inner suction box or an outer suction box as disclosed in U.S. Pat. No. 4,202,113. Web stabilizers as shown in U.S. application No. 321,761 are no more necessary.
The second drying group comprises four lower heatable drying cylinders 15 through 18 and five upper suction rolls 24a and 25 through 28. Passing through this drying group is a second backing belt 20, which from the last suction roll 28 runs over several belt rolls 29, 29a and 29b back to the first suction roll 24a. This latter suction roll 24a (or "pick-up roll") picks the paper web up from the backing belt 10, thereby avoiding an open web draw. At the end of this second drying group, i.e., downstream of the last suction roll 28, the paper web 9 is transferred by a further pick-up roll 28a to the next drying group; again an open web draw is avoided. Visible of that third group are only two drying cylinders 31 and 32, a backing belt 30, suction rolls 41, 42 and a belt roll 39. In the first dryer group, the underside or "first side" of web 9 contacts the drying cylinders 11-14. In the second dryer group, the upperside or "second side" of web 9 contacts the drying cylinders 15-18. In the third dryer group, the first web side again contacts the cylinders 31, 32.
The belt roll 19 (following to the last suction roll 24 of the first dryer group) is shiftable approximately horizontally. This roll is shown in three different positions: In full lines, it is in its normal position wherein the draw of belt 10 from roll 24 to roll 19 is straight and tangent to the periphery of pick-up roll 24a. In this position, the second belt 20 comes into contact with the first belt 10 approximately only at a "point" as seen in the drawing. A further possible position of belt roll 19 is shown in dot-dash-lines, wherein the second belt 20 comes into contact with the first belt 10 within a small portion of the periphery of pick-up roll 24a, said portion comprising an angle a of about 10°. This angle a may be varied between zero and at most 20° by shifting of belt roll 19. Thus, the operator is able to select any size of angle a according to the actual requirements, with the angle a depending from the type of the web to be dried or from the operating speed or from the amount of a speed difference sometimes needed between the two belts 10 and 20. In this way, the transfer of web 9 from the first to the second dryer group can be achieved safely even with the highest operating speeds, without the risk of web breaks. Furthermore, the threading of the so-called transfer strip (a narrow edge strip of the web) into the dryer section (e.g. after a shut down) may be accomplished automatically without the assistance of a so-called rope carrier system.
It should be noted that--irrespective of the size of angle a--the two belts 10 and 20, where travelling towards pick-up roll 24a are forming a wedge-like gap including a so-called convergence angle b. The size of this angle may be freely selected between about 3° and 30°, according to space conditions.
If the second support belt 20, travelling from belt roll 29b to pick-up roll 24a, transports air boundary layers which tend to impair the web transfer it is helpful to provide a prolonged suction gland 34 or a separate pre-suction zone in pick-up roll 24a at the side where belt 20 is running towards pick-up roll 24a.
For some reasons (e.g. one of the dryer groups must be shut down while the others are running) it may be helpful to provide temporarily a distance between the two belts 10, 20 at pick-up roll 24a. In this case, roll 19 may be shifted into the position shown with twin-dot-dash lines.
As convention, a doctor 40 is installed at the free surface of each drying cylinder. Furthermore, at some of the suction rolls 22-27 and 41, an air blow box 38 may be provided which may include a suction chamber (not shown) for the removal of moist air. Each of the blow boxes 38 envelopes the pertaining suction roll over approximately one-fourth of its periphery, namely in the second half of the zone looped by the support belt 10 or 20 or 30. For this reason, in the first and in the second dryer group, each of the suction rolls 21-27 is positioned asymmetrically with respect to the two associated drying cylinders, those three rolls forming a set comprising a "web delivering cylinder" (e.g. 12), the suction roll 22 and a "web receiving cylinder" 13. Now, while maintaining the very small distance A, mentioned above, between the peripheries of the web delivering cylinder and the suction roll, there is a larger distance B (about 2 to 10 times larger) between the peripheries of the suction roll and the web receiving cylinder. In this way, space is obtained for said doctor 40, the air blow box 38 and a relatively large gap needed therebetween as well as a gap needed between the air blow box and the web receiving cylinder. Furthermore, where web and support belt are running from the suction roll to the receiving cylinder, space is maintained where vapor escapes from the web, irrespective whether a blow box is present or not.
After the web has received a certain dryness, e.g. at the end of the second dryer group, the tendency that the web sticks to the cylinder surface may be less than before. Therefore, e.g. beginning in the third dryer group, the distance between the web delivering side of each cylinder and the following suction roll may be larger than before In other words: It may be possible then, to arrange each suction roll symmetrically with respect to the two associated cylinders as shown at 31, 32, 41.
In the dryer section shown, all drying cylinders are arranged in horizontal cylinder rows. However, the principles of the invention may also be employed in a dryer section having vertical cylinder rows, as disclosed in pending U.S. application Ser. No. 07/442,547.
Although the present invention has been described in relation to particular embodiments thereof, many other variations and modifications and other uses will become apparent to those skilled in the art. It is preferred, therefore, that the present invention be limited not by the specific disclosure herein, but only by the appended claims.
|
A dryer section with two dryer groups and a transfer for the paper web between the dryer groups. The receiving dryer group has a vacuum roll on which the felt of the proceeding dryer group is partially wrapped. An adjusting mechanism enables the wrap angle to be adjusted between an arc angle of 0 and 20 degrees.
| 3
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to support post assemblies and, more particularly, to connector brackets and hinge plate assemblies for attaching support posts to signs, luminaires, and the like.
2. Description of the Related Art
Typical support post installations involve securing one end of the post in the ground and attaching a sign, light fixture, or other object of interest to the other end. In certain installations, a plurality of posts are used to support each end of a large object or objects that span a distance, such as over a road.
In order to support the weight of large objects and to withstand the forces of nature, such as the wind, as well as impact from vehicles and other objects, the posts are sunk deep in the earth. When required, the posts are anchored in place with concrete or other anchoring methods. The disadvantage of such installations is that damage to a post requires replacement of the post and the anchoring system. For example, a vehicle impacting a post that supports a sign spanning a highway will cause damage to the impacted post, typically near the ground, necessitating excavation and replacement of the entire post and the anchoring system. In addition, the sign attached to the other end of the impacted post may remain suspended because it is supported by the other posts but become damage itself due to twisting and bending of the impacted post. This may also result in damage to the non-impacted posts.
In order to avoid replacement of the entire post and related anchoring system, a mounting bracket with breakaway connectors has been developed by the applicant, as disclosed in U.S. Pat. No. 4,923,319, entitled “Breakaway Connector” and U.S. Pat. No. 6,210,066, entitled “Breakaway Bracket Assembly,” both of which are incorporated herein by reference in their entirety. Briefly, the mounting bracket and breakaway connectors have preformed stress points that will fracture when subjected to a predetermined load. The bracket and connectors will separate from the anchoring system without damaging it. Replacement of the post becomes a matter of replacing the remaining bracket or connector fragment at the anchor point with a new component and re-attaching the repaired post or a replacement post.
While the foregoing is sufficient for its intended purpose, it does not address damage occurring at the other end of the impacted post. In most situations a post that is broken or deformed at impact will damage the sign attached to it and possibly other supporting posts. Hence, there is a need for an attachment assembly that prevents or reduces damage to the attached sign or other supported object and facilitates replacement of the impacted post.
BRIEF SUMMARY OF THE INVENTION
The present disclosure is directed to a support post assembly and to a hinge plate and a mounting bracket assembly used in conjunction with support posts. In accordance with one embodiment of the disclosure, a mounting bracket assembly is provided for holding a first post member to a second post member, the assembly includes a first bracket member having a plurality of openings to enable connection of the first bracket member to the first and second post members, and a second bracket member coupled to the first bracket member in a location that will be between the first and second post members. The second bracket member has a channel formed therein to define a first half portion and a second half portion, and to define a hinge point in the second bracket member about which the first half portion will bend with respect to the second half portion when subjected to a predetermined force. In this manner the first post member will remain attached to the second post member but be permitted to swing about the bend line, thus preventing damage to the second post member and facilitating replacement thereof. Ideally, the second bracket member forms shoulders that are adapted to provide a surface against which the first and second post members rest or bear against.
In accordance with another embodiment, a mounting bracket assembly is provided for holding a first post member to a second post member that includes a first bracket member having a plurality of openings to enable connection of the first bracket member to the first and second post members. A second bracket member is provided that is coupled to the first bracket member in a location between the first and second post members. A plurality of openings are formed transversely through the second bracket member that define a first half portion and a second half portion in the second bracket member, and further define a breakpoint about which the first half portion will break with respect to the second half portion when subjected to a predetermined force. In this manner, the second post member will be permitted to break free from the first post member, preventing damage to the first post member and enhancing replacement of the second post member. Ideally, the second bracket member is configured to provide shoulders that are adapted to have surfaces against which the first and second post members rest or bear against.
In accordance with yet a further embodiment of the disclosure, a hinge plate for holding a first post member to a second post member in fixed space relationship is provided. The hinge plate is formed to have a body configured to be attached to the first and second post members. The body includes an enhanced section having shoulders and a channel formed between the shoulders that divides the body into a first portion and a second portion and that defines a bend line about which the first portion will bend with respect to the second portion when subjected to a predetermined force. Ideally, the enhanced section has a thickness that is greater than the non-enhanced remaining sections of the body.
In accordance with another embodiment, the hinge plate described above is provided with an enhanced section that, instead of having a channel, includes a plurality of openings formed transversely thereacross that divide the body into a first portion and a second portion and define a break line about which the first portion will bend or break or both with respect to the second portion when subjected to a predetermined force.
In accordance with another aspect of the foregoing embodiments of the disclosure, the hinge plate described above is provided that includes a combination of the channel and the plurality of openings formed across the enhanced section, the plurality of openings intersecting with the channel.
In accordance with yet another embodiment of the disclosure, a post system is provided that includes a first post adapted to be connected to an object; a second post member adapted to be anchored to the ground; and a mounting bracket assembly for holding the first post member to the second post member. In one embodiment, the mounting bracket assembly comprises first and second bracket members, the first bracket member having a plurality of openings to enable connection of the first bracket member to the first and second post members, and the second bracket member coupled to the first bracket member in a location between the first and second post members and having a channel formed therein to define a hinge point about which the first and second post members will swing when either of the first and second post members are subjected to a predetermined force. Ideally, the second bracket member is configured to have shoulders that are adapted to provide a surface against which the first and second post members will bear.
In accordance with another aspect of the foregoing embodiment, the post support system utilizes a unitary hinge plate instead of the mounting bracket assembly, the unitary hinge plate configured to be attached to the first and second post members and includes an enhanced section having shoulders and a channel formed between the shoulders to define a bend line about which the first and second post members will bend when either or both are subjected to a predetermined force.
In accordance with still yet another embodiment of the disclosure, a connector for attaching a first post section to a second post section to form a unitary support post for road signs, lights, and the like, is provided. The connector includes a plate having a first plate section sized and shaped to be attached to the first post section, a second plate section sized and shaped to be attached to the second post section, and a channel formed entirely across at least one side of the plate to divide the first plate section from the second plate section and to provide a weakened portion of the plate to enable bending and tearing of the plate when the unitary post is subjected to a force from any direction.
In accordance with another aspect of the foregoing embodiment, the channel includes at least one opening formed therein through the plate to further direct the force for bending and tearing of the plate.
In accordance with yet another aspect of the foregoing embodiment, the channel includes two or more parallel grooves formed in the plate. In one embodiment, the channel is formed on both sides of the plate in back-to-back relationship. In another aspect of the foregoing embodiment, the channel is formed of two parallel adjacent grooves on at least one side and preferably on both sides of the plate.
In accordance with yet a further embodiment, the foregoing plate also includes at least one, and preferably two, sections that are cut out adjacent to the channel formed in the fuse plate. Ideally, the cutout sections are in the shape of a V wherein the point or apex of the V terminates in the channel and the width of the cutout increases to the side of the plate.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The foregoing and other aspects of the invention will be more readily appreciated as the same become better understood from the following detailed description when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is an isometric projection of a signpost assembly formed in accordance with the present invention;
FIG. 2 is an isometric projection of a unitary hinge plate formed in accordance with one embodiment of the present invention;
FIG. 3 is a cross-sectional view of the unitary hinge plate of FIG. 1 installed on a square tube post assembly;
FIG. 4 is an isometric projection of another embodiment of the unitary hinge plate formed in accordance with the present invention;
FIG. 5 is an exploded isometric projection of a two-piece hinge plate assembly formed in accordance with the present invention;
FIG. 6 is an isometric projection of a strap member of the two-piece hinge plate assembly formed in according with another embodiment of the invention as installed on an I-beam post;
FIG. 7 is an isometric projection of the strap member of FIG. 6 and a crosspiece of the hinge plate assembly of FIG. 5 installed on the I-beam post of FIG. 6 in accordance with the present invention;
FIG. 8 is an exploded isometric projection of a two-piece mounting bracket assembly formed in accordance with the present invention;
FIG. 9 is an exploded isometric projection of the mounting bracket assembly of FIG. 8 in conjunction with a U-channel post;
FIG. 10 is a plan view of a fuse plate formed in accordance with a further embodiment of the present invention;
FIG. 11 is an isometric view of the fuse plate of FIG. 10 in conjunction with a support post;
FIG. 12 is an isometric view of a fuse plate formed in accordance with yet a further embodiment of the invention;
FIGS. 13 and 14 are isometric views of alternative applications of the fuse plate of FIG. 12 ;
FIG. 15 is an isometric view of another alternative embodiment of the invention; and
FIG. 16 is an isometric view of the embodiment of FIG. 15 employed on the exterior of a post.
DETAILED DESCRIPTION OF THE INVENTION
Representative embodiments of the present disclosure will now be described in conjunction with FIGS. 1-9 . It is to be understood that while these embodiments are described in conjunction with a support post system for supporting road signs, it is to be understood that the present invention will have application with respect to luminaires, and to other objects supported above the ground where either or both of the support posts and the supported object are subjected to a predetermined load, such as from impact or from the wind.
Referring initially to FIG. 1 , shown therein is a support post system 10 that includes a sign 12 supported about the ground 14 by a support post assembly 16 . In this embodiment, the support post assembly 16 includes a first post member 18 attached to the sign 12 , and a second post member 20 attached to an anchor assembly 22 by a breakaway connector system 24 . It is to be understood that the breakaway connector system 24 can be formed of existing systems or the embodiments disclosed herein can be used where applicable.
The second post member 20 is attached to the first post member 18 by a joint splice 26 formed in accordance with the embodiments described in more detail below.
Turning next to FIG. 2 , shown therein is a hinge plate 28 formed in accordance with one embodiment of the disclosure. The hinge plate 28 in this embodiment comprises a unitary body 30 having a first substantially planar mounting portion 32 and a second substantially planar mounting portion 34 depending from an enhanced section 36 that forms the central portion of the body 30 . The enhanced section 36 has a thickness that is greater than the thickness of the unenhanced portions of the body 30 , i.e., the first and second mounting portions 32 , 34 . A channel 38 is formed in the enhanced section 36 that in this embodiment extends transversely across the entire width of the body 30 .
In one embodiment, the channel 38 has a substantially curved or arcuate cross-sectional configuration to facilitate bending without breaking. The channel 38 divides the body 30 into first and second halves and constitutes a weakened area that functions as a bend line. When one or the other or both of the first and second mounting portions 32 , 34 are subjected to a predetermined force normal to a face of the mounting portions 32 , 34 , the body 30 will bend about the channel 38 . This predetermined force can be a compound of a larger total force acting from a different direction. The enhanced section 36 projects from one side of the body 30 to form two shoulders 44 . Openings 40 , 42 in the first and second mounting portions 32 , 34 , respectively, provide access for fasteners (shown in FIG. 3 ). Ideally, they channel is adapted to permit bending while resisting breaking, thus retaining the attached post members in a connected relationship.
As shown in FIG. 3 , a pair of hinge plates 28 are used to hold the first post member 18 and second post member 20 in fixed spaced relationship. Each hinge plate 28 has the enhanced section 36 positioned so that the first and second first post members 18 , 20 bear against the respective shoulders 44 . A pair of fasteners 46 pass through the first and second first post members 18 , 20 and the openings 40 , 42 in the hinge plates 28 , which are then secured in place by nuts 48 .
When one or the other or both of the first and second first post members 18 , 20 are subjected to a force that is less than the maximum sustainable load of the first and second post members 18 , 20 , the hinge plates 28 will bend about their respective channel 38 , allowing the second post member 20 to move or swing with respect to the first post member 18 . Similarly, should the sign 20 be subjected to a wind force that is greater than the predetermined load of the hinge plate 28 , the first post member 18 will bend with respect to the second post member 20 about the channel 38 in the respective hinge plates 28 .
Turning next to FIG. 4 , shown therein is an alternative embodiment of a hinge plate 50 formed in accordance with the present disclosure. For ease of reference, elements in common with the hinge plate 50 and the hinge plate 28 will have the same reference numbers. In this embodiment, the enhanced section 52 has two channels 54 , 56 formed therethrough. The additional channel provides additional flexibility to the hinge plate 50 and enables it to swing more readily, i.e., at a lower amount of force.
Turning next to FIG. 5 , shown in an exploded view is a mounting bracket assembly 60 that includes a strap 62 and crosspiece 64 that attaches to the strap 62 with a fastener 66 and nut 68 . The strap 62 includes an elongate body 70 having a plurality of openings 72 formed therein and aligned along the longitudinal axis of the body 70 for attaching the body 70 to support posts (not shown). The fastener 66 passes through a central opening 74 in the crosspiece 64 and an opening 76 in the strap 62 to connect with the nut 68 .
The crosspiece 64 includes two channels 78 , 80 formed across its width. The crosspiece 64 has a top surface 82 and bottom surface 84 that function as shoulders when attached to the strap 62 . The shoulders 82 , 84 provide a surface against which post members will bear. The opening 74 is formed in the ridge between the channels 78 , 80 so as not to interfere with bending of the cross piece 64 .
This mounting bracket assembly 60 is configured to attached to first and second post members 18 , 20 , in the same manner as the hinge plate 28 shown in FIG. 3 . The fasteners 46 pass through the openings 72 of the strap 62 to hold the first and second post members in fixed spaced relationship. However, in this embodiment the strap 62 may be used alone or in combination with the crosspiece 64 . In one manner of use, the crosspiece 64 is preinstalled on the strap 62 before attachment to the post members 18 , 20 . Alternatively, the crosspiece 64 can be inserted between the first and second post members 18 , 20 after the strap 62 has been attached. The two channels 78 , 80 function in the same manner as described above with respect to the channels 54 , 56 of the hinge plate 50 of FIG. 4 .
Shown in FIG. 6 is another embodiment of the invention wherein a first strap 86 and another strap 88 are attached to either side of a first I-beam member 90 and a second I-beam member 92 to hold the first and second I-beam members 90 , 92 in fixed spaced relationship. Fasteners 98 are provided to hold the straps 86 , 88 to their respective I-beam members 90 , 92 . Here, the first and second straps 86 , 88 each have a plurality of openings 94 formed transversely across a central portion 96 thereof. The openings 94 may vary in size and number; however, their center points are aligned along a desired bend line. The function of the openings 94 is to provide a weakened area about which the strap 86 , 88 will bend when subjected to a predetermined force.
Shown in FIG. 7 is yet another alternative embodiment of the support post assembly of FIG. 6 wherein crosspieces 100 , 102 have been inserted between the first and second I-beam members 90 , 92 and bolted to the respective straps 86 , 88 by fasteners 104 . Each crosspiece 100 , 102 includes a plurality of channels 106 , 108 formed in the manner as described above with respect to the crosspiece 64 in FIG. 5 . The I-beams 90 , 92 bear against the shoulders 110 of the respective crosspieces 100 , 102 . In this embodiment, the channels 106 , 108 cooperate with the openings 94 in the straps 86 , 88 to ensure bending and breaking occurs at the desired location, i.e., along the channels 106 , 108 .
In FIG. 8 , yet a further embodiment of the invention is illustrated wherein a mounting bracket assembly 112 is provided to include a strap 114 and crosspiece 116 configured to be bolted to the strap 114 by fastener 118 and nut 120 . As with previous embodiments, the crosspiece 116 has shoulders 122 , 124 formed on the respect top and bottom sides thereof. The fastener 118 passes through a central opening 74 in the crosspiece 116 and an opening 76 in the strap 114 to connect with the nut 120 . A plurality of openings 72 are provided in the strap 114 for connection to appropriate post members (not shown).
In this embodiment, a plurality of openings 126 are formed transversely across the strap 114 , preferably in alignment with the opening 76 to define a linear breakpoint or bend line for the strap 114 . Openings 128 are formed across the width of the strap 114 that provide a similar function as the openings 126 in the strap 114 . This embodiment may be used in place of the mounting bracket assembly 130 shown in FIG. 7 .
Turning next to FIG. 9 , illustrated therein is a post support assembly 111 having the mounting bracket assembly 112 of FIG. 8 shown in exploded relationship with a U-channel post assembly 132 comprising a first post member 134 positioned above the mounting bracket assembly 130 and second post member 136 anchored in a concrete pad 138 formed in the ground. The first and second post members 134 , 136 each include openings 140 for aligning with the openings 72 in the strap 114 for attachment. The first and second post members 134 , 136 are positioned to bear against the crosspiece 116 on the shoulders 122 , 124 thereof.
The mounting bracket assembly 112 may be positioned on the inside of the U-channel post members 134 , 136 or on the outside. In either mounting position, the crosspiece 116 will be positioned between the first and second post members 134 , 136 .
Referring next to FIGS. 10 and 11 , shown therein is another embodiment of the invention in the form of a breakaway fuse plate 150 attached to a support post 152 . As shown in these figures, the support post 152 is formed of an upper post section 154 and a lower post section 156 that are held together by the fuse plate 150 to form a unitary support post 152 . Ideally, a corresponding plate is used on a reverse side of the web 158 . In this embodiment, the support post 152 is a typical I-beam or H-beam post having a web 158 with flanges 160 at each end of the web 158 . It is to be understood, however, that the present embodiment can be adapted for use by sizing and shaping it for attachment to support posts of different configurations, including channel, angle, and rectangular or square solid post construction, of either metal, wood, or metal alloys of varying forms. In one embodiment, the metal is ASTM-36 steel or 65-45-12 ductile iron or 60-40-18 ductile iron.
The plate 150 as seen in these views is of substantially a rectangular shape and is divided into a first plate section 162 and second plate section 164 by a channel 166 . In the embodiment shown, the plate 150 is substantially flat having mutually opposing parallel faces 168 that are circumscribed by a top edge 170 , first and second side edges 172 , 174 , and a bottom edge 176 .
The channel 166 extends from the first side edge 172 to the second side edge 174 to bisect the plate 150 and provide a weakened area about which the plate 150 can bend and break or tear when subjected to a predetermined force through the support post 152 . The channel 166 can have different cross-sectional configurations, and as shown here it is arcuate or circular. However, it can have a rectangular or square or V-shaped configuration to meet particular applications. Although the plate 150 shown in FIGS. 10 and 11 has the channel 166 formed only in the exposed face 168 , it is to be understood that the channel 166 can also be formed on the reverse side of the plate 150 , either alone or in combination with a matching channel on the opposite face. It is to be also understood that while the channel 166 is shown as a single groove, it is possible to form the channel as multiple parallel grooves, such as two or three grooves, either formed on one side or both sides of the plate 150 . When formed on both sides of the plate 150 , the opposing grooves should be back-to-back to facilitate bending of the plate 150 only about the channel 166 or tearing of the plate along the channel 166 .
To facilitate the tearing of the plate 150 , an opening 178 is formed completely through the plate 150 and positioned within the channel 166 . As shown in FIGS. 10 and 11 , the opening 178 in the channel 166 is positioned at the center of the plate 150 , both longitudinally and laterally. However, it is to be understood that one or more openings can be formed in the channel 166 and positioned at various points along the channel 166 . Ideally, the diameter of the opening extends to the vertical top and bottom sides of the channel 166 , and it can be laterally elongated as shown.
The plate 150 is preferably sized and shaped for attachment to the web 158 of each of the upper and lower post sections 154 , 156 . One manner of attachment is by use of fasteners extending through a plurality of openings (not shown) formed in the plate 150 . As shown in FIGS. 10 and 11 , the fasteners are in the form of a bolt 180 extending through a corresponding opening formed in the plate 150 , through the web 158 of the support post 152 , and ideally through a second plate 150 , where a nut 182 as shown in FIG. 11 is used to tighten the bolt, the plates 150 , and the two sections 154 , 156 of the support post 152 . An optional washer 184 can be used as shown in FIG. 11 . Other methods of attachment can include welding, bonding with adhesive, riveting, and the like. In this embodiment, six bolts are used, three on each of the first and second plate sections 162 , 164 . When so attached to the support post 152 , the channel 166 is aligned over the intersection 186 of the upper and lower post sections 154 , 156 . As shown in this embodiment, the post sections 154 , 156 are placed together in abutting relationship where they are held by the plates 150 . While two plates 150 are used, it is to be understood that only one plate 150 can be used in certain situations.
In accordance with another embodiment of the invention, and as an enhancement to all of the foregoing embodiments described in conjunction with FIGS. 2-11 , the breakaway hinges and fuse plates can be further designed to bend and tear at their respective weakened areas by completely removing additional material adjacent to the weakened area. The removal of the material will facilitate directing of forces to the weakened area and guiding the bending, and tearing where required, of the material of the breakaway bracket or fuse plate.
For example, in FIGS. 10 and 11 , a cutout section 188 is formed in each of the first and second side edges 172 , 174 . The cutout section 188 is formed by the removal of material from the plate 150 or by forming of the plate 150 such that the cutout section is generated. It is to be understood that the cutout section can be formed in only one of the side edges 172 , 174 , although preferably it is formed in both side edges 172 , 174 to direct forces generated from any direction.
The cutout section as shown in the embodiment of FIGS. 10 and 11 has a triangular shape such that an apex 190 of the triangle intersects with the channel 166 . The edges 192 of the cutout section 188 then extend away from the apex 190 such that the width of the cutout section 188 increases towards the edges 172 , 174 .
The design illustrated and described in conjunction with FIGS. 10 and 11 is configured to provide an omni-directional fuse plate that attaches to both the lower and upper sections of a support post for a sign structure, light pole, guardrail post, or any post system that will bend and tear when subjected to a force from any direction. Thus, the system described above will work on all types of posts. On sign structures, the intersection 186 of the upper and lower post sections 154 , 156 will be approximately nine feet off the ground. With guardrails and posts, it will be approximately four inches off the ground.
To install the present invention on existing posts, it will be necessary to cut the post where the installation is desired to form the upper and lower post sections 154 , 156 . When the plate 150 is installed with bolts 180 , there are no torque requirements in most applications. Thus, when subjected to an impact from any direction, the impact side of the omni-directional fuse plate system comes apart while the other side of the system holds the post, allowing the vehicle to pass under the sign structure. With guardrail posts or other systems that are required to break away close to the ground, the present invention allows the post to just lie down from the impact. This enables the vehicle to travel over the post. Hence, the invention provides a unique method and device that is mounted solely to the web of the post in one embodiment.
With respect to the fuse plate of FIGS. 10 and 11 , it is to be understood that the plate is preferably formed of a unitary flat piece of metal material. In one embodiment, the plate has a preferred thickness range of one-fourth inch to one-half inch, depending on the size of post or beam to which it is attached. In addition, the single channel 166 has a preferred width of has a preferred depth in the range of one-sixteenth of an inch to three-eighths of an inch, depending on the beam size. When two grooves are formed to create the channel, each groove will have a preferred depth in a range of one-sixteenth of an inch to three-eighths of an inch.
In another embodiment, the plate 150 is formed such that the first plate section and second plate sections 162 , 164 are in two pieces and are joined by a breakaway element that includes the channel 166 or grooves. The plate sections can be joined by welding, fasteners, or other means known to those skilled in the art so that the breakaway element is positioned at the desired breaking or tearing point.
FIGS. 12-14 illustrate yet another embodiment of the invention in which a plate 194 is provided having a configuration similar to the plate 150 described above and further including extensions or wings 196 on one or more corners thereof. For ease of reference, like reference numbers will be used to refer to identical components or features of the plates 150 and 180 .
In the embodiments shown in FIGS. 12-14 , the fuse plate 194 includes a plurality of flanges or wings 196 extending from each of the first and second side edges 172 , 174 on each of the first and second plate sections 162 , 164 for a total of four wings 196 . Each wing has a substantially square-shaped configuration and includes an opening 198 through which a fastener can pass. This particular configuration enables the plate 194 to be retrofit to existing applications where openings 198 can be used with existing fastener openings 200 in the flanges 160 of the support post 152 as shown in FIG. 13 . It is to be noted in the embodiment of FIG. 13 , the plate 194 utilizes substantially rectangular cutout sections 202 in association with the wings 196 instead of the V-shaped cutout section 188 shown in FIG. 12 . As previously explained, the shape of the cutout section can be adapted for the particular application of the fuse plate system.
FIG. 14 shows the plate 194 used with the upper post section 154 spaced apart from the lower post section 156 . This particular installation prevents the rubbing together and damaging of the post sections 154 , 156 that can occur when the support post 152 is subjected to the elements, particularly to wind. This particular mounting configuration prevents rubbing off of the galvanization and the subsequent rusting of the area. Hence, the plate 194 is attached to the web and to the flanges of the post 152 , whereas in the past other devices have been attached to only the flanges of the post.
FIGS. 15 and 16 illustrate yet another embodiment of the invention in which a fuse plate 210 is applied to the exterior of a square tube post 212 . Here, the fuse plate 210 has two additional openings 214 , 216 to accommodate fasteners 217 through the first and second plate sections 218 , 220 . In addition, the wings 222 , 224 extending from each side of the first and second plate sections 218 , 220 are formed to accommodate a fastener 219 between them, as shown in FIG. 16 , or cutout sections 188 , 202 disclosed above can provide clearance for the fastener.
The web design disclosed herein increases wind load capacity while bending, breaking, and releasing easier when impacted. On a 53×5.7 I-beam, the fuse plate of the present disclosure breaks 69% easier than existing connector plates, yet withstands greater wind loads.
Although a preferred embodiment of the invention has been illustrated and described, it is to be understood that various changes may be made therein without departing from the spirit and scope of the invention. Hence, the invention is to be limited only by the scope of the claims that follow and the equivalents thereof.
All of the above U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the Application Data Sheet, are incorporated herein by reference, in their entirety.
From the foregoing it will be appreciated that, although specific embodiments of the invention have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the invention. Accordingly, the invention is not limited except as by the appended claims.
|
A support post assembly with mounting bracket assembly and hinge plate with defined bend lines and break points are provided to prevent or reduce damage to objects attached to the support post assembly. The hinge plate has an enhanced section having a channel formed transversely thereacross to function as a bend line when the support post assembly is subjected to a predetermined force. A section of reduced or removed material further directs the force to the weakened area to guide the bending, and openings in the bend line guide breaking or tearing of the plate. Damage is limited to the hinge plate, which is easily replaced. A mounting bracket assembly having a two-piece body for connecting or splicing support posts together includes a strap with crosspiece configured to provide a desired bend line or breakpoint.
| 4
|
BACKGROUND OF THE INVENTION
The present invention relates generally to exposing or feeding a vaporous fluid to a combustion cylinder, particularly to exposing or feeding a combustible vaporous fluid to a combustion cylinder, and specifically to a rotatable structure for such which is timed with the stroke of the piston.
Fluid for combustion is typically introduced into the combustion cylinder of an internal combustion engine through an intake valve. The combustion fluid is typically mixed with air prior to being introduced into the combustion cylinder and is generally in a gaseous state. Fluid injectors typically inject a combustion fluid in the mist form directly into the combustion cylinder where it is mixed with air for combustion.
SUMMARY OF THE INVENTION
A general object of the invention is to provide a unique fluid feed mechanism for feeding fluid to the combustion cylinder of an internal combustion engine.
Another object of the invention is to provide a fluid feed mechanism which is uniquely rotatable. Specifically, the mechanism includes a rotatable structure with a cavity formed therein. The cavity is communicable at variable times with a fluid outlet and with the combustion cylinder. The structure rotates such that the cavity is moved from the fluid outlet to the combustion cylinder. Fluid flows into the cavity as the cavity passes the fluid outlet. Such fluid then mixes with other fluid in the combustion cylinder as the cavity passes the combustion cylinder.
Another object of the invention is to provide such a fluid feed mechanism which is uniquely timed. The rotating structure includes timing means to advance or retard the location of the fluid filled cavity relative to the stroke of the piston. The timing means includes a central shaft engaged with an angled splined arrangement with the structure such that axial movement of the shaft rotates the structure relative to the shaft and thus advances or retards the location of the cavity relative to the stroke of the piston.
Another object of the invention is to provide such a fluid feed mechanism which is uniquely connected to the piston. Specifically, a mechanical train runs from the piston to the means for rotating the structure. Accordingly, it is ensured that the fluid is fed to the combustion cylinder at the proper time.
Another object of the invention is to provide a fluid feed mechanism which uniquely includes a rotating disk. The cavity extends from one of the flat faces of the disk.
Another object of the invention is to provide such a fluid feed mechanism which includes a unique cavity. Specifically, the cavity includes a leading edge tailored to be substantially equidistant to the edge of the combustion cylinder at one point during rotation of the structure such that fluid from the cavity mixes as quickly as possible with fluid from the cylinder.
Another object of the invention is to provide such a fluid feed mechanism which includes a unique means for purging the cavity of exhaust gases that may be present. Specifically, the cavity is purged after the cavity has finished communicating with the combustion cylinder, but prior to communication with the combustible inlet fluid line.
Another object of the invention is to provide a unique location for the rotatable structure. Specifically, the structure is-seated in the cylinder head of the engine. Such a location provides for efficient manufacture, operation, maintenance, repair, and modification.
Another object of the invention is to provide unique methods for feeding fluid to the combustion cylinder of an internal combustion engine.
Another object of the invention is to direct the combustion toward the center of the combustion cylinder.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a side, partially diagrammatic view of the present fluid feed mechanism.
FIG. 2 shows an isolated, partially diagrammatic view of the fluid feed mechanism relative to a combustion cylinder and shows the fluid feed mechanism in position to accept fluid from a fluid outlet.
FIG. 3 shows an isolated, partially diagrammatic view of the fluid feed mechanism relative to a combustion cylinder and shows the fluid feed mechanism in position to feed the fluid into the combustion cylinder.
FIG. 4 shows an isolated, partially diagrammatic view of the fluid feed mechanism relative to a combustion cylinder and shows the fluid feed mechanism in position to purge exhaust gases from the cavity.
FIG. 5 shows a perspective, partially diagrammatic view of an internal combustion engine relative to the fluid feed mechanism.
FIG. 6 shows a partially diagrammatic, side, partially section view of the fluid feed mechanism mounted relative to the head and block of an internal combustion engine, further shows the preferred embodiment for transmitting rotational power to the shaft of the disk of the fluid feed mechanism while permitting axial movement of the shaft, and further shows the preferred embodiment for transmitting axial movement to the shaft for timing the disk.
FIG. 7 shows another embodiment for transmitting rotational power to the shaft of the disk of the fluid feed mechanism while permitting axial movement of the shaft relative to the means for transmitting rotational power.
FIG. 8 shows another embodiment for transmitting axial movement to the shaft for timing the disk.
All Figures are drawn for ease of explanation of the basic teachings of the present invention only; the extensions of the Figures with respect to number, position, relationship, and dimensions of the parts to form the preferred embodiment will be explained or will be within the skill of the art after the following description has been read and understood. Further, the exact dimensions and dimensional proportions to conform to specific force, weight, strength, and similar requirements will likewise be within the skill of the art after the following description has been read and understood.
Where used in the various figures of the drawings, the same numerals designate the same or similar parts. Furthermore, when the terms "axial", "end", "upper", "lower", "radial", "inwardly", "side", "upright", "first", "second", "over", and similar terms are used herein, it should be understood that these terms have reference only to the structure shown in the drawings as it would appear to a person viewing the drawings and are utilized only to facilitate describing the preferred embodiment.
DETAILED DESCRIPTION
As shown in FIG. 1, the present fluid feed mechanism or rotatable timed mechanism for feeding fluid to a combustion cylinder is generally indicated by the reference numeral 10. The mechanism 10 includes a disk or rotatable structure 12 with a cavity 14, and a rotational power transmitting and timing adjustment shaft 16 engaged centrally with the disk 12. As shown in FIGS. 5 and 6, the mechanism 10 is preferably mounted in an internal combustion engine 18 having a piston 20, piston rings 22, a connecting rod 24, a crankshaft 26, a flywheel 28, a camshaft drive 30, a timing belt 32 engaging the crankshaft 26 and camshaft drive 30, a camshaft 34 with cams 36, a spark plug or ignition means or combustion means 38, and valve assemblies 40 with a poppet valve 42 and a valve spring 44. A mechanical train 46 includes the piston 20, connecting rod 24, crankshaft 26, timing belt 32, camshaft drive 30, and camshaft 34. As shown in FIG. 6, the internal combustion engine 18 further includes an engine head 47, an engine block 48, an intake fluid line 50 formed in the head 47, an exhaust line 52 formed in the head 47, fluid lines 53 and 54 formed in the block 48, rocker ends 55, a compression ring 56 on the piston 20, an oil scrapper ring 58 on the piston 20, and a combustion cylinder or combustion chamber 60 formed in the block 48 by a cylinder sidewall 62.
As shown in FIGS. 1-4, and 6, the disk 12 includes a pair of generally flat, parallel, axially spaced apart, upper and lower end surfaces or end walls 64 and 66, and a cylindrical side surface or sidewall 68. The disk 12 further includes a central opening 70 having angled splined grooves 72. The disk 12 is seated in a disk seat 74 formed in the engine head 47. The disk seat 74 includes a cylindrical seat side surface or sidewall 76 and a generally flat upper end surface or end wall 78 which is circular or disk like in shape. The end wall 78 may include oil grooves formed therein and extending radially relative to the shaft 16 and communicating with the upper surface 64 of the disk 12 for lubricating such. These oil grooves are spaced from the cylinder 60 at a distance greater than the breadth of the cavity 14. The disk 12 acts as an oil seal between these oil grooves and the combustion chamber. The disk seat 74 further includes a lower end surface or end wall 82. The lower end wall 82 of the disk seat 74 is circular or disk like in shape except for a cutout section having an edge 86 formed in the shape of an arc for being tailored to the cylindrical sidewall 62 of the combustion cylinder 60. The lower end wall 82 may include oil grooves formed therein and extending radially relative to the shaft 16 and communicating with the lower surface 66 of the disk 12 for lubricating such. The end walls 78 and 82 include openings 88 for permitting portions of the shaft 16 to extend therethrough. The lower end wall 82 further includes openings for the fluid lines 53 and 54. The disk seat 74 may be formed of a material harder than the engine head 47. The sidewall 76 of the disk seat 74 overlaps or intersects the combustion cylinder sidewall 62 as shown in FIGS. 2-4 and 6 such that the cavity 14 communicates with the combustion cylinder 60.
The disk seat 74 may be mounted on a hardened plate 83. The plate 83 may have generally the shape of a disk with the exception of a cut-out section where the plate 83 otherwise would overlap with the cylinder 60. The plate 83 does includes an integral lip 84 which partially overlaps with the cylinder 60 and extends to and partially over the piston 20. The lip 84 includes a beveled edge 85. The lip 84 extends over the cavity entrance zone into the cylinder 60 to reduce heat build-up and pressure on the rings 56 and 58 and cylinder wall 62 at the point of combustion which is preferably in the cavity 14. It should be noted that the lip 84 may extend along the entire edge 86 of the cut-out section of the disk seat 74. Edge 86 runs preferably in line with the cylinder wall 62. At one point during the rotation of the disk 12, as shown in FIG. 3 the leading edge 92 of the leading wall 90 of the cavity 14 is substantially equidistant from the beveled edge 85 which is also equidistant from the upper edge of the cylinder wall 60 to permit the fluid in the cavity 14 to quickly mix with fluid in the cylinder 60. The disk seat 74 and the plate 83 and its lip 84 may be considered as part of the combustion chamber since such is fixed relative to the disk 12. Further, the plate 83 may be considered to be part of the disk seat 74.
The cavity 14 extends inwardly and upwardly from the lower surface 66 of the disk 12. The cavity 14 includes a leading curved upright sidewall 90 having a lower curved leading edge 92 which may be tailored to be equidistant or substantially equidistant from the combustion cylinder sidewall 62 at one point during rotation of the disk 12, as shown in FIG. 3, to maximize the flow of fluid between the cavity 14 and the cylinder 60. At such a point, the arc of the edge 92 has an axis in common with the central longitudinal axis of the cylinder 60. The cavity 14 is further formed by an upright curved sidewall 94. The distance between each of the points on the lower edge of the sidewall 94 and the opening 70 is greater than the closest distance between the combustion cylinder sidewall 62 or disk seat edge 86 and the axis of the opening 70 to permit each portion of the cavity 14 to directly communicate with the combustion cylinder 60. The cavity 14 is further formed by an upright curved trailing end wall 96 with a lower edge tailored to be equidistant from the combustion cylinder sidewall 62 or disk seat edge 86 at one point during rotation of the disk 12 to maximize the size of the cavity 14 relative to the distance between the cylinder sidewall 62 or disk seat edge 86 and the outlet of the fluid line 54, the distance between the outlet of fluid line 54 and the outlet of fluid line 53, and the distance between the outlet of fluid line 53 and the cylindrical sidewall 62. Such distances are greater than the distances between corresponding points on the lower edges of leading wall 90 and trailing wall 96 such that fluid does not flow directly among the outlets and cylinder 60 but rather is conveyed among the outlets and the cylinder 60 by the cavity 14 of the disk 12. The cavity 14 is further formed by an upright outer curved sidewall 98 and a hemi-spherical ceiling 100. The hemi-spherical ceiling 100, as opposed to a flat ceiling, lends greater strength to the top of the disk and permits a cavity 14 of greater volume to be formed in the disk 12 and further permits a smoother flow and better mixing of combustible fluid.
The disk 12 further includes a pair of counter-balance weights 101 fixed or molded in the disk 12 near the walls 90, 96. The weights 101 compensate for cavity 14.
The power transmitting shaft 16 includes an angled splined arrangement portion 102 having angled splined gears 104 for engaging the grooves 72 such that axial movement of the shaft 16 rotates the disk 12 relative to the shaft portion 102. The shaft portion 72 includes axially extending oil grooves 105 milled into the shaft portion 102. The grooves 105 extend through the gears 104. The oil grooves 105 may further be milled on the shaft portion 110 and radially into the thrust bearing 136. Axial movement of the shaft portion 102 in one direction advances the location of the cavity 14 relative to the stroke of the piston 20 and in the other direction retards the location of the cavity 14 relative to the stroke of the piston 20. The engine block 48 includes a bore 106 for receiving an end 108 of the shaft portion 102 for permitting axial movement of the shaft portion 102. The bore 106 also extends through the upper and lower walls 78 and 82 of the disk seat 74 and through the engine head 47.
The shaft 16 further includes a power transmitting portion 110 preferably rigidly affixed or integral with the angled splined arrangement shaft portion 102. Preferably the power transmitting portion includes a plurality of axially and radially extending gear teeth 112 for engaging a gear 114 of a reduction gear box 116. The gear 114 is connected through a mechanical train such as a gear train in the gear box 116 to a gear 118 rigidly affixed to the cam 34. The gear box 116 through its arrangement of gears or mechanical train may vary the relative rates of rotation of the camshaft 34 and the toothed portion 110 of the shaft 16 to increase or decrease the rate of rotation of the toothed portion 110 relative to the camshaft 34. Gear 114 includes axially extending gear teeth running parallel to the elongate teeth 112 of shaft portion 110 such that the shaft portion 110 may move axially or slidingly along the gear 114 while still permitting the gear 114 to drive the toothed shaft portion 110. It can be appreciated that the gear box 116 forms part of the mechanical train 46. The housing of the gear box 116 may be rigidly affixed such as to the engine head 47.
The shaft 16 further includes a portion 120 for receiving the transmission of axial movement and for transmitting the axial movement to the shaft 16. Axial movement to shaft portion 120 is accomplished by a rotating gear 122 keyed to a hub 124 fixed, for example, relative to the engine head 47. The gear 122 may be hand driven or rotated by handle 126 fixed to the gear 122 radially relative to the hub 124, or the gear 122 may be driven by an electric motor driving the hub 124. The gear 122 includes straight axially and radially extending gear teeth 128 which engage a toothed rack 130 rigidly fixed on the shaft portion 120. The toothed rack 130 includes teeth 132 extending in a plurality of planes at right angles to the shaft portion 120. Rotation of the gear 122 drives the shaft portion 120 in the desired axial direction. Shaft portion 120 may slide axially and be supported relative to the engine 18 via a bushing 134 slidingly engaging the upper end of the shaft portion 120. The bushing 134 may be fixed, for example, relative to the engine head 47. The bushing 134 includes a slot 135 to permit reception of the toothed rack 130.
A thrust bearing 136 between the shaft portions 110 and 120 permits the transmission of axial movement to the shaft portion 110 while permitting rotational movement of the shaft portion 110. Or, in other words, the bearing 136 permits axial movement between the shaft portions 110, 120 without transmitting relative rotational movement therebetween. The bearing 136 is seen diagrammatically in FIG. 1 as having an upper race 138 rigidly affixed to the shaft portion 120 and a lower race 140 rigidly affixed to the shaft portion 110. As seen in FIG. 6, the shaft portion 120 includes an annular locking collar 142 and the shaft portion 110 includes an integral disk shaped head 144 rotatable in the collar 142. The lower end of the shaft portion 120 includes an annular clamp 146 for supporting the shaft portion 120 relative to the collar 142. If desired, the shaft portion 120 and locking collar 142 may be formed of two integral pieces later welded together or held together by clamp 146 along a seam line 147 for ready connection of head 144.
The fluid inlet line 53 includes adjacent its outlet a one way check valve 148. Valve 148 permits the fluid to be accurately pressurized in the cavity 14 and maintains the pressure in the cavity 14 when the cavity 14 is in communication with the fluid line 53. Along with the trailing wall 96, the valve 148 is also a barrier against fluid in line 53 igniting. Fluid introduced through line 53 preferably is hydrogen, propane, or butane. Hydrogen is most preferred.
The fluid line 54 includes two fluid line portions 150 and 152 separated by a divider or strip 154 running the length of the line 54. One of the line portions communicates with an inlet 156 formed in the disk seat floor 82 and the other line portion communicates with an outlet 158 formed in the disk seat floor. Air or other fluid such as an inert gas or even the combustible fluid which normally is pumped to the cavity 14 through line 53 may be forced through inlet 156 to in turn evacuate the cavity 14 or force or purge fluid, such as exhaust fluid, therefrom.
Now that the construction of the fluid feed mechanism according to the teachings of the preferred embodiment of the present invention has been set forth, subtle features and advantages of the preferred construction of the present invention can be appreciated. It can be appreciated that in operation, as the piston 20 moves through its intake, compression, power, and exhaust strokes, rotational movement is transmitted to the shaft 16 from the piston 20 by the mechanical train 46. The shaft 16 then drives the disk 12 to rotate. The engagement between the angled splined shaft portion 102 and the grooves 72 is sufficiently tight and precise to permit the shaft portion 102 to transmit rotation to the disk 12 without relative rotational slippage, yet the engagement permits axial movement of the shaft portion 102 relative to the disk 12 for timing purposes. As the disk 12 rotates, the cavity 14 rotates in one direction from the fluid inlet 53 to the cylinder 60 to the purging inlet and outlet 156 and 158 and back to the fluid inlet 53.
It can be appreciated that, as the cavity 14 passes over inlet 53, the cavity 14 is filled under pressure. Fluid may continually be fed to and through the valve or valve chamber 148. The fit between the disk 12 and the disk seat floor 82 is sufficiently precise to minimize fluid leakage therebetween. As the fluid filled cavity 14 is rotated to the cylinder 60, it may flow under pressure from the cavity 14 almost immediately as leading edge 92 passes over disk seat edge 86 adjacent to the cylinder sidewall 62. Or, more preferably, if the pressure of fluid such as air in the cylinder 60 is greater than pressure in the cavity 14, such fluid flows into the cavity 14 almost immediately as the leading edge 92 passes adjacent to the disk seat edge 86. The fluid thus mixes with other fluid such as the air which has been introduced through inlet 44, whereupon the fluid mixture in the cylinder 60 and cavity 14 is ignited by combustion means such as the spark plug 38 seen in FIG. 5 or, preferably, by compression ignition in diesel engines such as represented in FIG. 6. At combustion, combustion gases flow from the cavity 14, over the lip 85 toward the center of the cylinder 60. At the time of combustion, it is preferred that the leading edge 92 be located only a small distance, such as from 1° to 10° past the cylinder sidewall 62 or disk seat edge 86. However, if desired, combustion may occur after the cavity 14 is more completely in communication with the cylinder 60. As the disk 12 continues to rotate, the leading edge 92 of cavity 14 passes over the fluid inlet 156 and outlet 158 at the same time. Any exhaust gases in the cavity 14 are thereby forced therefrom. The cavity 14 is then rotated by the disk 12 back to the fluid inlet 53.
It can further be appreciated that the disk 12 may be timed relative to the stroke of the piston 20 or the time of ignition in the cylinder by operation of gear 122. Rotation of gear 122 imparts a linear motion to shaft portion 120 which in turn imparts a linear motion to shaft portion 110 which slides past gear 114 while still permitting the gear 114 to transmit rotational movement to the shaft portion 110. In turn, shaft portion 110 imparts a linear movement to shaft portion 102 to move the angled splined gears 104 linearly relative to the disk 12 to rotate the disk 12 relative to the shaft portion 102. Accordingly, the cavity 14 is advanced or retarded relative to the piston stroke for timing the ignition.
It can further be appreciated that the fluid introduced through line 53 is preferably in gaseous form.
It can still further be appreciated that combustible fluids such as hydrogen, propane, and butane are preferred. However, it can be appreciated that the fluid itself may not be combustible but may instead be an additive to facilitate the combustion of fluids in the cylinder 50 or function of the engine.
It can be further appreciated that the rack 130 may be of sufficient length to permit the cavity 14 to be advanced at least 90° and retarded at least 90°. More preferably, the rack 130 is shorter to be more compact but still of sufficient length to permit the cavity 14 to be advanced at least 45° and retarded at least 45°.
It can be further appreciated that the cavity advantageously includes only one opening to and from the cavity. The fluid enters and exits the cavity or pocket only through one opening. Such minimizes the surface area in contact with fluid, exhaust gases or combustion products and minimizes the force of expansion of combustion gases being directed through and around the disk.
It can be appreciated that FIG. 7 shows an alternate embodiment of the invention to permit rotation and linear movement of the timing adjustment shaft. In such an arrangement, the timing adjustment shaft 160 is splined so as to include axially extending splines 162. A disk shaped gear 164 having corresponding splines mates with the shaft 160 such that the shaft 160 is movable axially and such that the gear 164 transmits rotational movement to the timing adjustment shaft 160. The gear 164 is mounted in a housing or gear box 166 having bearings 168 engaged with both faces of the gear 164 to support the gear 164. The gear 164 is driven by a worm 170 fixed to and rotating with the camshaft 34. Annular races 171 may be fixed in the box 166.
It can be appreciated that FIG. 8 shows an alternate embodiment for moving the timing adjustment shaft 16 in the axial direction. Such an arrangement includes a hand or electrically driven gear or pulley 172 having a chain or line 174 engaged with the timing adjustment shaft portion 176 to urge the shaft portion 176 in one direction. A coil spring 178 urges the shaft portion in the other direction. The coil spring 178 is mounted on the shaft portion 176 between an annular stop 180 fixed to the shaft portion 176 and a bushing 182 fixed relative to the engine 18 such as to the engine head 47.
It can further be appreciated that the rotating injector structure, preferably in the shape of a disk, may be formed in other shapes. For example, such a rotating injector structure may take the form of a sphere, or half-sphere, or may be frustoconical in shape. It is preferred that the rotating injector structure include a generally flat face or portion, from which the fluid cavity extends inwardly into the structure, for permitting fluid communication at the upper or outer generally flat end of the combustion cylinder, and another face or portion for permitting rotation in the engine head or block.
It can further be appreciated that the rotating structure 12 may be mounted in the engine head or block. It can further be appreciated that fluid lines may be introduced to the rotating structure 12 through the engine head or block.
It can further be appreciated that the pressure in the combustion cylinder 60 is preferably higher than the pressure in the fluid filled cavity 14. In such a case, the cavity 14 acts as a stratified charge chamber, with the compressed fluid in the combustion cylinder 60 flowing into the cavity 14 and mixing with the fluid in the cavity 14 for combustion.
Advantageously, the disk 12 may be timed so as to correspond to the degree of mixing desired. In the case of gaseous fluid, such mixing is almost instantaneous. Still further, the disk 12 may be timed according to the kinds of fluids exposed to the cylinder 60 by the cavity 14 and the intake 50.
It can further be appreciated that the timing adjustment shaft 16 may be driven by means other than an overhead camshaft. For example, chains may be connected from the camshaft mounted in a lower portion of the engine, in which case push rods are utilized to open and close the valves. Still further, chains may be connected to the shaft 16 from the crankshaft. In any case, it is preferred that a mechanical train running from the piston 20 drives the shaft 16.
It can further be appreciated that more than one disk may be provided for each cylinder, that the size and width of the disk is variable, that the disk may rotate faster for a two stroke engine, and that more than one fluid cavity 14 may be formed in the disk.
It can be appreciated that the present invention includes a method for exposing a fluid to the combustion chamber of an internal combustion engine, with the method including the steps of providing a structure with a cavity formed therein, with the structure being mounted on the engine, and with the cavity communicable with the fluid outlet and the combustion chamber; then introducing fluid from the fluid outlet to the cavity; then rotating the structure such that the cavity rotates from the fluid outlet to the combustion chamber; then permitting the fluid in the cavity to mix with other fluid in the combustion chamber and permitting such other fluid to have entered the combustion chamber from the intake valve; and then combusting the mixed fluid in the combustion chamber or cavity and rotating the structure such that the cavity rotates from the combustion chamber to the fluid outlet. The steps of rotating the structure may include the step of rotating the structure in one direction. The step of rotating the structure in one direction may further include the step of retarding the location of the cavity relative to the piston stroke or the step of advancing the location of the cavity relative to the piston stroke. The method may further include the step of purging the cavity during the step of rotating the structure such that the cavity rotates from the combustion chamber to the fluid outlet, with the step of evacuating the cavity occurring after the cavity has communicated with the combustion chamber and prior to the cavity communicating with the fluid outlet.
It can be appreciated that the reference character A generally designates means for moving the timing adjustment shaft in the axial direction. The reference character B generally designates means for transmitting axial movement without transmitting rotational movement. This means B includes a seal for containing oil within the thrust bearing 136, the shaft portion 110, and disk 12, which otherwise may work its way into means A. The seal also prevents exterior dirt from contaminating the oil of the thrust bearing 136, shaft portion 110, and disk 12. The reference character C generally designates means for rotating the timing adjustment shaft and the injector disk while permitting axial movement of the timing adjustment shaft.
It may further be appreciated that the disk 12 may be counter-balanced by forming another cavity diametrically opposite of cavity 14. Such a cavity may then be sealed relative to the upper and lower surfaces 64 and 66.
It can further be appreciated that the disk 12 may be related via a computer to the stroke of the piston. In such a case, one sensor is preferably placed in or on the peripheral region of the disk 12 and the other sensor in the peripheral region of the disk seat or such adjacent region of the head. Preferably, the sensor in or on the disk travels through the combustion chamber during the exhaust or intake strokes to minimize heat and pressure forces on the sensor in the disk. If desired, sensors may be placed in other areas, such as in the shaft or in the block. The sensors communicate with the computer and with each other such as by magnetic pulses. However, it should be noted that a mechanical train is preferred.
It can further be appreciated that the cavity 14 may be coated or lined. Such a coating may include a reactive coating such as a catalyst to enhance combustion and increase the number of combustible fluids suitable for use, or include a protective coating such as a metal or chemical coating to minimize thermal stress from combustion on the disk or especially on the portion of the disk forming the cavity. For example, in the case of the combustible fluid being hydrogen, the preferred coating is a durable material which withstands extreme thermal stresses.
It can be further appreciated that the angled splined shaft gear arrangement may be modified to be the equivalent of an Egbert type arrangement. An Egbert type arrangement according to the present invention is an oval spiraled shaft, replacing shaft portion 102, traversing in an oval spiraled aperture, replacing opening 70, formed in the center of the disk 12.
Thus since the invention disclosed herein may be embodied in other specific forms without departing from the spirit or general characteristics thereof, some of which forms have been indicated, the embodiments described herein are to be considered in all respects illustrative and not restrictive. The scope of the invention is to be indicated by the appended claims, rather than by the foregoing description, and all changes which come within the meaning and range of equivalents of the claims are intended to be embraced therein.
|
A timeable fluid feed mechanism for feeding or injecting combustible vapors into an internal combustion engine, primarily compression ignition. The mechanism includes a rotating disk with a cavity that passes repeatedly and consecutively over a fuel inlet pipe, cylinder, piston crown, vent pipes, and then again over the fuel inlet pipe. Combustion occurs when fluid in the cavity is exposed to the cylinder and mixes with the other fluid in the cylinder. Timing is accomplished by the axially located driving shaft with angled splined gears meshing with angled splined gears in the disk. Axial movement of the shaft causes the disk and its fluid feed cavity to change position relative to the shaft, thereby changing timing. The features of a nonrotating axial motion input to the injector disk drive shaft, ease of operation, and a curved leading edge of the injector cavity improve combustion. Power input to the rotatable disk shaft is over a suitable length of the shaft to avoid moving the power input gears axially.
| 5
|
FIELD OF THE INVENTION
The present invention relates to improving a fluid drive or steam assisted gravity drainage (“SAGD”) process for recovering oil from a subterranean, oil-containing, water-wet sand reservoir. More particularly the invention relates to altering the nature of the sand in the near bore region of the production well to an oil-wet condition, to thereby obtain enhanced oil recovery.
BACKGROUND OF THE INVENTION
In a SAGD process, steam is injected into a reservoir through a horizontal injection well to develop a vertically enlarging steam chamber. Heated oil and water are produced from the chamber through a horizontal production well which extends in closely spaced and parallel relation to the injection well. The wells are positioned with the injection well directly over the production well or they may be side by side.
SAGD was originally field tested with respect to recovering bitumen from the Athabasca oil sands in the Fort McMurray region of Alberta. This test was conducted at the Underground Test Facility (“UTF”) of the present assignee. The process, as practiced, involved:
completing a pair of horizontal wells in vertically spaced apart, parallel, co-extensive relationship near the bottom of the reservoir;
starting up by circulating steam through both wells at the same time to create hot elements which functioned to slowly heat the span of formation between the wells by heat conductance, until the viscous bitumen in the span was heated and mobilized and could be displaced by steam injection to the production well, thereby establishing fluid communication from the developing chamber down to the production well; and
then injecting steam through the upper well and producing heated bitumen and condensate water through the lower well. The steam rose in the developing bitumen-depleted steam chamber, heated cold bitumen at the peripheral surface of the chamber and condensed, with the result that heated bitumen and condensate water drained, moved through the interwell span and were produced through the production well.
This process, as practised at the UTF, is described in greater detail in Canadian patent 2,096,999.
Successful recovery of bitumen during the SAGD process depends upon the efficient drainage of the mobilized bitumen from the produced zone to the production well.
One object of the present invention is to achieve improved drainage, as evidenced by increased oil recovery.
SUMMARY OF THE INVENTION
The present invention had its beginnings in a research program investigating the effect of wetting characteristics of oil reservoir sand on oil recovery. Athabasca oil sand from the Fort McMurray region is water-wet in its natural state. The following experiments were performed using water-wet sand saturated with oil to mimic the naturally occurring oil sand.
Three pressure driven flood experimental runs from the program were of interest. In each of these runs, oil-saturated, water-wet sand was packed into a horizontal, cylindrical column and several pore volumes of brine were injected under pressure through one end of the column (the “injection end”). Oil and brine were produced at the opposite end of the column (the “production end”). The oil and brine were separated and the amount of oil quantified. In the first run, the column was packed entirely with oil-saturated water-wet sand and the brine was pumped continuously. In the second run, a thin, oil-wet membrane was added to the production end of a column that had been packed with water-wet sand and oil-saturated as in run 1 . Again, the injection of the brine was continuous. There was no appreciable difference in oil recovery between runs 1 and 2 . In the third run, the column was packed as in run 2 and a thin, oil-wet membrane added to the production end. However, in this run the injection of brine was intermittent. There were significant pauses or shut-downs (having a length anywhere from several hours to several days) in pumping of the brine. The oil recovery from the third run was significantly greater than had been the case for runs 1 and 2 .
From these experiments and additional work, it was concluded and hypothesized:
that provision of an oil-wet oil membrane at the production end of a column of oil-saturated, water-wet sand was beneficial to recovery;
that the pumping shut-downs or cyclic injection provided quiescent periods during which we postulated that oil was drawn by capillary effects or imbibed into the oil-wet membrane with corresponding displacement of resident water; and
that this combination of features enabled oil to flow more easily through the production end, leading to improved oil production rate and recovery.
From this beginning it was further postulated that adding oil-wet sand to surround the production well and then practising the SAGD process might provide an opportunity for imbibing to materialize (the SAGD process typically does not involve large pressure differentials and might therefore provide a quiescent condition similar to that occurring during the cyclic injection used in the third pressure driven flood run).
At this point, a bench scale cell was used in a laboratory circuit, to simulate an SAGD process. More specifically, an upper horizontal steam injection well was mounted to extend into the cell, together with a lower horizontal oil/water production well. Two runs of interest were conducted. In the first run, the cell was packed entirely with oil-saturated, water-wet sand. Steam was injected through the upper well and oil and condensed water were produced through the production well. In the second run, oil-wet sand was provided to form a lower layer in the cell and the production well was located in this layer; oil-saturated, water-wet oil sand formed the upper layer and contained the injection well. As in the first run, steam was injected through the upper well and oil and condensed water were produced through the production well. In the first run, about 27% of the oil in place was recovered after 200 minutes of steam injection. In the second run, about 40% of the oil was recovered over the same period. The oil production rate in the second run was also higher than that for the first run.
In summary then, the invention has two broad aspects.
In one aspect, the invention provides an improvement to a conventional pressure driven fluid flood or drive process conducted in an oil-containing reservoir formed of water-wet sand using injection and production wells. The improvement comprises: providing a body of oil-wet sand in the near-bore region of the production well and injecting the drive fluid intermittently.
In another aspect, the invention provides an improvement to a conventional steam-assisted gravity drainage process conducted in an oil-containing reservoir formed of water-wet sand using injection and production wells. The improvement comprises: providing a body of oil-wet sand in the near-bore region of the production well and then applying the SAGD process.
The body of oil-wet sand may be emplaced in the near-bore region by any conventional method such as: completing the well with a gravel pack-type liner carrying the sand; or circulating the sand down the well to position it in the annular space between the wellbore surface and the production string.
The “near well-bore region” is intended to mean any portion of that region extending radially outward from the center line of the production string to a depth of about 3 feet into the reservoir and extending longitudinally along that portion of the production well in the reservoir.
By way of explanation, we believe that placement of oil-wet sand in the near well-bore region serves to maintain a continuous oil flow. This, when combined with a low pressure differential regime, causes oil to imbibe into the region and has the effect of easing oil flow into the well, which leads to enhanced recovery.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified schematic vertical cross-section of a well configuration for practicing the invention in the field;
FIG. 2 is a schematic end view in section of the well configuration of FIG. 1;
FIG. 3 is a schematic of the laboratory column circuit used to carry out the pressure drive runs;
FIG. 4 is a schematic of the laboratory visualization cell circuit used to carry out the SAGD runs;
FIG. 5 is an expanded view of the cell of FIG. 4 showing the sand packing for the 2 nd SAGD run;
FIG. 6 is a plot of oil displacement versus pore volume injected showing the effect of cyclic imbibition on oil recovery;
FIG. 7 is a plot of the percent oil recovery versus time;
FIG. 8 is a bar graph showing the percent recovery of oil after 200 minutes; and
FIG. 9 is a plot of the cumulative oil production versus time in days.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention is concerned with modifying a conventional SAGD system. Having reference to FIGS. 1 and 2, an SAGD system comprises steam injection and oil/water production wells 1 , 2 . The wells have horizontal sections 1 a, 2 a completed in an oil sand reservoir 3 so that the injection well section 1 a overlies the production well section 2 a. The reservoir 3 is formed of water-wet sand or other solids. The injection well 1 is equipped with a tubular steam injection string 4 having a slotted liner 5 positioned in the horizontal section 1 a. The production well 2 is equipped with a tubular production string 6 having a slotted liner 7 positioned in the horizontal section 2 a. Fluid communication is established between the wells 1 , 2 , for example by circulating steam through each of the wells to heat the span 8 by conduction, so that the oil in the span is mobilized and drains into the production well. Steam injection is then commenced at the injection well. The steam rises and heats oil which drains, along with condensed water, down to the production well and is produced. An expanding steam chest 9 is gradually developed as injection proceeds.
In accordance with the invention, a layer 10 of oil-wet sand is emplaced along at least part of the horizontal section 2 a of the production well. This may be accomplished by circulating the sand into place or packing it at ground surface into a gravel-pack type liner before running it into the well as part of the production string. Alternatively, one could treat the sand in-place with a suitable solution to render the sand oil-wet. For example, one could apply an acid wash to the formation in the near well-bore region.
The experimental work underlying the invention is now described.
Water-wet sand was used in the following experiments unless otherwise stated. The water-wet sand was packed in either a column or a test cell and saturated with oil. About eighty-five percent (85%) of the pore volume of the packed sand was oil saturated.
EXAMPLE I
This example describes the treatment used to convert water-wet sand to an oil-wet condition. This treatment involved coating the sand with asphaltene to render it oil-wet.
It further describes a test used to assess the wetted nature of the treated sand.
More particularly, water-wet sand was first dried by heating it at 500° C. for several hours. Asphaltenes were extracted from Athabasca bitumen and diluted in toluene to give a 10 weight % asphaltene/toluene solution. The asphaltene/toluene solution was added to the dry sand in an amount sufficient to totally coat the sand particles with asphaltene without having the sand particles sticking together. Typically the amount of the asphaltenes added per volume of sand was about 0.1%. The asphaltene/toluene/sand mixture was put in a rotary evaporator to evaporate the toluene. As the toluene evaporated, the asphaltene stuck to the sand particles in a thin film. The treated sand was then heated in an oven at 150° C. for several hours.
Wetting tests were conducted on the treated sand to determine whether it was oil-wet. More particularly, treated sand saturated with oil was placed in a glass tube and water was poured into the tube. Observation that no oil was displaced from the sand by the water was accepted as an indication that the grains were oil-wet. In the case of non-treated water-wet sand, the oil was easily displaced by water and flowed to the top by gravity. This was accepted as an indication that the sand grains were water-wet.
The effect of steam on the oil-wet properties on the treated sand was also tested. It was observed that when the treated sand was subjected to steam at 115° C. for 20 hours, it maintained its oil-wet properties in accordance with the test described above.
EXAMPLE II
This example describes 3 runs that showed that the provision of an oil-wet membrane at the production end of a column would increase oil recovery when coupled with intermittent flooding with brine.
More particularly, a laboratory circuit shown in FIG. 3 was used. The entire volume of a 30 cm×10 cm diameter column was packed with water-wet sand and then saturated with oil so that about 85% of the pore volume was oil. The column was run in the horizontal position.
In run 1 , brine was pumped through one end of the column (the “injection end”) at a constant rate of 25 cc/hr until it had been washed with 6 pore volumes of brine. Fractions of eluate were collected from the opposite end of the column (the “production end”). The oil and brine were separated and the amount of oil in each fraction quantified.
In runs 2 and 3 , the column was packed with water-wet sand and saturated with oil as in run 1 . However, an oil-wet membrane (a 5 mm metallic porous membrane that had been treated with organosaline) was placed at the production end in both runs.
In run 2 , the column was washed at a constant rate of 25 cc/hr with three pore volumes of brine, fractions of eluate collected and the oil content in each fraction quantified.
In run 3 , the column was washed intermittently with brine. Brine was pumped through the column at a rate of 25 cc/hr. However, after one pore volume of brine had been pumped, the pump was shut off and the column allowed to “rest” for several hours. Pumping of brine was resumed at a rate of 25 cc/hr for a short period of time and then pumping was stopped again. The pumping of brine was resumed after several hours. The pumping was stopped and restarted at least 15 times in total until 3 pore volumes of brine had been added to the column. The stop periods would vary anywhere from several hours to several days. Throughout the stop-start procedure, fractions of eluate were collected and oil content measured.
FIG. 6 is a plot of oil displacement versus pore volume injected for each of runs 1 , 2 and 3 . After injection of 2.7 pore volumes of brine, run 1 displaced 47.5% of the oil, run 2 displaced 49.2% of the oil and run 3 displaced 62.5% of the oil. The results indicate that the addition of the oil-wet membrane in run 2 did not markedly affect oil recovery. However, when the oil-wet membrane was coupled with intermittent washes as in run 3 , oil recovery increased by about 50% relative to run 1 .
EXAMPLE III
This example describes 2 SAGD runs conducted in a test cell. The runs show that provision of oil-wet oil sand in the near-bore region of the production well, when coupled with SAGD, increases recovery when compared to the case where only water-wet oil sand is used.
More particularly, a 0.6 m×0.21 m×0.03 m thickness scaled visualization cell 1 was used. The sides of the cell were transparent. An upper injection well 2 and a lower production well 3 were provided. The wells were horizontal and spaced one above the other in parallel relationship. Both wells were constructed from 0.64 cm diameter stainless steel tube that was slotted with 0.11 cm wide by 5.1 cm long slots. A schematic illustration of the experimental set-up is shown in FIG. 4 . Steam flow rate was measured using an orifice meter 4 . A control valve 5 was used to deliver steam to the injection well at about 20 kPa (≈3 psig). An in-line ARI resistance heater 6 and a heat trace were used to maintain a maximum of 10° C. superheating at the point of injection. To achieve “enthalpy control” (steam trap) control over the production of fluids, a valve 7 was thermostatically controlled to throttle the production well and ensure that only oil and condensate were produced.
In the baseline first run, the cell was entirely filled with oil-saturated, water-wet sand. In the second run, as shown in FIG. 5, the bottom section 8 of the cell was packed with a layer of oil-wet sand treated in accordance with Example I and the upper section 9 was packed with non-treated oil-saturated, water-wet sand. In the second run, the steam injection well 2 was located in the upper water-wet section 9 and the production well 3 was located in the lower oil-wet section 8 .
The initialization of gravity drainage was achieved by injecting steam for 30 minutes into both wells at once for about 30 minutes while producing from both wells at the same time. Following the initialization period, steam was injected into the top well only and production fluids were obtained from the bottom well. The experiment lasted for a total of 700 minutes. The production fluids were collected every 15 minutes, the oil and water separated, and the amount of oil recovered measured.
Both runs were done in duplicate and FIG. 7 is a plot of the percent oil recovery versus time in minutes for all four runs. It can be clearly seen from this plot that the addition of oil-wet sand around the production well increased both the rate of oil recovery and the percent of oil recovery. Having reference to FIG. 7, is can be seen that in the runs without the addition of oil-wet sand, it took an average of 425 minutes to achieve 40% oil recovery. However, in the runs where an oil-wet sand layer surrounded the production well, it took less than half the time (175 minutes) to achieve 40% oil recovery. FIG. 8 is a bar graph showing the percent recovery of oil for all runs after 200 minutes. The average recovery of oil for the runs without the oil-wet sand layer was 27.5%. However, the average recovery of oil for the runs with the oil-wet sand layer was 43%. This represents a 64% increase in the percent of oil recovered.
EXAMPLE IV
The improvement in oil production observed during laboratory experiments when an oil-wet region surrounded the production well was further investigated using a numerical simulator to examine if the above phenomenon would prevail on a field scale. A 500 m deep reservoir was assumed in a numerical model, which had a pay-zone thickness of 21 m. Two superimposed horizontal wells, each 500 m long, were placed near the bottom of the pay-zone 4 m apart from one another. A SAGD process was simulated whereby steam was injected into the top well (the “injection well”) at a pressure of 3.1 MPa and oil was collected in the bottom well (the “production well”). In one instance, the reservoir surrounding the production well remained water-wet. In another instance, an oil-wet zone was placed around the production well. This was achieved by using capillary pressure and relative permeability functions for water-wet and oil-wet sands.
The field scale numerical results are shown in FIG. 9, a plot of the cumulative oil production versus time in days. It was clear that oil production rates increased when an oil-wet region was added to the production zone. Further, the results show that the starting of oil production can be advanced when an oil-wet zone is placed around the production well. The effect of the oil-wet region was most significant during the first two years of operation.
EXAMPLE V
Bottom water drive experiments were done in order to test the effectiveness of various anti-coning agents in preventing penetration of the production well by reservoir water. It was observed that when the porous region around the production well was rendered oil-wet, the coning of the water was significantly reduced. The oil recovery in the oil-wet case was higher by as much as 20% over that of the water-wet case.
Bottom-water drive experiments were done using visualization cells as described in Paper 96-13 of the Petroleum Society of the CIM 47 th Annual Technical Meeting, Jun. 10-12, 1996. It was observed that when only water-wet sand was used, coning around the production well occurred due to imbibition and early breakthrough of water. By contrast, when oil-wet sand was packed around the production well, water breakthrough to the producer was delayed and therefore coning was also delayed.
|
A process is disclosed for enhancing oil recovery in oil-containing reservoirs formed of water-wet sand. The process involves placing oil-wet sand in the near-bore region of a production well. The process can be used to provide an improvement to both a conventional pressure driven fluid drive process and a conventional steam-assisted gravity drainage process. In the fluid drive process, the drive fluid is injected intermittently.
| 4
|
This is a divisional of application Ser. No. 07/940,239 filed Sep. 3, 1992 now U.S. Pat. No. 5,530,474.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an image pickup apparatus such as a video camera or an electronic still camera, and more particularly to the white balance control function thereof.
2. Related Background Art
A video camera or the like usually incorporates a white balance correcting device, in order to obtain an appropriate balance of different colors at the image taking operation. FIG. 1 is a block diagram of a prior art video camera including an automatic white balance correcting device, disclosed in a U.S. patent application Ser. No. 070,493 of the present applicant. There are shown an image pickup device 1; a circuit 2 for generating luminance and chromaticity signals; gain control circuits 3, 4 respectively inserted in red (R) and blue (B) signal lines; a color difference signal generating circuit 5; an encoder 6; gate circuits 7, 8; an (R-B) signal detection circuit 9; an averaging circuit 10; a differential amplifier 11; a limiting circuit 12; a tracking correction circuit 13; and a lens 15, wherein the gain control circuits 3, 4 and the circuits 7 to 13 constitute an automatic white balance correction device 14.
The above-explained image pickup apparatus functions in the following manner. Light entering the image pickup device 1 is photoelectrically converted therein, and the obtained signal is supplied to the luminance signal-chromaticity signal generating circuit 2, which generates a high frequency component YH of the luminance signal, a low frequency component YL of the luminance signal, a red signal (R) and a blue (B) signal. Among these signals, the R and B signals are respectively amplified in the gain control circuits 3, 4, according to the characteristics controlled by control signals from the tracking correction circuit 13, to provide color signals R', B' which are supplied, together with a luminance signal YL, to the color difference signal generation circuit 5 for generating color difference signals (R-YL) and (B-YL). Said color difference signals are supplied, together with a luminance signal YH, to the encoder 6 for conversion into a standard television signal. Said color difference signals (R-YL) and (B-YL) are also supplied to the automatic white balance correction device 14. In said device, the color difference signals are respectively supplied to the gate circuits 7, 8 for eliminating an unnecessary signal in the blanking period, an abnormal color difference signal resulting from a signal saturation for a high luminance object etc.
The signals released from said gate circuits 7, 8 are supplied to the (R-B) signal detection circuit 9, which generates an (R-B) signal by calculating the difference of the (R-YL) and (B-YL) signals from the gate circuits 7, 8. The averaging circuit 10 averages the (R-B) signal from the (R-B) signal detection circuit 9, thereby obtaining a DC signal. The differential amplifier 11 compares the output signal level from the averaging circuit 10 with a reference voltage V ref1 , and generates a signal corresponding to the difference, for supply to the limiting circuit 12, which limits the level of the output signal from the amplifier 11 within a range between V 2r and V 3r , respectively corresponding to the upper and lower limits of color temperature, in order that the white balance is controlled within a practical color temperature range (for example 2000° to 10000° K.). Thus the output from the limiting circuit 12 is limited within the range from V 2r and V 3r ,
The output signal of the limiting circuit 12 is supplied to the tracking correction circuit 13, in response, provides the gain control circuits 3, 4 with control signals R cont , B cont for controlling the gains of the gain controlling circuits 3, 4 so as to correct the white balance, namely for reducing the (R-B) signal component of the object to zero.
In the following there will be explained an example of the relation between the signals R cont , B cont and the color temperature, with reference to FIGS. 2 and 3.
In a vector chart shown in FIG. 3, points X1, X2 and X3 respectively correspond to white color at 6000° K, 2000° K and 10000° K. If the control signals R cont , B cont have voltages V 1r , V 1b corresponding to X1 as shown in FIG. 2, said control signal will have voltages V 2r , V 2b for correcting X2 toward the center of the vector chart, and voltages V 3r , V 3b for correcting X3 toward said center.
Since the control signals R cont , B cont are limited to V 3r , V 3b , an image corresponding to a point X4 in FIG. 3 cannot be corrected to the center X1 of the vector chart even under the function of the white balance correcting device.
Since the automatic white balance correction device 14 has a negative feedback loop explained above, color difference signals with a white balance can be supplied to the encoder 6 within a practical color temperature range.
However the above-explained conventional white balance correction device has been associated with a drawback of generating an error in the white balance correction in cases where the distribution of color temperature of the object is not uniform or in cases where the object contains a large proportion of monochromatic area of a high saturation. In the following there is shown a representative example of such a drawback. In the following description, for the purpose of simplicity, the gain of the gain control circuits 3, 4 shown in FIG. 1 is assumed to be unity.
As an example of the above-mentioned drawback, there will be explained a case of taking white balance on an object 1 shown in FIG. 4, composed of white color by 50% and blue color by 50%.
It is assumed that the object 1 is illuminated with light of a high color temperature, for example of 9000° K. In FIG. 6, V 4r , V 4b indicate the values of the control signals R cont , B cont for bringing the white point to the center of the vector chart shown in FIG. 5. When the object 1 is taken with the properly corrected white balance at R cont =V 4r and B cont =V 4b , the white color and the blue color are respectively positioned at W 0 , B 0 in FIG. 5.
If the conventional white balance correction device 14 is activated in this state, the negative feedback loop thereof so functions as to reduce the (R-B) signal component of the object to zero, as explained before. Consequently, on the vector chart shown in FIG. 5, the white and blue points are moved upwards, parallel to the (R-B) axis (namely perpendicularly to a line R-B=0). Thus, when the negative feedback operation becomes stable, and if the limiting circuit 12 is assumed inactive, the white and blue points finally stay at positions W 1 , B 1 satisfying a condition: line segment B 0 B 1 =line segment B 1 A=line segment W 0 W 1 , wherein the line segment B 0 A is parallel to the (R-B) axis, and the point A is on a line R-B=0 which passes through the original point W 0 and is perpendicular to the (R-B) axis. The upward movements of the white and blue points in FIG. 5 correspond to increases in the control signals R cont and B cont and the signals R cont , B cont required to move the white and blue points to W 1 , B 1 are V 7r , V 7b in FIG. 6.
In practice, however, the control signals R cont , B cont are limited respectively to V 3r , V 3b by the function of the limiting circuit 12, so that, after the correction of white balance, the white and blue points do not move to W 1 , B 1 on FIG. 5 but respectively remain at W 2 , B 2 . The aberrations of the white point W 2 and the blue point B 2 respectively from W 0 , B 0 (lengths of line segments W 0 W 0 and B 0 B 2 ) in this state are respectively defined by the differences of the signals R cont , B cont from the ideal values, namely (V 3r -V 4r ) and (V 3b -V 4b ).
In this case, the control singals R cont , B cont which should read V 7r , V 7b as explained above, are limited to V 3r , V 3b by the effective function of the limiting circuit 12, so that the aberrations of the white point W 2 and the blue point B 2 from W 0 , B 0 do not become excessively large.
However the limiting circuit 12 does not function effectively for example in the following two cases, and the correction error of the white balance becomes not negligible in such situations.
(1) Let us consider a situation where the object 1 is illuminated with light of a low color temperature, for example of 2000° K. In such state the values of the control signals R cont , B cont which bring the white point to the center of the vector chart shown in FIG. 5 are V 2r , V 2b as shown in FIG. 6. On the other hand, if said object 1 is taken under the function of the white balance correction device 14, the negative feedback loop thereof functions so as to reduce the (R-B) signal component of the object to zero, as explained before. Consequently, when said negative feedback operation is stabilized, the white and blue points eventually reach, as in the foregoing example, positions W 1 , B 1 satisfying a condition: line segment W 0 W 1 =line segment B 1 A=line segment B 0 B 1 .
In this state, the signals R cont , B cont released from the white balance correction device 14 have values V 5r , V 5b shown in FIG. 6.
Thus, since the control signals R cont , B cont from the white balance correction device 14 are V 5r , V 5b instead of proper V 2r , V 2b , the white and blue points on FIG. 5 are aberrated from W 0 , B 0 by line segments W 0 W 1 and B 0 B 1 corresponding to the differences (V 5r -V 2r ) and (V 5b -V 2b ) in said control signals. In this case, since there is no limit for preventing the control signals R cont , B cont from increasing to V 5r , V 5b , the white and blue points W 1 , B 1 are aberrated from the properly corrected positions W 0 , B 0 more significantly than in the foregoing example, so that the originally white area appears as pale orange while the originally blue area appears as pale blue.
(2) Also an object 2 consisting of a white area by 50% and a yellow area by 50% as shown in FIG. 7 leads to the following drawback.
It is assumed that said object 2 is illuminated with light of a high color temperature, for example of 9000° K. In such state, the values of the control signals R cont , B cont bringing the white point to the center of a vector chart shown in FIG. 8 are V 4r , V 4b shown in FIG. 6. Thus, when the object 2 is taken with the proper white balance correction at R cont =V 4r and B cont =V 4b , the white and yellow points appear at W 0 , Ye 0 shown in FIG. 8.
If the white balance correction device 14 is activated in this state, the negative feedback loop thereof so functions as to reduce the (R-B) signal component of the object to zero, so that the white and yellow points eventually reach positions W 3 and Ye 1 satisfying a condition: line segment W 0 W 3 =line segment Ye 1 B=line segment Ye 0 Ye 1 , when said negative feedback operation is stabilized.
In this state, the control signals R cont , B cont released from the white balance correction device 14 have values V 6r , V 6b shown in FIG. 6.
Thus, since the control signal R cont , B cont from the white balance correction device 14 are V 6r , V 6b instead of proper V 4r , V 4b , the white and yellow points on FIG. 8 are aberrated from W 0 , Y 0 by line segments W 0 W 3 and Ye 0 Ye 1 corresponding to the differences (V 6r -V 4r ) and (V 6b -V 4b ) in said control signals. In this case, since there is not limit for preventing the control signals R cont , B cont from decreasing to V 6r , V 6b , the white and yellow points W 1 , Ye 1 are aberrated from the properly corrected positions W 0 , Ye 0 significantly as in the foregoing case (1), so that the originally white area appears bluish and the originally yellow area appears paler.
FIG. 9 shows the configuration of a image pickup apparatus capable of further reducing the undesirable influence of a single object of high saturation on the white balance control. In FIG. 9, same components as those in FIG. 1 are represented by same numbers.
The image pickup apparatus shown in FIG. 9 is designed to only extract signals suitable for white balance control.
FIG. 10 is a color difference vector representation of the color video signal, for explaining the signals extracted in the apparatus of FIG. 9. If a color video signal obtained by taking a white object at a color temperature of 10000° K with appropriate white balance corresponds to a point P0, a color video signal obtained from the same object taken at a color temperature of 3000° K corresponds to a point P1.
On the other hand, if a color video signal obtained by taking the white object at a color temperature of 3000° K with appropriate white balance corresponds to the point P0, a color video signal obtained from the same object at a color temperature of 10000° K corresponds to a point P2.
Thus, the color of the color video signal varies along a thick line A in FIG. 10 when the white object changes in the color temperature.
When this color difference vector is represented in a two-dimensional coordinate system:
X=(R-Y)-(B-Y)=R-B
y=(R-Y)+(B-Y)=R+B-2Y,
y-coordinate is little affected by the color temperature, and x-coordinate alone varies by the color temperature.
Let us consider, then, to control the white balance in a color temperature range of 3000° to 10000° K as explained above. The variation of a white or almost white object, in response to a change in the color temperature of 3000 to 10000° K, can be anticipated within a range (c≧x≧d) in the x-direction and a range (a≧y≧b) around the thick line A in the y-direction, or a hatched area SI in FIG. 10.
The image pickup apparatus shown in FIG. 9 is designed according to such concept, and the function of said apparatus will be explained in the following.
Light from an object, entering through a lens 21 and an iris (diaphragm) 22 is photoelectrically converted in an image pickup device 1, and a signal obtained by said photoelectric conversion is supplied to a luminance signal/chromaticity signal generating circuit 2, which generates a high frequency component YH and a low frequency component YL of Y signal, an R signal and a B signal. Among these signals, the R and B signals are respectively supplied to gain control circuits 3, 4.
The gain control circuits 3, 4 respectively amplify the R and B signals with gains determined by control signals R cont , B cont supplied from an automatic white balance correction circuit 38, thus releasing gain controlled signals R', B'.
The R' and B' signals are supplied, together with the YL signal, to a color difference signal generating circuit 5, which generates two color difference signals (R-Y) and (B-Y). Said color difference signals are supplied, together with the YH signal, to an encoder 6 for conversion into a standard television signal, which is released from a terminal 23.
The color difference signals (R-Y), (B-Y) are also supplied to said automatic white balance correction circuit 38, which will be explained in the following.
The color difference signals (R-Y), (B-Y) are respectively supplied to clamping circuits 27, 28 for matching the DC level thereof. Thereafter said signals are supplied to a subtraction circuit 29 and an addition circuit 30. The subtraction circuit 29 calculates the difference of the color difference signals (R-Y), (B-Y) from the clamping circuit 27, 28, thereby generating the abovementioned signal x (=R-B). On the other hand, the addition circuit 30 calculates the sum of said signals thereby generating the above-mentioned signal y (=R+B-2Y).
Comparators 31, 32 compare the y signal with reference levels corresponding to a, b in FIG. 10. The comparator 31 releases a low (L) or high (H) level output signal for supply to an OR circuit 33, respectively if a≧y or a≦y. The comparator 32 releases a low or high level output signal respectively if y≧b or y≦b. Consequently the output of the OR circuit 33, controlling a gate circuit 34, assumes a low level state only when the y signal is in a range a≧y≧b, but otherwise assumes a high level state.
On the other hand, the x signal released from the subtraction circuit 29 is intercepted or transmitted by the gate circuit 34 respectively when the output signal of the OR gate 33 is the high or low level state. Thus the output signal from the gate circuit 34 is supplied to a control signal generating circuit 36, after clipping of portions c<x and d>x by a clipping circuit 35.
The control signal generating circuit 36 generates a correction signal z for controlling the gain control circuits 3, 4 in such a manner that the average of the input signal becomes equal to a reference potential, corresponding to a state with white balance.
The correction signal z is supplied to a tracking correction circuit 13, and is corrected therein so as to effect white balance control along the trajectory of the color video signal responding to the change of color temperature, thereby providing the control signals R cont and B cont , which control the gains of the gain control circuits 3, 4.
In the image pickup apparatus of the above-explained configuration, since the signal x from the subtractor 29 is extracted only when the signal y is positioned within a range b≦y≦a, so that the white balance control signal z is not affected by a colored object portion. Also thus extracted signal x is limited within a predetermined range by the clipping circuit, and is prevented from unnecessary gain control. Based on these facts, the white balance correction can be attained without the influence of the colored objects.
However, in the above-explained image pickup apparatus shown in FIG. 9, the colored and colorless objects are clearly distinguished by a predetermined boundary, and, whether the white balance can be attained depends on a slight difference in the saturation or hue. Also the hue of the output color video signal may vary by a slight change of the object.
For example, in case the object is composed of orange and blue colors, the color difference vectors for orange and blue respectively correspond to points Pa and Pb shown in FIG. 11. Since these points are both positioned within the above-mentioned hatched area SI, the white balance becomes stabilized in this state. However, if the orange color difference vector varies to a point Pa' outside said hatched area SI in FIG. 11, the signal from the original object portion is reflected in the white balance correction.
Consequently the white balance correction is conducted solely with the blue object portion, whereby the color difference vector representing the blue object portion is shifted from the point Pb to Pb', and the white balance becomes aberrated. This means that the white balance correcting function is significantly affected by a slight change in the hue, resulting from a variation in the image frame at the phototaking operation, a fluctuation among the cameras or a movement of the object.
The white balance correction is required for responding to the variation in the color temperature, but the range of video signal corresponding to a nearly white object also varies with such variation of the color temperature. Since the image pickup apparatus shown in FIG. 9 only employs the signals within the hatched area SI for white balance correction, the video signal corresponding to a same object may be employed or not for white balance correction, depending on the color temperature.
For this reason, the white balance correction may become different from the desired correction, depending on the color temperature. More specifically, depending on the color temperature, a colored object may have a color difference vector within the hatched area. For example, under illumination of a high color temperature, the light from the object tends to have a color difference vector with an enhanced blue component, whereby the color difference vector of a reddish object often enters the hatched area, and said reddish color is not reproduced but appears in faded state. Similarly, under a low color temperature, the bluish colors appear faded.
SUMMARY OF THE INVENTION
In consideration of the foregoing, an object of the present invention is to provide an image l pickup apparatus with white balance controlling function capable of resolving the above-mentioned drawbacks.
Another object of the present invention is to provide an image pickup apparatus capable of white balance control providing little visual error in white balance correction and matching the object to be taken.
The above-mentioned objects can be attained, according to an embodiment of the present invention, by an image pickup apparatus comprising:
a) image pickup means for forming, from the light coming from an object, a video signal including plural color singals;
b) gain control means for receiving a gain control signal, and controlling the gains of said plural color signals according to said gain control signal; and
c) calculation means for calculating color temperature information relative to the color temperature, based on said plural color signals, and forming said gain control signal according to said color temperature information;
wherein said calculation means includes range setting means for setting the variable range of said gain control signal, at either one of mutually non-overlapping plural ranges.
Still another object of the present invention is to provide an image pickup apparatus capable of stable white balance control, which is not affected by the image frame at the phototaking operation, movement of the object or a slight change in the color temperature and not influenced by the object.
The above-mentioned object can be attained, according an embodiment of the present invention by an image pickup apparatus, comprising:
a) image pickup means for forming, from the light coming from an object, a video signal including plural color signals;
b) gain control means for receiving gain control signals, and controlling the gains of said plural color signals according to said gain control signal; and
c) calculation means for forming said gain control signal according to plural color information relating to said plural color signals;
wherein said calculation means includes weighting means for weighting said plural color information with a coefficient which is determined by the value of said plural color signals and which can assume at least three values, and calculates said gain control signal, according to said plural color information weighted by said weighting means.
Still other objects of the present invention, and the features thereof, will become fully apparent from the following detailed description of the embodiment of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a prior art image pickup apparatus;
FIG. 2 is a chart showing the relation between the color temperature and a gain control signal in the apparatus shown in FIG. 1;
FIG. 3 is a vector chart showing the function of the apparatus shown in FIG. 1;
FIG. 4 is a view showing an example of the object;
FIG. 5 is a vector chart showing the function of the apparatus shown in FIG. 1, in response to the object shown in FIG. 4;
FIG. 6 is a chart showing the detailed relation between the color temperature and a gain control signal in the apparatus shown in FIG. 1;
FIG. 7 is a view showing another example of the object;
FIG. 8 is a vector chart showing the function of the apparatus shown in FIG. 1, in response to the object shown in FIG. 7;
FIG. 9 is a block diagram showing another prior art image pickup apparatus;
FIG. 10 is a color difference vector chart showing a white discrimination area in the image pickup apparatus shown in FIG. 9;
FIG. 11 is a chart showing a drawback in the apparatus shown in FIG. 9;
FIG. 12 is a block diagram of a first embodiment of the image pickup apparatus of the present invention;
FIG. 13 is a flow chart showing the control sequence of a correction signal calculation unit in the apparatus shown in FIG. 12;
FIG. 14 is a chart showing the relation between the color temperature and a gain control signal in a data table provided in a microcomputer of the apparatus shown in FIG. 12;
FIG. 15 is a chart showing the relation between the output of an iris position detector and the luminance in the apparatus shown in FIG. 12;
FIG. 16 is a flow chart showing the control sequence of a correction signal limiting unit in the apparatus shown in FIG. 12;
FIGS. 17 and 18 are vector charts showing a white balance correcting operation in the apparatus shown in FIG. 12;
FIG. 19 is a chart showing the relation between the output of an iris position detector and a luminance coefficient in a second embodiment of the present invention;
FIG. 20 is a view showing a data table representing the function of a correction signal limiting unit in the second embodiment of the present invention;
FIG. 21 is a block diagram of a third embodiment of the image pickup apparatus of the present invention;
FIG. 22 is a block diagram showing an essential part of a fourth embodiment of the image pickup apparatus of the present invention;
FIG. 23 is a chart showing the function of an iris position detector in the image pickup appaaratus shown in FIG. 22;
FIGS. 24, 25 and 26 are charts showing the function of determining the weighting coefficient in the image pickup apparatus shown in FIG. 22;
FIG. 27 is a view showing the effect resulting from the determination of the weighting coefficient in the image pickup apparatus shown in FIG. 22;
FIG. 28 is a chart showing the determination of a determining factor of the white discrimination area in the image pickup apparatus shown in FIG. 22;
FIG. 29 is a chart showing the setting of another determining factor of the white discrimination area in the image pickup apparatus shown in FIG. 22; and
FIGS. 30, 31 and 32 are color difference vector charts showing the change in the white discrimination area in the image pickup apparatus shown in FIG. 22.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Now the present invention will be clarified in detail by preferred embodiments thereof shown in the attached drawings.
1st embodiment
FIG. 12 is a block diagram of an image pickup apparatus including an automatic white balance correction circuit, constituting a first embodiment of the present invention. In FIG. 12, components same as or equivalent to those in the conventional apparatus shown in FIG. 1 or 9 are represented by same symbols, and will be omitted from the following description.
In FIG. 12, there are provided an A/D converter 50 for converting an analog luminance signal YH to a digital signal; an A/D converter 51 for converting an analog (R-YL) signal into a digital signal; an A/D converter 52 for converting an analog (B-YL) signal into a digital signal; an A/D converter 53 for converting an analog output signal of an iris position detector 40, to be explained later, into a digital signal; a correction signal calculation unit 54 for calculating the (R-B) signal component of the object by eliminating unnecessary signals during the blanking period and the abnormal signals in the high luminance areas, based on the data from the A/D converters 50, 51, 52, 53, and calculating a digital value for bringing the (R-B) signal component; a correction signal limiting unit 55 for limiting the output data from the correction signal calculation unit 54, based on the iris position data from the A/D converter 53; a D/A converter 56 for converting the digital signal from the correction signal limiting unit 55 into an analog signal constituting the control signal R cont ; and a D/A converter 57 for converting the digital signal from the correction signal limiting unit 55 into an analog signal constituting the control signal B cont . These components 50-57 are constructed in the microcomputer 60. The iris position detector 40 is composed for example of a Hall element.
In the following there will be explained the function of the correction signal calculation unit 54. Said calculation unit 54 receives data YHD digitized from the signal YH in the A/D converter 50, data RYD digitized from the signal (R-YL) in the A/D converter 51, and data BYD digitized from the signal (B-YL) in the A/D converter 52. These A/D converters 50-53, capable of high-speed function, can finely digitize the input signals. Also since the microcomputer 60 receives the synchronization signals from a synchronization signal generator 70, the correction signal calculation unit 54 can eliminate the unnecessary signals during the blanking period and the abnormal signals in the high luminance areas, and can calculate the (R-B) signal component of the object. Furthermore, the microcomputer 60 is provided therein with a data table as shown in FIG. 14, and can calculate the white balance correction data by comparing the (R-B) signal component with data corresponding to V ref1 in FIG. 1, based on said data table, thereby sending the control signals R cont , B cont to the correction signal limiting unit 25.
The function of said correction signal calculation unit 54 will be further clarified, with reference to a flow chart shown in FIG. 13.
At first in a step S100, the YHD signal from the A/D converter 50 is fetched in the correction signal calculation unit 54. In a step S102, the correction signal calculation unit 54 discriminates whether the level of the fetched YHD signal is lower than a reference value for high luminance. If the level of said YHD signal is at least equal to said reference, the sequence proceeds to a step S110.
On the other hand, if the step S102 identifies that the YHD signal level is lower than said reference value, the sequence proceeds to a step S104 for discriminating whether the function of the entire image pickup apparatus is currently in a blanking period, and, if within a blanking period or not, the sequence respectively proceeds to a step S110 or S106.
In the step S106, the correction signal calculation unit 54 fetches the RYD and BYD signals from the A/D converters 51, 52. Then, in a step S108, the correction signal calculation unit 54 generates the (R-B) signal from the RYD and BYD signals fetched in the step S106.
The step S110 discriminates whether the (R-B) signal has been generated over the entire image frame, and, if not, the sequence returns to the step S100 and the sequence of steps S100 to S110 is repeated. In case the step S102 identifies that the YHD signal level is at least equal to the reference value for high luminance, or in case the step S104 identifies that the operation is within a blanking period, the sequence skips the steps S106 and S108 so that the generation of the (R-B) signal over the entire image frame is naturally incomplete in the step S110. Thus, in case the sequence proceeds to the step S110 from the step S102 or S104, it returns to the step S100.
If the step S110 identifies that the (R-B) signal has been generated over the entire image frame, the sequence proceeds to a step S112 for comparing the (R-B) signal with V ref1 . If the former is larger, indicating that the levels of the control singals R cont , B cont have to be lowered in order to correct the white balance, a step S118 reduces the levels of said control signals according to the data table shown in FIG. 14, and the sequence proceeds to a step S120.
On the other hand, if the step S112 identifies that the (R-B) signal does not exceed V ref1 , a step S114 discriminates whether the (R-B) signal is smaller than V ref1 . If the step S114 identifies that the (R-B) signal is smaller than V ref1 , signifying that the levels of the control signals R cont , B cont have to be elevated for correcting the white balance, a step S116 elevates the levels of said control signals according to the data table shown in FIG. 14.
Also if the step S114 identifies that the (R-B) signal is at least equal to V ref1 , the (R-B) signal level is equal to V ref1 , so that the sequence proceeds directly to the step S120.
The step S120 releases the set data of the control signals R cont , B cont to the correction signal limiting unit 55, and the function of the correction signal calculation unit 54 is terminated.
In the following there will be explained the function of the correction signal limiting unit 55.
The correction signal limiting unit 55 receives a signal of which level is high or low respectively when the iris is fully open or closed, as shown in FIG. 15, from the iris position detector 40, after digitization in the A/D converter 53. According to the level of said signal, the control signals R cont , B cont received from the correction signal calculation unit 54 are limited.
In general, when the color temperature is high, the light source is often outdoor daytime solar light, with a high luminance. On the other hand, when the color temperature is low, the light source is often indoor light of an incandescent lamp or solar light at sunset, with a low luminance.
Utilizing these facts, the correction signal limiting unit 55 functions according to a flow chart shown in FIG. 16.
At first in a step S200, the correction signal limiting unit 55 fetches a signal, Vi, digitized in the A/D converter 53, from the output signal of the iris position detector. In a step S201, the correction signal limiting unit 55 fetches the control signals R cont , B cont released from the correction signal calculation unit 54.
A step S202 discriminates whether the signal Vi is larger than Vi 1 shown in FIG. 15. If Vi is larger than Vi 1 , indicating that the iris is widely open, the object is estimated to have a low luminance and a low color temperature. Thus the sequence proceeds to a step S210 for limiting the levels of the control signals R cont , B cont within an area 1 shown in FIG. 14, then to a step S212. On the other hand, if the step S202 identifies that Vi is equal to or smaller than Vi 1 , the sequence proceeds to a step S204.
The step S204 discriminates whether Vi is smaller than Vi 3 shown in FIG. 15, and, if not, the sequence proceeds to a step S208 for limiting the levels of the control signals R cont , B cont within an area 2 shown in FIG. 14 and then to a step S212. If the step S204 identifies that Vi is still smaller than Vi 3 , indicating that the aperture of the iris is very small, the object can estimated to have a high luminance and a high color temperature. Thus the sequence proceeds to a step S206 for limiting the levels of the control signals R cont , B cont within an area 3 shown in FIG. 14, and then to the step S212.
The step S212 releases the limited control signals R cont , B cont to the D/A converters 56, 57, and the function of the correction signal limiting unit 55 is terminated.
Because of the above-explained configuration and functions, in the aforementioned situation (1), the correction signal calculation unit 54 releases the signals R cont =V 5r and B cont =V 5b , but if the iris position detector releases a value equal to or larger than Vi 1 in a low luminance situation, the correction signal limiting unit 55 releases the signals R cont =V 2r and B cont =V 2b , due to the output limitation within the area 1. These control signals are converted into analog signals in the D/A converters 56, 57 and supplied to the gain control units 3, 4. This situation will be explained in relation to a vector chart shown in FIG. 17.
In response to the object 1 shown in FIG. 4, illuminated with an incandescent lamp of a low color temperature of 2000° K, the correction signal calculation unit 54 releases the signals R cont =V 5r and B cont =V 5b for effecting the aforementioned correction to achieve a condition: line segment B 1 A=line segment W 0 W 1 . However, because the correction signal limiting unit 55 releases the control signals R cont =V 2r ' and B cont =V 2b ', the white and blue colors are only corrected respectively to W 4 and B 1 , so that the error in correction can be significantly reduced in comparison with the conventional case.
Also in the aforementioned situation (2), the correction signal calculation unit 54 releases the signals R cont =V 6r , B cont =V 6b , but, when the iris position detector enters a value equal to or less than Vi 3 because of a high luminance, the correction signal limiting unit 55 releases the signals R cont =V 3r , B cont =V 3b , because of the limitation within an area 3. Said control signals are converted into analog signals by the D/A converters 56, 57 and supplied to the gain control units 3, 4. Referring to a vector chart shown in FIG. 18, in response to the object 2 shown in FIG. 5, illuminated with solar light of a high color temperature, for example, of 9000° K, the correction signal calculation unit 54 releases the signals R cont =V 6r , and B cont =V 6b for effecting the aforementioned correction to achieve a condition: line segment Ye 1 B=line segment W 0 W 3 . However, because the correction signal limiting unit 55 releases the control signals R cont =V 3r ' and B cont =V 3b the white and yellow colors are only corrected respectively to W 5 and Ye 2 , so that the error in correction can be significantly reduced in comparison with the conventional case.
Also the output of the correction signal limiting unit 55 may be given a suitable time constant, in order to prevent rapid variation in the output when the limiting range varies for example from the area 3 to 1. In this manner a natural correction can be obtained, since the white balance does not vary rapidly.
Though the present embodiment employs three areas, it is also possible to utilize more finely divided areas. Also sufficient improvement can be obtained by employing only two areas.
2nd Embodiment
In the following there will be explained a second embodiment of the image pickup apparatus of the present invention, wherein the configuration of the apparatus is identical with that in the first embodiment, and will not, therefore, be explained further. It is different from the first embodiment, in the function of the correction signal limiting unit 55.
This second embodiment is designed to provide proper white balance correction for certain rare situations which cannot be properly corrected by the first embodiment, such as an object of a low luminance and a high color temperature (such as an outdoor object in the shadow of a tree), or an object of a high luminance and a low color temperature (such as an object illuminated with a halogen lamp).
FIG. 19 shows a data table, provided in the microcomputer 60 and showing the relation between the output data of the iris position detector, released from the A/D converter 53, and the luminance coefficient K. Said coefficient K is zero when the luminance is equal to or lower the EV8, namely when the output of the iris position detector is equal to or higher than Vi 1 , and increases with the increase in luminance, reaching a value K5 at a luminance equal to or higher than EV12.
FIG. 20 shows a data table, indicating the function of the correction signal limiting unit 55 provided in the microcomputer 60. The ordinate of FIG. 20 indicates the signal R cont , while the abscissa indicates the sum of the luminance coefficient determined in FIG. 19 and the white balance correction signal R cont and the control range of the control signal R cont is divided into two areas according to said sum. In an area A the signal R cont is variable in a range V 2r -V 2r ', and in an area B the signal R cont is variable in a range V 2r -V 3r . The control signal B cont , corresponding to thus limited control signal R cont , is calculated from the data table shown in FIG. 14.
At the start of the white balance correcting operation, the signals R cont , B cont start from initial values V 3r , V 3b .
In the following, the function of two data tables shown in FIGS. 19 and 20, and of the correction signal control unit 55 with three examples.
EXAMPLE 1
In case an entirely white image frame, illuminated with light of a low luminance and a low color temperature (for example less than EV8; 2000° K) is taken and the white balancing operation is conducted, the control signal R cont is initially positioned at P0 in FIG. 20 (R cont +K=V 3r , where K==0). Then, when the white balance correcting operation is stabilized, the correction signals reach R cont =V 2r , B cont =V 2b at a point P1 in FIG. 20 (R cont +K=V 2r , where K=0).
If blue color is introduced into the object as in FIG. 4, the white balance correction signals tend to increase to R cont =V 5r , B cont =V 5b as explained before, but remain at V 2r , V 2b since the maximum value of R cont in the area A is V 2r . Thus the white balance correction with little error can be attained as in the first embodiment. This situation corresponds to a point P2 in FIG. 20 (R cont +K=V 2r , where K=0).
EXAMPLE 2
In case a white object of a low luminance and a high color temperature (for example less than EV8; 9000° K) is taken and the white balancing operation is conducted, the control signal R cont is initially positioned at P0 in FIG. 20. When the white balance correcting operation is thereafter stabilized, the correction signals reach R cont =V 4r , B cont =V 4b to provide proper white balance correction, corresponding to a point P3 in FIG. 20 (R cont +K=V 4r ; where K=0).
EXAMPLE 3
In case a white object of a high luminance and a low color temperature (for example equal to or higher than EV12; 2000° K) is taken and the white balancing operation is conducted, the control signal R cont is initially positioned at P0 in FIG. 20. When the white balance correcting operation is thereafter stabilized, the correction signals reach R cont =V 2r , B cont =V 2b corresponding to P4 in FIG. 20 (R cont =V 2r , K=K5), thus providing proper white balance correction.
Thus the white balance correction starts from the wider area B, and thereafter enters the narrower area A according to the condition of the object, as shown in the example 1, thereby reducing the error in correction.
In this embodiment, once the correcting operation enters the area A, it does not return to the area B unless the luminance coefficient K becomes at least equal to K4, or the signal R cont becomes at least equal to V 2r' and the luminance coefficient K becomes at least equal to K1. Stated differently, the entry into the area B occurs only when the sum of the white balance control value and the luminance coefficient reach a given value. Though this embodiment employs two areas, it is also possible to a larger number of areas. Also the iris position detector 40 may naturally be replaced by a luminance sensor capable of detecting the object luminance.
3rd Embodiment
FIG. 21 is a block diagram of a third embodiment of the image pickup apparatus of the present invention, wherein the iris position detector 40 is replaced by a luminance sensor 45. Limiting circuits 12r, 12b are provided for limiting the signals R cont , B cont according to the output of the luminance sensor 45.
Also in this case, the white balance correction as in the first embodiment can be attained by employing the limiting area 1 shown in FIG. 14 if the external luminance is detected equal to or lower than EV8, the area 3 shown in FIG. 14 in case the external luminance is equal to or higher than EV11, and the area 2 otherwise.
The above-explained embodiment can be modified or varied within the spirit and scope of the present invention.
The above-explained first, second or third embodiment of the image pickup apparatus of the present invention limits the control ranges of the gains of the different colors according to the luminance level of the object, thereby reducing the error, namely excessive or deficient correction of the white balance even in case the object contains a large proportion of a single color, thereby realizing visually satisfactory white balance correction. ps 4th Embodiment
FIG. 22 is a block diagram showing an essential part of a 4th embodiment of the image pickup apparatus of the present invention, wherein components same as or equivalent to those shown in FIG. 9 or 12 are represented by same numbers and are omitted from the following description.
In FIG. 22 there are shown a weighting calculation unit 64 for receiving the outputs of the aforementioned A/D converters 50-53 and effecting the weighting for white balance control as will be explained later; a correction signal calculation unit 65 for receiving a signal from the weighting calculation unit 64 and forming control signals for white balance correction; and D/A converters 56, 57 for converting digital correction signal, from the correction signal calculation unit, into analog signals.
The D/A converters 56, 57 supply the gain control circuit 3 for controlling the gain of the R signal, and the gain control circuit 4 for controlling the gain of the B signal, respectively with the control signals R cont B cont .
The iris position detector 40, consisting for example of a Hall element, detects the position of the iris 22, and releases a signal of which level is high or low respectively when the iris is open or closed, as shown in FIG. 23, for supply to the A/D converter 53.
The above-mentioned components 64, 65 are illustrated as hardwares for facilitating the understanding of the present embodiment, but in fact are constructed in a microcomputer 61, which receives synchronization signals, from the synchronization signal generator 70, for addition to the standard television signal to be released from the terminal 23, for defining the timings necessary for various calculations.
The weighting calculation unit 64 receives data YHD, digitized from the YH signal in the A/D converter 50, data RYD, digitized from the (R-Y) signal in the A/D converter 51, data BYD, digitized from the (B-Y) signal in the A/D converter 52, and data IRD released from the iris position detector 40 and digitized in the A/D converter 53. These A/D converters 50-53, being capable of high-speed operation, can digitize the input video signal in small area units.
Also the above-mentioned synchronization signals are supplied to the microcomputer 61, and are utilized in the weighting calculation unit 64 for excluding the unnecessary portion of the video signal corresponding to the blanking period from the calculation process.
Therefore the weighting calculation unit 64 effects the calculation utilizing the signals RYD, BYD and YHD excluding said blanking period. A further detailed explanation will be given in the following on the function of said weighting calculation unit 64.
At first the weighting calculation unit 64 calculates the x (=R-B) component and y (=R+B-2Y) component in each of the above-mentioned small areas, based on the A/D converted RYD and BYD signals.
It then determines the weighting coefficient K for RYD and BYD, based on said y and x components and the YHD signal. In the present embodiment, the relation between said weighting coefficient and the y and x components is variably determined according to IRD, as will be explained later, but in the following there will be explained, for the purpose of simplicity, a case in which the IRD assumes a standard value IRD2.
In the present embodiment, said coefficient K is given by K=K1×K2×K3, wherein the coefficient K1 is determined, according to the above-mentioned y-component as shown in FIG. 24, as K1=1.0 in a range -L3≦y≦+L1, and monotonously decreases within a range from 1.0 to 0.0 within ranges of y of -L3≦y≦-(L3+L4) or L1≦y≦(L1+L2). Stated differently, the coefficient K1 indicates the level of whiteness of the object as a function of the y component, the whiteness level being higher as the coefficient K1 becomes closer to unity.
Similarly the coefficient K2 is given as a function of the x-component as shown in FIG. 25. If the x-component is very large or very small, it can be considered to be derived from the color of the object itself, so that the object can be considered not white. Consequently the coefficient K2 is defined as 1.0 within a range -L7≦x≦L5, but monotonously decreases within a range from 1.0 to 0.0 within ranges of x of -L7≦x≦-(L7+L8) or L5≦x≦(L5+L6).
The coefficient K3 is defined as 1.0 if the level of the YHD signal is higher than (L9+L10) as shown in FIG. 26, as the probability of object color being white is high. As the YHD signal becomes lower than (L9+L10), the coefficient K3 is monotonously decreased from 1.0 to 0.0 until the YHD signal reaches a level L9, since the probability of object being white becomes lower. The coefficient K3 is defined as 3.0 when the YHD signal is at or lower than L9. However, if the YHD is larger than (L9+L10+L11), it is regarded as an abnormal signal, so that coefficient K3 is defined as 0.0.
In this manner the coefficient K is calculated from the coefficients K1, K2 and K3, and utilized for weighting the RYD, BYD signals supplied from the A/D converters 51, 52. The weighted signals RYD', BYD' are given by:
RYD'=K×RYD=K1×K2×K3×RYD
BYD'=K×BYD=K1×K2×K3×BYD
In such weighting calculation, the RYD' and BYD' become smaller than the original RYD, BYD as the absolute values of the x and y components become larger, and become closer to the original RYD, BYD as the YHD component becomes larger.
The weighting calculation unit 64 effects such weighting on all the RYD and BYD signals on the entire image frame, and sends the weighted data RYD', BYD' to the succeeding correction signal calculation unit 65.
The correction signal calculation unit 65 averages the RYD', BYD' over the entire image frame, then compares the obtained average values AVR (RYD'), AVR(BYD') with reference values RER, REB corresponding to a white balanced video signal, and calculates the correction signals R cont , B cont for bringing said average values to said reference values, for supply to the D/A converters 56, 57.
A swill be apparent from the foregoing explanation, the RYD', BYD' in which any of the coefficients K1, K2, K3 is 0 are not used in the calculation of the correction signals. This is because the influence of data of the white object portion will be diluted in the white balance determination, if an object portion identified as not white is included in the average calculation over the entire image frame.
Therefore, in case the A/D conversion is conducted by dividing the entire image frame into N portions to obtain N sets of RYD', BYD', including M sets of RYD'=BYD'=0 because of K=0.0, the above-mentioned averages AVR(RYD'), AVR(BYD') are calculated as follows:
AVR(RYD')=(RYD'.sub.1 +RYD'.sub.2 +RYD'.sub.3 + . . . +RYD'.sub.N-1 +RYD'.sub.N)/(N-M)
AVR(BYD')=(BYD'.sub.1 +BYD'.sub.2 +BYD'.sub.3 + . . . +BYD'.sub.N-1 +BYD'.sub.N)/(N-M)
In the following there will be explained the advantage of calculating the white balance correction singals R cont , B cont for controlling the gain control circuits 3, 4 according to the above-explained configuration.
Let us consider a case in which, by taking an object consisting of orange color by 50% and blue color by 50%, there are obtained color difference vectors Pa, Pb in white balanced state, as shown in FIG. 27. However, each color difference vector is variable according a slight change in the object as explained before, and it is assumed that the color difference vector for orange color has varied from Pa to Pa'.
In such case, the conventional image pickup apparatus shown in FIG. 9 does not extract the signal corresponding to the color difference vector at Pa, but only extracts the blue signal corresponding to the vector at Pb and effects the white balance correction in such a manner that said vector for blue signal moves to a point Pb'. For this reason, satisfactory white balance cannot be attained. On the other hand, in the image pickup apparatus shown in FIG. 22, the signal corresponding to a color difference vector at Pa' is not completely excluded but the weighting coefficient K is slightly reduced from 1.0 depending on the whiteness level.
For example, if the x and y components of said point Pa' are respectively x1, y1 shown in FIGS. 25 and 24 and the YHD signal is at YHD1 in FIG. 26, the coefficients K1, K2 and K3 are respectively 0.8, 1.0 and 1.0 so that the coefficient K is equal to 0.8. Therefore the RYD, BYD signals corresponding to the color difference vector at Pa' is multiplied by 0.8. Thus the white balance is not significantly aberrated, and the orange and blue color difference vectors are stabilized respectively at Pa" and Pb".
As explained in the foregoing, the image pickup apparatus of the present embodiment enables white balance correction without error even if hue varies for example by image framing at the phototaking operation, fluctuations among the cameras or movement of the object.
In the following there will be explained the utilization of output of the iris position detector 40 in the present embodiment, for variably setting the relationship among the weighting coefficient K and the y and x components according to IRD.
As explained in the foregoing, the aberration or instability of the white balance resulting from a slight change in hue can be alleviated by continuously varying the coefficients K1-K3 according to the x and y components and the YHD signal. The above-mentioned variable setting of the relation among the weighting coefficient K and the y and x components prevents an error in the white balance correction, such as fading of a particular color, on objects of colors present in the vicinity of the trajectory of color temperature variation.
In general, if the color temperature is high, the light source is often outdoor daytime solar light, with a high luminance. On the other hand, if the color temperature is low, the light source is often an indoor incandescent lamp or the solar light at sunset, with a low luminance. Utilizing these faces, the weighting calculation unit 64 of the present embodiment variably selects the area in which the object is identified as white, namely the relationship among the weighting coefficient K and the y and x components, according to the data IRD digitized from the output of the iris position detector 40.
This variable setting operation will be explained in more details, with reference to FIGS. 28 to 32. The object is identified as white within an area of the y and x components defined by -L3≦y≦+L1 and -L7≦x≦+L5, and the parameters L1, L3, L5, L7 are variably set according to IRD.
FIG. 28 shows the relation among IRD, L5 and L7. When IRD becomes larger, namely when the iris 22 approaches the open state, L5 is increased while L7 is decreased.
The relation among IRD, L1 and L3 is shown in FIG. 29, in which the abscissa indicates the x component while the ordinate indicates the lengths of L1, L3. As IRD increases, L1 and L3 become smaller in the negative region of the x component and larger in the positive region.
FIGS. 30 to 32 show the change of the area in which the object is identified as white, respectively at a large IRD value (IRD3), a standard IRD value (IRD2) and a small IRD value (IRD1). In fact said area varies continuously from the state shown in FIG. 30 to that in FIG. 32, according to the IRD value.
As will be apparent from FIGS. 28 to 32, in a low luminance situation, the apparatus of the present embodiment increases L5 and also increases L1 and L3 in the positive region of the x-component, thereby fetching a larger proportion of the signals with orange or red color difference vectors into said area of identifying the white object, thus preventing the fading of blue objects.
On the other hand, in a high luminance situation, where IRD becomes smaller, the present embodiment reduced L5 and increases L1 and L3 in the negative region of the x component, thereby fetching a larger proportion of the signals with blue color difference vectors into said area, thus preventing the fading of orange or red objects.
Also since said area in which the object is identified as white is variably set according to the luminance of the object, said area varies in the course of a phototaking operation, following the change in the color temperature in said operation. It is therefore rendered possible to prevent a phenomenon that the color difference vector of a same object fluctuates between inside and outside said area, and the control operation for white balance can therefore be stabilized.
As explained in the foregoing, the image pickup apparatus of the present embodiment can achieve stable white balance correction without error, even in the presence of a slight change in the hue of the object at the phototaking operation, by multiplying the RYD, BYD signals with a continuously variable coefficient K. Also the variable setting of the area, in which the object is identified as white, according to the luminance of the object enables white balance correction which is faithful of the original colors of the objects without color fading phenomenon, and which is stable regardless of the eventual change in the color temperature in the course of the phototaking operation.
In the present embodiment, the signals RYD, BYD are multiplied by the continuously variable coefficient K, but stable white balance correction without error can be attained by giving at least three different values to said coefficient K.
Also in the present embodiment, the data RYD, BYD indicating the values of the color difference singals R-Y and B-Y are directly multiplied by the coefficient K, but it is also possible to obtain a similar effect in a configuration in which other color information representing other plural color signals, such as x component (=R-B) are multiplied by the coefficient K and the white balance correction is achieved by said multiplied color information, by assigning at least three different values to said coefficient K.
Furthermore, the present embodiment variably sets the value of the coefficient K according to the values of the x and y components, but the value of said coefficient K may be variably set according to data corresponding to plural color signals such as RYD and BYD.
Furthermore, the present embodiment variably sets the area, in which the object is identified as white, according to the iris position, but the variable setting of said area may also be achieved according to the YL signal, or another signal indicating the luminance, such as the output of an external light metering circuit.
As explained in the foregoing, the fourth embodiment of the image pickup apparatus of the present invention is capable of preventing a large fluctuation in the white balance correction resulting from a change in the hue of the object, thereby achieving stable white balance correction with little visual error, by weighting the color information, employed in the white balance control, with at least three different coefficients determined by the values of plural color signals.
Also the relationship between the weighting coefficients, defined for the color information employed in the white balance control, and the plural color signals is rendered continuously variable according to the luminance of the object. Consequently the white balance correction is not affected by a slight change in the color temperature of the light source illuminating the object, but can be attained stably with little error such as the fading of particular colors.
|
In controlling the gain of plural color signals, for the purpose controlling the white balance of a video signal released from an image pickup device and including the abovementioned plural color signals, there is provided a calculation circuit for calculating color temperature information according to the plural color signals and forming a gain control signal according to the color temperature information, and the variable range of the gain control signal is set at one of mutually nonoverlapping plural ranges, whereby the correction error of the white balance is rendered visually inconspicuous. Also in the calculation circuit, the plural color information are weighted according to the result of multiplication of plural coefficients which are variably set according to the mutually different plural hue components of the video signal, and the gain control signal is calculated according to thus weighted plural color information, whereby the white balance is stably controlled despite of the movement of object, variation in image frame or variation in color temperature.
| 7
|
BACKGROUND OF THE INVENTION
The present invention relates to a rotation mechanism for a waveguide feeder which is applicable to an antenna rotating section of a satellite tracking antenna system and others.
Generally, an antenna system of the kind described includes an antenna assembly having a predetermined construction and an antenna support and drive structure adapted to support and drive the antenna assembly. The antenna support and drive structure is made up of a foundation, a fixed section rigidly mounted on the foundation, and an antenna drive section rotatably mounted on the fixed section to rotate the antenna assembly. Both of the fixed section and the antenna drive section are implemented with hollow yokes so as to accommodate therein a waveguide feeder which is connected to an antenna side and another waveguide feeder which is connected to a device side. The waveguide feeder on the antenna side is rotatable together with the rotary yoke of the antenna drive section.
A majority of mechanisms heretofore proposed to rotate a waveguide feeder as stated above use a rotary joint. In a rotary joint type rotation mechanism, the stationary and the rotary yokes are rotatably interconnected through a bearing which is adapted for the rotation of the antenna. The waveguide feeders on the antenna side and the device side are interconnected by a rotary joint and allowed to rotate smoothly by a bearing associated with the rotary joint.
A problem with the prior art waveguide feeder rotation mechanism constructed as described above is that the structure is complicated due to the need for the bearing for the rotatable connection of the yokes and the bearing for the rotation of the rotary joint, resulting in a prohibitive cost.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a simple and cost-effective rotation mechanism for a waveguide feeder which is applicable to an antenna rotating section of a satellite tracking antenna system and others.
It is another object of the present invention to provide a generally improved rotation mechanism for a waveguide feeder.
A rotation mechanism for a waveguide feeder installed in a satellite tracking antenna system of the present invention includes an antenna and an antenna rotating section which includes a rotary yoke for rotating the antenna about a predetermined axis and a stationary yoke. A first waveguide feeder is fixed to the rotary yoke in parallel to the axis of rotation. A second waveguide feeder is fixed to the stationary yoke in parallel to the axis of rotation. A first flexible waveguide is connected to that end of the first waveguide feeder which adjoins the second waveguide feeder, the first flexible waveguide extending perpendicular to the first waveguide feeder. A second flexible waveguide is connected to that end of the second waveguide feeder which adjoins the first waveguide feeder, the second flexible waveguide extending perpendicular to the second waveguide feeder. A coupling waveguide couples the other end of the first flexible waveguide and the other end of the second flexible waveguide to each other.
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description taken with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partly sectional side elevation of the structure of a prior art satellite tracking antenna system;
FIG. 2 is a fragmentary sectional side elevation of a prior art rotary joint type rotation mechanism for a waveguide feeder;
FIG. 3 is a fragmentary sectional side elevation showing the structure of a rotation mechanism embodying the present invention; and
FIGS. 4A and 4B are sections along line A--A of FIG. 3 showing that portion of the rotation mechanism where flexible waveguides are interconnected, in conditions before and after rotation, respectively.
DESCRIPTION OF THE PREFERRED EMBODIMENT
To better understand the present invention, a brief reference will be made to the structure of a prior art satellite tracking antenna system, shown in FIG. 1. The prior art satellite tracking antenna system of FIG. 1, generally 10, is made up of an antenna assembly 12 and an antenna support and drive structure 14 adapted to support and drive the antenna assembly 12. The antenna assembly 12 comprises an antenna dish, or surface panel, 16, a support member 18 which supports the surface panel 16, a feeder horn 20 adapted to introduce a feeder 22 through the center of the surface panel 16, a subreflector 24, and a support 26 adapted to support the subreflector 24. The antenna support and drive structure 14, on the other hand, comprises a foundation 28, a hollow mount tower, or stationary yoke, 30 which is rigidly mounted on the foundation 28 by anchor bolts 32, and a hollow rotary yoke 34 rotatably mounted on the yoke 30 through an azimuth bearing 36 so as to rotate the antenna assembly 12. The rotary yoke 34 is connected to the support member 18 of the antenna assembly 12 through an elevation bearing 38. An elevation angle detector 40 and an azimuth angle detector 42 are provided to detect elevation angle and azimuth angle, respectively. Also provided are a fixed ladder 44 and a detachable ladder 46.
A prior art rotary joint type rotation mechanism is disposed in the vicinity of that portion of the system 10 where the stationary and rotary yokes 30 and 34 are interconnected, i.e. a hollow portion adjacent to the azimuth bearing 36. The structure of that particular portion of the system 10 is shown in an enlarged scale in FIG. 2. Specifically, as shown in FIG. 2, the rotary yoke 34 which is mounted on the antenna assembly 12 and rotatable about an axis X is joined to the stationary yoke 30 by the azimuth bearing 36, which is adapted for the rotation of the antenna. A waveguide feeder 50 connected to the antenna assembly 12 and a waveguide feeder 52 connected to a stationary device, not shown, are interconnected by a rotary joint 54 which is rotatable smoothly with the aid of a exclusive bearing 56.
A drawback inherent in this type of prior art rotation mechanism for a waveguide feeder is that the structure is complicated and, therefore, expensive, as previously discussed.
Referring to FIGS. 3, 4A and 4B, a waveguide feeder rotation mechanism embodying the present invention is shown which is free from the above-described drawback. In FIGS. 3, 4A and 4B, the same or similar structural elements as those shown in FIG. 2 are designated by like reference numerals.
As shown in FIG. 3, a flexible waveguide 60 is connected to the lower end of and perpendicular to a waveguide feeder 50 which leads to an antenna. Another flexible waveguide 62 is connected to the upper end of and perpendicular to a waveguide feeder 52 which leads to a stationary device, not shown. The waveguides 60 and 62 are interconnected at their other end by a generally U-shaped waveguide 64. The waveguides 60 and 62 may be of the convoluted type.
FIGS. 4A and 4B show that part of FIG. 3 where the flexible waveguides 60 and 62 are interconnected, in conditions before and after rotation, respectively. Specifically, before the axis of rotation X is rotated, the waveguides 60 and 62 extend one above the other and parallel to each other, as shown in FIG. 4A. When the axis is rotated counterclockwise as seen from the above, i.e., -90 degrees, as represented by solid lines in FIG. 4B, the waveguides 60 and 62 are individually bent to allow the waveguide feeder 50 to move to a position which is angularly spaced 90 degrees from the other waveguide feeder 52. Even under the deformation as shown in FIG. 4B, the waveguides 60 and 62 assure the interconnection of the feeders 50 and 52. When the axis X is rotated clockwise as seen from the above, i.e., +90 degrees from the position of FIG. 4A, the waveguides 60 and 62 are bent as represented by phantom lines in FIG. 4B, again maintaining the feeders 50 and 52 in perfect interconnection.
In summary, it will be seen that the present invention provides a rotation mechanism for a waveguide feeder which is simple and cost-effective since a complicated and expensive rotary joint is needless.
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.
|
A rotation mechanism for a waveguide feeder is disclosed which is applicable to an antenna rotating section of a satellite tracking antenna system and others. The mechanism includes two flexible waveguides which extend parallel to each other. The flexible waveguides are connected at one end to each other and at the other end to an upper waveguide feeder and a lower waveguide feeder, respectively.
| 7
|
BACKGROUND OF THE INVENTION
The invention relates to a process for the preparation of a polymerizable or copolymerizable composition consisting of a polymerizable unsaturated polyester or a mixture of such an ester and a monomer copolymerizable therewith and a peroxide initiator, and to the polymerization or copolymerization of like mixtures and to articles entirely or substantially composed of (co)polymerisates obtained by (co)polymerization of the compositions according to the invention.
Unsaturated polyesters may be obtained by reaction of approximately equivalent amounts of a polyvalent alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, propylene glycol, pentaerythritol and other diols or polyols with an unsaturated dibasic carboxylic acid or carboxylic anhydride such as maleic acid, maleic anhydride, fumaric acid, itaconic acid or citraconic acid. These unsaturated dibasic carboxylic acids or anhydrides are often used in combination with aromatic and/or saturated aliphatic dicarboxylic acids or the anhydrides derived therefrom, such as phthalic acid, phthalic anhydride, isophthalic acid, tetrachlorophthalic acid, malonic acid, adipic acid, sebacic acid, tartaric acid, etc.
Unsaturated polyesters containing vinyl group or vinylidene groups may be obtained by polycondensation of α,β-unsaturated mono carboxylic acids such as acrylic or methacrylic acid, with mono-, di- or polyhydric alcohols. As examples of these alcohols may be mentioned: methanol, ethanol, isopropanol, cyclohexanol, phenol, ethylene glycol, propylene glycol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-bis(4-β-hydroxyethyloxyphenyl)-propane, pentaerythritol and dimers thereof, trimethol propane and glycerol, and the complex diols or polyols as described in the Netherlands Patent Application No. 6 808 040, the German Patent Application DAS No. 1 645 379, the U.S. Pat. Nos. 2,895,950 and 2,628,178, the British Pat. Nos. 928,307 and 965,826 and the French Pat. No. 1 404 000.
Unsaturated polyester containing vinyl groups or vinylidene groups also may be obtained by reacting α,β-unsaturated monocarboxylic acids with compounds containing epoxy groups, such as bisphenol A bis (glycidyl ether).
The unsaturated polyesters required to this end may be dissolved in monomers copolymerizable with the polyester, which contain one or more CH 2 ═C< groups such as styrene, vinyl toluene, methylmethacrylate, ethyleneglycolmethacrylate, etc.
The solutions that are used most are those that contain 70-50% by weight of unsaturated polyester and 30-50% by weight of copolymerizable monomer. Preference is given to styrene as copolymerizable monomer.
In order to improve the stability of the unsaturated polyesters, inhibitors are incorporated in them in amounts ranging from 0.001 to 0.03% by weight. The most commonly used inhibitors are hydroquinone, quinone and paratert.butyl catechol.
The above-described unsaturated polyester or mixtures thereof with copolymerizable monomers can be (co)polymerized under the influence of hydrogen peroxide and organic hydroperoxides, ketone peroxides and diacyl peroxides, that generate free radicals.
If this (co)polymerization is to be carried out at room temperature or at a slightly elevated temperature use should be made of combinations of the afore-mentioned peroxides and accelerators, such as organic metal compounds or a tertiary amine.
DESCRIPTION OF THE INVENTION
It has now been found that the peroxidic polymerization of an unsaturated polyester or the copolymerization of such an ester with a suitable monomer can be accelerated considerably if in addition to the peroxide initiator there is incorporated in the polyester or the polyester-monomer mixture a compound having the general formula: ##STR2## where Y is a hydroxy group, an alkoxy group or an alkyl group, having 1-12 C-atoms and Z represents hydrogen, a hydroxycarbonyl group, an alkyl group, cycloalkyl group, or aralkyloxy carbonyl group with 1-20 C-atoms, a benzoyl group, or an alkanoyl group, having 1-4 C-atoms, and the resulting composition is subsequently heated to the desired polymerization temperature.
As examples of compounds that may be used according to the invention may be mentioned:
floroglucinol; mono- and dialkyl ethers of floroglucinol, such as floroglucinol monomethyl ether, floroglucinol dimethyl ether, floroglucinolmonolauryl ether; 3,5-dihydroxy alkyl benzenes, such as 3,5-dihydroxy toluene, 3,5-dihydroxyisopropyl benzene; 2,4,6-trihydroxy benzoic acid; 2,4,6-trihydroxy(cyclo)alkyl benzoates such as 2,4,6-trihydroxy methyl benzoate, lauryl 2,4,6-trihydroxy benzoate, 4-t.butylcyclohexyl-2,4,6-trihydroxy benzoate, benzyl-2,4,6-trihydroxy benzoate; 2,4,6-trihydroxy phenyl ketones, such as 2,4,6-trihydroxy-acetophenone, 2,4,6-trihydroxybutyrophenone and 2,4,6-trihydroxybenzophenone.
The compounds according to the invention can be used in amounts ranging from 0.01 to 5.0% by weight, and preferably from 0.05 to 2.0% by weight, calculated on the polymer to be polymerized or the polymer monomer mixture to be copolymerized.
As initiators for the polymerization or copolymerization may be used hydrogen peroxide; ketone peroxides, such as acetylacetone peroxide, methylethylketone peroxide, cyclohexanone peroxide and methylisobutylketone peroxide; diacyl peroxide, such as benzoyl peroxide; peresters, such as tert.-butyl peroxide-2-ethyl hexanoate; perketals, such as 1,1-ditert.-butylperoxy-3,3,5-trimethyl cyclohexane and dialkyl peroxides, such as 1,3-bis(tert.-butylperoxyisopropyl)benzene.
If the (co)polymerization is to be carried out at room temperature or at slightly elevated temperature, tertiary amines, such as N,N-diethyl aniline, N,N-dimethyl toluidine or N,N-diethyl aniline or metal compounds are to be used as an accelerator. As metal compounds may be used organic cobalt, iron, copper, vanadium, cerium, manganese, tin, silver and mercury compounds and preferably cobalt naphthenate and cobalt octoate.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention will be further illustrated in the following examples. In these examples the gel time was determined by introducing mixtures in a test tube which was placed in a thermostatted bath of 20° C. and measuring the time elapsed between the preparation of these mixtures and their gelling moment. The curing at room temperature was measured with the aid of a Persoz hardness tester on unsaturated-polyester sheets having a thickness of 1 mm. During curing these sheets were covered with tin foil to prevent evaporation of the monomer, if present, and/or to prevent inhibition of atmospheric oxygen.
The (co)polymerization at elevated temperature was followed by placing a thermocouple in a sample present in a thermostatted bath of the desired temperature and recording the change of temperature with time. From the temperature-time curve thus obtained the minimum cure time and the time to peak exotherm were determined.
By minimum cure time is to be understood the time needed for the sample to reach a particular hardness; by peak exotherm is to be understood the highest temperature reached.
The test were carried out on the following samples:
Sample A:
the reaction product of 1.0 mole of maleic anhydride, 1.0 mole of phthalic anhydride, 1.1 moles of ethylene glycol and 1.1 moles of propane-1,2-diol made up with styrene to a styrene content of 35%.
Sample B:
the reaction product of 2 moles of bisphenol A bis (glycidyl ether) and 2 moles of methylmethacrylate made up with styrene to a styrene content of 45%.
EXAMPLE I
To 100 parts by weight of Sample A were added 0.5 parts by weight of a solution of cobalt naphthenate in dimethylphthalate containing 1% by weight of cobalt, 1 part by weight of hydrogen peroxide with an active O-content of 4% and 0.08 parts by weight of floroglucinol. Of the resulting composition the gel time at 20° C. and the Persoz hardness after 2, 6 and 24 hours were determined. The same measurements were done on a composition which did not contain floroglucinol and on compositions containing different amounts of accelerator.
The various compositions used and the gel times and hardness values measured are given in the following table.
TABLE I__________________________________________________________________________Sample A 100 100 100 100 100 100 100 100 100 100__________________________________________________________________________Cobaltaccelerator 1 0.5 0.5 0.5 1 1 1 2 2 2Hydrogenperoxide 1 1 1 1 1 1 1 1 1 1Floroglucinol -- 0.08 0.16 0.32 0.08 0.16 0.32 0.08 0.16 0.32Geltime at20° C. in min 6 8 6 4.6 5.0 4.0 3.3 2.4 2.4 1.8Persoz hard-nessafter 2 hours -- 64 90 108 85 101 141 81 108 145after 6 hours 26 103 122 139 115 138 160 111 136 164after 24 hours 71 149 160 175 154 171 189 151 171 194__________________________________________________________________________
EXAMPLE II
To 100 parts by weight of sample A were added 1 part by weight of the cobalt accelerator described in Example I, 1 part by weight of hydrogen peroxide with an active O-content of 4% and 0.35 parts by weight of floroglucinol monomethyl ether. Of the resulting composition the gel time at 20° C. and the Persoz hardness after 2, 4 and 24 hours were determined.
The same measurements were carried out on composition which contained no compounds according to the invention or other compounds according to the invention.
The various compositions prepared and the gel times and hardness values measured are given in the following table.
TABLE II__________________________________________________________________________Sample A 100 100 100 100 100 100 100 100 100 100 100 100 100 100__________________________________________________________________________Cobalt accelerator 1 1 1 1 1 1 1 1 1 1 1 1 1 1Hydrogen peroxide 1 1 1 1 1 1 1 1 1 1 1 1 1 1Floroglucinol monomethyl ether -- 0.35 -- -- -- -- -- -- -- -- -- -- -- --Floroglucinol dimethyl ether -- -- 0.39 -- -- -- -- -- -- -- -- -- -- --Floroglucinol monolauryl ether -- -- -- 0.74 -- -- -- -- -- -- -- -- -- --3,5-dihydroxytoluene -- -- -- -- 0.31 -- -- -- -- -- -- -- -- --2,4,6-trihydroxy benzoic -- -- -- -- -- 0.43 -- -- -- -- -- -- -- --acid2,4,6-trihydroxy methyl -- -- -- -- -- -- 0.46 -- -- -- -- -- -- --benzoateLauryl-2,4,6-trihydroxy- -- -- -- -- -- -- -- 0.85 -- -- -- -- -- --benzoate4-t.-butylcyclohexyl-2,4,6- -- -- -- -- -- -- -- -- 0.77 -- -- -- -- --trihydroxybenzoateBenzyl-2,4,6-trihydroxy- -- -- -- -- -- -- -- -- -- 0.65 -- -- -- --benzoate2,4,6-trihydroxy- -- -- -- -- -- -- -- -- -- -- 0.42 -- -- --acetophenone2,4,6-trihydroxy -- -- -- -- -- -- -- -- -- -- -- 0.58 -- --benzophenone2,4,6-trihydroxy -- -- -- -- -- -- -- -- -- -- -- -- 0.49 --butyrophenone3,5-dihydroxyisopropyl -- -- -- -- -- -- -- -- -- -- -- -- -- 0.38benzeneGel time at 20° C. (in min) 6 4 4 3 6 1 5 4 5 3 4 4 5 7Persoz hardnessafter 2 hours -- 141 118 150 103 130 26 38 30 70 80 89 64 96after 6 hours 26 161 144 172 147 150 55 65 61 120 111 117 105 132after 24 hours 71 196 184 203 188 181 107 130 123 174 155 158 160 170__________________________________________________________________________
EXAMPLE III
To 100 parts by weight of Sample A were added 1 part by weight of the cobalt accelerator described in Example I, 1 part by weight of acetylacetone peroxide and 0.08 parts by weight of floroglucinol. Of the resulting composition the gel time at 20° C. and the Persoz hardness after 2, 6 and 24 hours were determined.
The same measurements were done on compositions not containing floroglucinol or containing floroglucinol in a different amount. The same measurements were also carried out on compositions containing a peroxide other than acetylacetone peroxide.
The compositions prepared and the measured gel times and hardness values are listed in the following table.
TABLE III__________________________________________________________________________Sample A 100 100 100 100 100 100 100 100 100 100 100 100__________________________________________________________________________Cobalt accelerator 1 1 1 1 1 1 1 1 1 1 1 1Acetyl acetone peroxide 1 1 1 -- -- -- -- -- -- -- -- --(4.0% AO)Methylethyl ketone -- -- -- 1 1 1 -- -- -- -- -- --peroxide (9.0% AO)Cyclohexane peroxide (6.5% -- -- -- -- -- -- 1 1 1 -- -- --AO)Methylisobutyl ketone -- -- -- -- -- -- -- -- -- 1 1 1peroxide (10.2% AO)Floroglucinol -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32Gel time (in min) 20° C. 15 9 8 15 7 6 54 27 17 47 11 7Persoz hardnessafter 2 hours 73 100 122 33 68 101 27 48 65 -- 45 68after 6 hours 127 149 168 80 115 132 68 106 112 59 109 125after 24 hours 169 178 210 136 167 182 132 162 171 135 163 177__________________________________________________________________________
EXAMPLE IV
To 100 parts by weight of sample B were added 1 part by weight of the accelerator described in Example I, 1 part by weight of acetylacetone peroxide and 0.8 parts by weight of floroglucinol. Subsequently, the gel time at 20° C. and the Persoz hardness after 2, 4 and 24 hours were determined. The same measurements were carried out on compositions which contained no floroglucinol or 0.32 parts by weight of floroglucinol and/or other peroxides.
The resulting compositions and the measured gel times and the hardness values are shown in the following table.
TABLE IV__________________________________________________________________________Sample B 100 100 100 100 100 100 100 100 100 100 100 100__________________________________________________________________________Cobalt accelerator 1 1 1 1 1 1 1 1 1 1 1 1Acetyl acetoneperoxide (4.0% AO) 1 1 1 -- -- -- -- -- -- -- -- --Methylethyl ketoneperoxide (9.0% AO) -- -- -- 1 1 1 -- -- -- -- -- --Cyclohexanoneperoxide (5.5% AO) -- -- -- -- -- -- 1 1 1 -- -- --Methylisobutylketone peroxide(10.2% AO) -- -- -- -- -- -- -- -- -- 1 1 1Floroglucinol -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32Gel time (in min) 1440 32 8 180 20 9 -- 11 8 119 19 10Persoz hardnessafter 2 hours -- 128 203 -- 111 202 -- 151 203 -- 126 179 6 hours -- 203 251 20 197 258 -- 210 255 55 204 239 24 hours -- 269 298 205 270 284 -- 266 284 198 271 294__________________________________________________________________________
EXAMPLE V
To 100 parts by weight of sample A were added 2 parts by weight of a benzoyl peroxide paste composed of 50% by weight of benzoyl peroxide and 50% by weight of softener and 0.08 parts by weight of floroglucinol. Subsequently, at a temperature of 70° C., the gel time, the minimum cure time, the time to peak exotherm, and the peak exotherm were determined. The same measurements were carried out on compositions which are listed in the following table.
TABLE V__________________________________________________________________________Sample A 100 100 100 100 100 100 100 100 100 100 100 100__________________________________________________________________________Benzoyl peroxidepaste (50% -) 2 2 2 -- -- -- -- -- -- -- -- --Tert. butyl-per-2-ethylexanoate -- -- -- 1 1 1 -- -- -- -- -- --1,1-di-tert-butyl-peroxy-3,3,5-trimethylcyclohexane(50% -) -- -- -- -- -- -- 2 2 2 -- -- --1,3-bis (tert. butylperoxy-isopropyl)benzene -- -- -- -- -- -- -- -- -- 1 1 1Floroglucinol -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32Bath temperature(°C.) 70 70 70 70 70 70 70 70 70 100 100 100Gel time (min) 12.7 5.8 5.8 12.8 6.7 6.3 19.9 10.9 12.9 17.4 4.6 3.5Minimum curetime (min) 13.5 8.9 9.8 15.5 9.5 9.5 24.4 15.4 19.6 19.7 7.1 6.9Time to peakexotherm (min) 18.9 12.3 13.3 18.7 12.7 12.3 27.1 18.4 22.4 21.6 9.9 9.6Peak exotherm(°C.) 227 223 211 229 229 221 223 220 212 238 261 248__________________________________________________________________________
EXAMPLE VI
Of compositions listed in Table VI the gel time, the minimum cure time, the time to peak exotherm and the peak exotherm were determined in the way described in Example V. The results obtained are also included in this table.
TABLE VI__________________________________________________________________________Sample B 100 100 100 100 100 100 100 100 100 100 100 100__________________________________________________________________________Benzoyl peroxidepaste (50% -) 2 2 2 -- -- -- -- -- -- -- -- --Tert. butylper-2-ethyl hexanoate -- -- -- 1 1 1 -- -- -- -- -- --1,1-ditert-butyl-peroxy-3,3,5-tri-methylcyclohexane(50% -) -- -- -- -- -- -- 2 2 2 -- -- --1,3-bis (tert. bu-tylperoxy-isopropyl)benzene -- -- -- -- -- -- -- -- -- 1 1 1Floroglucinol -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32 -- 0.08 0.32Bath temperature(°C.) 80 80 80 80 80 80 90 90 90 110 110 110Gel time (min) 13.5 6.5 -- 20.6 14.8 10.1 28.2 17.5 12.0 17.7 7.7 6.6Minimum curetime (min) 16.9 9.8 -- 22.9 17.2 13.1 30.6 20.2 16.0 21.2 10.6 9.0Time to peakexotherm (min) 19.6 12.7 12.0 26.1 20.4 16.1 34.0 23.5 19.4 23.5 13.2 11.4Peak exotherm(°C.) 202 199 83 211 214 198 228 221 217 251 253 252__________________________________________________________________________
The invention is not limited to the afore-described examples, the scope of the invention allowing of many variants.
The cured unsaturated polyester/monomer mixture thus obtained can be used e.g. for the manufacture of casings for refrigerators, automobile parts, articles for the electronic industry, glass reinforced pipes, drains, tanks and the like.
|
A polymerizable or copolymerizable unsaturated polyester composition contains a peroxide initiator and a compound of the formula: ##STR1## wherein Y is hydroxy, alkoxy having 1-12 carbon atoms, or alkyl having 1-12 carbon atoms, and Z is hydrogen, hydroxycarbonyl, alkyl, cycloalkyl, aralkyloxycarbonyl having 1-20 carbon atoms, benzoyl, or alkanoyl having 1-4 carbon atoms.
| 2
|
CLAIM OF PRIORITY FROM A COPENDING PROVISIONAL PATENT APPLICATION
[0001] This patent application claims priority under 35 U.S.C. 119(e) from Provisional Patent Application No.: 60/222,411, filed Aug. 2, 2000, incorporated by reference herein in its entirety.
TECHNICAL FIELD
[0002] These teachings relate generally to optically-based detection systems and, more specifically, to systems and methods that operate on braided or woven structures, such as monofilament braided structures that form sheaths, during the processing thereof and during the manufacture of components made from portions of the structures, such as protective sheaths for wiring, piping and mechanical components.
BACKGROUND
[0003] Monofilament strands are frequently woven or braided into sleeves in order to create protective structures. These sleeves may be designed to contain electrical wires, piping, hoses, or mechanical assemblies. The sleeve may serve to protect the contained assembly or component from heat, vibration, abrasion, dirt, oil, moisture, acids, caustics, or solvents. The protective sleeves are frequently found in environments such as internal combustion engines, aircraft fuselages, and within machinery.
[0004] During the braid or sheath manufacturing process the structures are commonly manufactured in one continuous length. In order to cut the braid into shorter lengths, without fraying of the ends, an adhesive or an epoxy may be applied to the structure at the locations where cuts are desired, thereby providing coated regions along the length of the braided structure. During an automated manufacturing process the proper cutting of the braided structure relies upon the accurate determination of the location of the coated regions. However, there may be variations in the size and placement of the coated regions, making the automatic cutting of the braided structure at predetermined locations or lengths, as it passes through a cutting machine or stage, less than an optimum approach.
[0005] It can be appreciated that it would be desirable to provide a non-contact and accurate methodology for locating the coated regions on the moving braided structure so that the braided structure can be cut at the desired location(s).
SUMMARY
[0006] The foregoing and other problems are overcome by methods and apparatus in accordance with embodiments of these teachings.
[0007] A system is disclosed for determining a location of a coated region on a braided structure, as is a method for determining the location of the coated region. The system includes at least one light source for illuminating the braided structure and at least one detector for detecting an optical contrast between the braided structure and the coated region. A data processor may be provided for determining the location of the coated region based on the detected optical contrast. The light source may be an ultraviolet light source, and the detector detects a fluorescent emission from at least one strand or filament, e.g. a monofilament, that forms a part of the braided structure. More specifically, the detector detects at least one of a reduction or an increase in a fluorescent emission from the least one filament, where the reduction and/or the increase is due to the presence of the coated region that overlies the at least one filament.
[0008] The detector may be coupled to a data processor for determining an average fluorescence intensity collected by a plurality of line scans made parallel to the braided structure. The detector may include an area array having rows and columns of radiation detector elements, such as a CCD imager.
[0009] In another embodiment the detector detects a difference in reflection between light reflecting from the braided structure and light reflecting from the coated region, while in a further embodiment the detector detects a difference in transmission between light passing through the braided structure and any light that passes through the coated region.
[0010] The system further includes apparatus for performing at least one desired operation within the coated region in response to determining the location of the coated region. In the preferred embodiment the apparatus includes a cutter for cutting through the braided structure within the coated region, where the coated region is provided so as to inhibit the unraveling of the cut ends of the braided structure. The apparatus may also include some mechanism, such as an ink jet printer or a laser, for placing indicia within the coated region.
[0011] These teachings also encompass a braided structure made from a plurality of filaments, monofilaments or strands that are woven or braided together for forming a hollow sheath-like structure. The braided structure has a length along which are disposed a plurality of coated regions. In one embodiment at least one of the strands is provided so as to emit a characteristic fluorescent emission in response to excitation light for use in detecting the locations of the plurality of coated regions, while in another embodiment the plurality of coated regions are formed of a material selected for emitting a characteristic fluorescent emission in response to excitation light for use in detecting the locations of the plurality of coated regions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The above set forth and other features of these teachings are made more apparent in the ensuing Detailed Description of the Preferred Embodiments when read in conjunction with the attached Drawings, wherein:
[0013] [0013]FIG. 1 is a block diagram of an optically-based braid cutting system in accordance with these teachings.
[0014] [0014]FIG. 2 shows a representation of a fluorescence image captured at the edge of the coated region on a monofilament braid, showing that the fluorescence from the monofilament strands on the left is completely extinguished by the coated region.
[0015] [0015]FIG. 3 is a graph that plots the average fluorescence intensity collected by 21 line scans made parallel to the braid depicted in FIG. 1 by the optical system of FIG. 1.
[0016] [0016]FIG. 4 depicts an embodiment wherein the optical system relies upon detecting variations in surface reflectivity of the braided structure for detecting the location of the coated region.
[0017] [0017]FIG. 5 depicts an embodiment wherein the optical system relies upon detecting varying amounts of light transmission through the braided structure for detecting the location of the coated region.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] As employed herein an optical contrast may indicated by a presence or an absence (complete or partial) of a fluorescent emission, the presence or absence (complete or partial) of reflected light, the presence or absence (complete or partial) of transmitted light, the presence or absence (complete or partial) of a specific wavelength or wavelengths or, more generally, any characteristic of light, such as intensity or wavelength, that is detectable by a suitable optical detector, and that can be shown to differ from one spatial location to another.
[0019] [0019]FIG. 1 is a block diagram of an optically-based braid cutting system 10 in accordance with a presently preferred embodiment of these teachings. The system 10 is assumed to operate on a braided structure 12 that includes a continuous woven or braided section 14 that is periodically coated along its length with an adhesive or an epoxy or some other similar material for forming coated regions 16 , a purpose of which is to prevent the unraveling of the braided section 14 after the braided section is cut. A typical length of the coated region 16 may be about an inch, and the distance between coated regions 16 is a function of the intended application for the braided sections 14 . As an example, for an application where the braided section 14 is intended to cover a wiring harness in an aircraft or automotive application, the distance between coated regions 16 may range from inches to tens of feet or even longer.
[0020] The braided section 14 is comprised of a plurality of strands or filaments 14 A that may be a monofilament polymeric material such as nylon or polyester, and may be formed using a conventional type of braiding machine. There may be any suitable number of filaments 14 A in the braided section 14 , such as 32 filaments. The braided structure 12 is sized according to its intended application, and may have a diameter from fractions of inch to some number of inches.
[0021] In accordance with an aspect of these teachings the system 10 includes a camera 18 , such as a solid state camera that includes a CDD imager array 18 A. The imager array 18 A may be an area (2-D) array having rows and columns of pixels, or the imager array 18 A could be a linear (1-D) array having a single row of pixels. An output of the camera 18 is coupled via link 18 B to an input of a suitable data processor 20 , such as a personal computer (PC), a workstation, a portable computer, or a computer, microprocessor or microcontroller embedded within some device or system, or the data processor 20 could be embodied in a mainframe computer. The data processor 20 may be locally situated, or it may be located at some at distance from the camera 18 , and the link 18 B may include a data communications network, including the internet, and/or a wireless (e.g., RF or IR) link.
[0022] It is assumed for the purposes of this specification that it is desired to cut the braided section 14 within the coated regions 16 , thereby forming cut ends 16 A, 16 B that are located within one of the coated regions 16 .
[0023] It is thus also assumed for the purposes of this specification that the system 10 includes some suitable mechanism for severing the braided structure 12 , such as a fixed or rotating cutting blade 22 having an actuator 22 A that is controlled by the data processor 20 . In other embodiments a laser could be used to cut the braided structure 12 .
[0024] In still other embodiments a cutting operation may not be performed, but instead some other type of operation is performed wherein it is desired to first accurately locate the coated regions 16 . As but one example, instead of cutting the braided structure 12 it may be desirable to instead imprint some type of indicia or information onto the coated regions, such as a part number, a manufacturer's logo, and/or an indication of length. The printing device could be an ink jet printer or a laser-based writing device. In this case it can be appreciated that it is also required to accurately detect the location of the coated regions 16 . It is also within the scope of these teachings to place indicia onto the coated regions 16 prior to cutting them.
[0025] It is also assumed that some relative motion exists between the braided structure 12 and the camera 18 /cutter 22 , as indicated by the arrow A in FIG. 1. Typically the braided structure 12 is in motion with some velocity relative to the fixed camera 18 and cutter 22 , although in other embodiments the reverse could be true.
[0026] In a presently preferred embodiment of these teachings at least one, and preferably a plurality of visually non apparent, fluorescent monofilament strands 15 are incorporated during manufacture into the braided structure 12 . These monofilament strand(s) 15 may be deemed non apparent by selecting a monofilament with a color close to the other strands 14 A in the braided structure 12 (e.g., white), or by using a transparent monofilament material such as a naturally clear nylon or polyester. It is not, however, a requirement that the fluorescent monofilament strands 15 be visually non apparent relative to the other strands or filaments 14 A.
[0027] A fluorescent material that is coated onto or incorporated into the monofilament strands 15 , if the strands are not normally fluorescent, is preferably selected so that its excitation and emission wavelengths are absorbed to some degree by the material of the coated regions 16 . By using a camera system 18 which uses an illumination source 19 A matched to an absorption band of the fluorescent material, the location of the edge of the coated region 16 can be determined with a high signal to noise ratio by measuring the fluorescence from the monofilament strand(s) 15 . The camera system 18 is preferably made “blind” to the excitation wavelength of the source 19 A, and an optical passband filter 19 B may be provided to accept only the emission wavelength in order to improve contrast and increase the speed of image processing. In addition, the situation could be reversed such that fluorescence (either natural or from an additive) of the coated region 16 is used to discern the location of the coated region 16 .
[0028] As one suitable example, the light source 19 A may be a pulsed or continuous UV excitation source operating in a wavelength range that includes about 300 nm, more preferably about 370 nm, the fluorescent material that comprises the monofilament strand(s) 15 could comprise a member of the Stilbene family that is visually clear or uncolored but that fluoresces in the wavelength range of about 325 nm to about 450 nm (e.g., Stilbene 420), and the filter 19 B then is selected to exclude 370 nm excitation UV light and to pass the emission light from the monofilament strand(s) 15 . This example is not to be construed in a limiting sense upon the practice of these teachings, as other suitable fluorescent materials may be employed, as may other excitation wavelengths and filter passbands. For example, certain Coumarin and Rhodamine dyes could be used as well.
[0029] The algorithm for detecting a fluorescent monofilament strand 15 in relation to an optically thick coating 16 accurately distinguishes the border between the braided section 14 and the coated region 16 . Assuming that the braided structure 12 is constructed entirely using the fluorescent monofilament strands 15 , a relatively simple line scan of the fluorescent emission intensity along the braided structure 12 is sufficient to locate the point of demarcation between the braided section 14 and the coated region 16 . However, if only some fraction of the monofilament strands 15 are fluorescent (e.g., eight out of 32), the algorithm cannot rely upon a simple measurement along one line of pixels of the camera's CCD array 18 A, as a particular strand 15 , due to the braiding, will typically pass in and out of view of the camera 18 .
[0030] Preferably, detection of the coated regions 16 is assured by either incorporating several monofilament strands 15 , several cameras 18 , or both, in order to provide visual coverage of the entire perimeter of the braided structure 12 . For example, if eight fluorescent monofilament strands 15 are used with 24 non-fluorescent strands 14 A, a single camera 18 will always detect at least two monofilament strands 15 .
[0031] By taking a series of line scans parallel to the length of the braided structure 12 by reading signal out of multiple rows of the CCD imager 18 A, and in such a manner as to cover the profile of the braid, an average fluorescence intensity along the length of the braided structure 12 may be obtained. Judicious selection of an intensity threshold results in an accurate detection of the location of the coated region 16 . For example, as the average fluorescence intensity along the braid length falls off, the edge of the coated region may be determined by the algorithm executed by the processor 20 to be the 20% intensity point.
[0032] [0032]FIG. 2 depicts an example of a fluorescent image seen by the camera system 18 , while FIG. 3 graphs the average fluorescence intensity collected simultaneously by 21 line scans of the CCD imager 18 A. The scans in this example were made parallel to the length of the braided structure 12 , and traversed the visible perimeter. The rapid fall-off in the average fluorescent intensity emitted by the monofilament strands 15 is readily apparent, and is indicative of the edge of the coated region 16 .
[0033] Upon detecting the edge of the coated region 16 the algorithm executed by the data processor 20 is enabled to send a command to the cutter actuator 22 A to cut the braided structure 12 . It may be assumed that the relative velocity of the braided structure 12 with respect to the cutter blade 22 is known, as is the response time of the cutter actuator 22 A, and the command may be delayed for a suitable period of time to place the cut at a desired location within the coated region 16 . In another embodiment it may be desirable to detect both the leading edge (declining average flourescent intensity) and the trailing edge (increasing average flourescent intensity) of the coated region 16 , and to then issue the cut command to more precisely position the cut within the coated region 16 . This later embodiment may be particularly desirable where the length of the coated regions 16 varies from one to another. These same considerations apply for the case where some operation other than cutting, such as printing, is be performed within the coated region 16 .
[0034] In conclusion, a high contrast, fluorescence-based detection method has been outlined to aid in the accurate determination of the presence of a coating or protective layer, i.e., the coated region 16 , on a braided sleeve that is to be cut from the braided structure 12 . This information may be used to determine the length of the part and/or to locate the coated region 16 for cutting or other purposes.
[0035] Other approaches than the high contrast, fluorescence-based detection method may also be employed in accordance with these teachings. For example, one may employ a fluorescent coating region 16 on a non-fluorescent braid 14 , or one may employ a coating region that fluoresces at a first wavelength on a braid 14 that fluoresces at a second wavelength, and to then also employ one or more camera assemblies 18 that are responsive to both of the emission wavelengths.
[0036] In a further embodiment the optical system may rely instead upon variations in the surface reflectivity for detection of the coated region 16 . For example, and referring to FIG. 4, if the monofilament braided section 14 has a glossy appearance while the coated region 16 has a matte or less reflective finish, observing changes in the specular reflection from a collimated light source 30 with one or more light detectors 32 , such as photodiode(s) or CCD imager array(s), the algorithm executed by the data processor 20 is enabled to distinguish between the coated sections 16 and the uncoated sections 14 . In general, the specular reflection from the glossy braided region 14 exhibits a narrower diffraction angle than a reflected spot from a matte finish applied to the coated regions 16 . By placing the light detector(s) 32 at one or more locations where they are best positioned to receive the reflected light from the braided section 14 , the reduction in intensity due to the increased scattering of the light from the coated regions 16 is detectable and indicative of the presence of the coated region 16 in the path of the beam from the collimated source 30 .
[0037] Since the coating material of the coated regions 16 also serves to increase the opacity of the braided structure at those locations, in the further embodiment shown in FIG. 5 an optical measurement is used to locate the coated regions 16 by measuring light transmission through the braided structure 12 between a light source 34 and a light detector 36 .
[0038] In a somewhat similar fashion, the presence of the coated region 16 may be identified by ultrasonics, where the coated region 16 is assumed to be less transparent to ultrasonic waves. However, this approach may require that physical contact be made to the braided structure 12 .
[0039] In a further embodiment, and assuming that there exists an optical contrast (e.g. colored monofilament strand(s) 15 and a black coating material in the coated regions 16 ), the camera system 18 may be used to image in the visible regime and to then detect the coated regions 16 by employing some type of image processing algorithm. For braided structures 12 that lack a discernible color contrast (e.g., a black coating on a black monofilament braid or a white coating on a white monofilament braid), one or more of the other approaches described above are preferably employed.
[0040] While described above in the context of a CCD or similar type of area array camera 18 , it should be appreciated that the teachings herein may be practiced as well by using one or more discrete photodetectors provided with suitable filter(s), and then using threshold detection to locate the edge(s) of the coated regions 16 .
[0041] Thus, while these teachings have been particularly shown and described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that changes in form and details may be made therein without departing from the scope and spirit of these teachings.
|
Disclosed is a system and method for determining a location of a coated region on a braided structure. The system includes at least one light source for illuminating the braided structure and at least one detector for detecting an optical contrast between the braided structure and the coated region. A data processor may be provided for determining the location of the coated region based on the detected optical contrast. The light source may be an ultraviolet light source, and the detector detects a fluorescent emission from at least one strand or filament, e.g. a monofilament, that forms a part of the braided structure. More specifically, the detector detects at least one of a reduction or an increase in a fluorescent emission from the least one filament, where the reduction and/or the increase is due to the presence of the coated region that overlies the at least one filament. The detector may be coupled to a data processor for determining an average fluorescence intensity collected by a plurality of line scans made parallel to the braided structure. In another embodiment the detector detects a difference in reflection between light reflecting from the braided structure and light reflecting from the coated region, while in a further embodiment the detector detects a difference in transmission between light passing through the braided structure and any light that passes through the coated region.
| 3
|
[0001] The present application relates to U.S. Provisional Patent Application Ser. No. 61/517,613 filed on Apr. 21, 2011 and claims priority therefrom.
[0002] The present application was not subject to federal research and/or development funding.
TECHNICAL FIELD
[0003] Generally, the invention relates to a method and machine for dewatering paper webs. More specifically, the invention is a process and machine which produces paper having more uniform fiber orientation, sheet structure and improved paper strength characteristics. The improved method and machine includes devices that are arranged in the forming or wet section of a Fourdrinier machine, hereinafter referred to as “Fourdrinier.” The devices are adjusted manually or through a computer and associated drive mechanisms.
[0004] An improved method of forming paper using a Fourdrinier is composed of a plurality of foil and vacuum assisted drainage elements that are equipped with on-the-run adjustable angle and/or height dewatering foil blades starting from a paper dryness of 0.1% and extending all the way to 5% dryness within the forming section of a Fourdrinier. The foil blade angle, height, and vacuum level are adjusted as applicable along the entire length of the Fourdrinier dewatering table until a paper dryness of 5% is achieved. These adjustments allow for control of the dewatering rate and turbulence (shear) produced from a paper dryness of 0.1% to 5% on the Fourdrinier dewatering table. Controlling drainage and shear along this entire range of dryness has a direct influence on paper fiber orientation. This has a significant influence on paper strength.
[0005] The claimed invention works in unison with the paper machine headbox shear forces to promote maximum fiber orientation in either the cross-machine or machine direction orientation of the paper. The headbox controls fiber orientation through a speed difference between its stock jet speed and the dewatering fabric speed. Once the stock jet lands on the dewatering fabric, it is operated at an overspeed compared to the dewatering fabric “rush” or the same speed “square” or an underspeed “drag” to control the orientation of the fibers during the sheet forming process. Operating the headbox in a rush or drag mode will align fibers in the machine direction which is beneficial for machine direction related strength properties in the finished paper product. Operating in a square mode will produce a maximum cross-machine direction fiber orientation of the fibers in the finished paper product which is beneficial for paper strength properties in the cross-machine direction.
[0006] The claimed invention provides control of drainage and turbulence anisoptropic shear after the headbox stock jet lands on the dewatering fabric. After the stock lands, the claimed invention is adjusted to preserve or amplify the fiber orientation characteristics produced by the headbox. In this manner, a higher quality of paper is produced with the instant process and machine. Moreover, existing machines may be retrofitted with various devices and operated in the manner disclosed herein to achieve a superior quality of paper stock.
[0007] For example, if machine direction fiber orientation is desired, the headbox jet speed is operated in a rush or drag mode to promote an initial strong machine direction alignment of the paper fibers. From here, the foil blade angles and height, along with the vacuum levels on the vacuum assisted dewatering units are adjusted to produce a high early drainage rate in the initial sheet dewatering zone (0.1% to 2% paper dryness) to immediately freeze the machine direction fiber orientation produced by the headbox. In addition to this, the foil blade angles, heights and vacuum levels are also adjusted to produce a high amount of turbulence in this paper dryness zone (0.1% to 2%). This keeps the fibers mobile and prevents entanglement allowing the headbox shear to become more effective in orientating fibers in the machine direction. After 2% paper dryness, the angle and height and vacuum levels are adjusted to gradually achieve a paper dryness of 5%. However, the foil angle and height are adjusted to achieve only moderate turbulence levels to prevent disruption of the machine direction fiber orientation achieved earlier in the sheet dewatering and forming process.
[0008] For cross-machine direction fiber alignment, the process is completely reversed. The headbox stock jet is adjusted to produce a speed difference close to zero (square mode) to promote the highest possible cross-machine direction fiber orientation. However, due to contraction created within the headbox nozzle, a certain unavoidable degree of machine direction fiber alignment is still always present in the fiber slurry when it lands on the dewatering fabric that cannot be reversed through normal Fourdrinier dewatering equipment. To break this natural machine direction fiber orientation up and produce the most random fiber orientation and highest amount of cross-machine direction fiber orientation, the claimed invention is operated as follows. First, the foil blade angles and heights along with the vacuum levels of the vacuum assisted dewatering elements are adjusted to significantly retard drainage in the early sheet forming zone (0.1% to 2% dryness). This is completely opposite of the previously described process for machine direction fiber orientation. In addition to this, the angle and height of the foil blades are adjusted to produce a very high degree of turbulence to prevent fiber entanglement and generate the most random fiber orientation possible for the highest level of cross-machine direction fiber alignment. After a dryness of 2% is achieved, the foil angle and height is adjusted to maintain this high level of turbulence all the way until a paper dryness of 5% is achieved. A very gentle early drainage along with high turbulence all the way until a dryness of 5% will create the most random fiber network resulting in the highest amount of cross-machine direction fiber alignment.
[0009] The ability of the claimed process and machine improvement to be adjusted in conjunction with shear significantly increases paper sheet strength properties such as Mullen, Burst. Bending Stiffness, or Concora (machine direction strength properties) and Ring Crush, S.T.F.I, SCT (cross machine direction strength properties) and all other strength properties associated with paper manufacturing.
[0010] In addition to this, the claimed invention and sheet forming process also improves other paper properties such as formation, smoothness, uniformity, printability, ply bond strength, and the like.
BACKGROUND OF THE INVENTION
[0011] The forming or wet section of a Fourdrinier consists mainly of the head box and forming wire. Its main purpose is to generate consistent slurry, or paper pulp, for the forming wire. Several foil, suction boxes, a couch roll, and a breast roll commonly make up the rest of the forming section. The press section and dryer section follow the forming section to further remove water from the stock.
[0012] Historically, the main tools used to control paper strength have been fiber species and fiber refining energy along with the orientating shear generated by the speed difference between the headbox jet speed and the dewatering (forming) fabric speed. The first method of continuous sheet forming and dewatering was the Fourdrinier dewatering table which is still the dominant tool used for paper manufacturing today. Since the time of its invention, its impact on sheet strength has been misunderstood or vaguely understood. Also, the ability to directly influence sheet strength through changing the drainage or shear rates produced during the Fourdrinier dewatering and forming process have also been misunderstood. Past technologies such as the VID, Deltaflo or Vibrefoil have been able to adjust drainage and turbulence on the Fourdrinier table. However, these technologies have been used prior to a sheet consistency on the Fourdrinier table of 1.5% or less. The impetus behind their design was simply to generate turbulence in a very short area in an effort to improve paper uniformity (formation) which was claimed to influence sheet strength.
[0013] It has been discovered through the use of the claimed improved Fourdrinier papermaking process that controlling drainage and turbulence from a paper dryness of 0.1% to 5% on a dewatering table has a far more significant impact of fiber orientation and paper strength. In addition, the previously described methods of adjusting the headbox shear in conjunction with adjusting drainage and turbulence in this zone to control fiber orientation and paper strength up to this point been has been unknown to anyone other than the inventors of the claimed improved process.
BRIEF SUMMARY OF THE INVENTION
[0014] An improved process of Fourdrinier papermaking is used for dewatering and paper quality control and achieved in the forming end of the Fourdrinier. The process uses a plurality of gravity and vacuum assisted drainage elements that are equipped with on-the-run adjustable angle and height dewatering foil blades starting from a paper dryness of 0.1% and extending all the way to 5% dryness. The foil blade angles and heights along with vacuum level are adjusted manually or automatically along the entire length of the Fourdrinier dewatering table until paper dryness of 5% is achieved.
[0015] The claimed invention uses a series of gravity assisted drainage elements in the beginning of the Fourdrinier dewatering table. These units are the forming board and hydrofoil section that are equipped with a combination of static and adjustable angle foil blades, as well as foil blades which are height adjustable depending on the paper grade being produced. A low-vacuum section is arranged on the dewatering table after the hydrofoil section. The low-vacuum section includes vacuum assisted drainage elements which are equipped with vacuum control valves, fixed angle and angle adjustable foil blades, as well as foil blades which are height adjustable depending on the paper grade being produced. A high-vacuum section is arranged between the low-vacuum section and a couch roll.
[0016] Adjusting the angle and height of the dewatering foil blades along with the vacuum level allows for control of the dewatering rate and turbulence (shear) produced from a paper dryness of 0.1% to 5% on the Fourdrinier dewatering table. Controlling drainage and shear along this entire range of dryness in conjunction with fiber orientation shear produced by the headbox has a direct influence on paper fiber orientation. This has a significant influence on paper strength.
[0017] Adjustable dewatering technologies are typically used on the Fourdrinier table in an area directly after the forming board or within a short distance of the forming board and dry the stock to a dryness content of 3.5%. Previously, the design and operation of a Fourdrinier has been focused on fiber orientation control to improve sheet strength.
[0018] Other technologies such as the dandy roll or top dewatering machines have been used at a dryness content of 1.5% or greater. However, their purpose has simply been water removal or paper formation improvement, not fiber orientation control liked the claimed invention. Moreover, none of the existing technologies are directed towards precisely controlling fiber orientation as in the disclosed manner.
[0019] It is an object of the invention to disclose an improved process for controlling the fiber orientation of paper stock to achieve a better quality paper than is currently produced on a Fourdrinier.
[0020] It is a further object of the invention to teach a Fourdrinier having adjustable on-the-run mechanisms for adjusting the height and angle of foils or blades to easily switch over operation of the Fourdrinier to produce paper of higher quality through controlling the orientation of the fibers.
[0021] Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned from practicing the invention. The objects and advantages of the invention will be obtained by means of instrumentalities in combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0022] Other objects and purposes of this invention will be apparent to person acquainted with apparatus of this general type upon reading the following specification and inspecting the accompanying drawings, in which:
[0023] FIG. 1 illustrates a Fourdrinier papermaking machine incorporating the present invention therein.
[0024] FIG. 2 is an enlarged view showing a formline element with stationary and adjustable height foil blades and which forms part of the forming board section of the Fourdrinier.
[0025] FIG. 3 shows a Hydroline element with adjustable angle and height foil blades and which forms part of the hydrofoil section of the Fourdrinier.
[0026] FIG. 4 shows a Varioline element with stationary and adjustable height foil units and being part of the low-vacuum section.
[0027] FIG. 5 shows a Vaculine element with stationary and angle adjustable foil blades and being part of the low-vacuum section.
[0028] FIG. 6A shows a detailed view of an adjustable angle foil blade mounted on a C-channel and with the leading edge of the angle adjustable blade raised to +1°. FIG. 6B shows the blade of FIG. 6A having a −3° separation from an underside of the forming fabric. FIG. 6C shows a detailed view of an adjustable height foil blade mounted on a T-bar and with the leading edge of the angle adjustable blade raised to +1°. FIG. 6D shows the blade of FIG. 6C having a −3° separation from an underside of the forming fabric.
[0029] FIG. 7A shows a detailed view of an adjustable height activity blade mounted on a C-channel and with the height being at 0 mm where it is in contact with the underside of the forming fabric. FIG. 7B shows the blade of FIG. 7A at a −5 mm height below the forming fabric. FIG. 7C shows a detailed view of an adjustable height blade mounted on a T-bar and with the height being at 0 mm where it is in contact with the underside of the forming fabric. FIG. 7D shows the blade of FIG. 7C at a −5 mm height below the forming fabric.
[0030] FIG. 8A shows a control subassembly for an angle adjustable blade taken from an end of the Fourdrinier. FIG. 8B shows a cutaway view of the drive that is actuated to adjust the angle of a respective blade.
[0031] FIG. 9A shows a control subassembly for the height adjustable blade taken from an end of the Fourdrinier. FIG. 9B shows a cutaway view of the drive that is actuated to adjust the height of a respective blade.
DETAILED DESCRIPTION OF THE INVENTION
[0032] The embodiments of the invention and the various features and advantageous details thereof are more fully explained with reference to the non-limiting embodiments and examples that are described and/or illustrated in the accompanying drawings and set forth in the following description. It should be noted that the features illustrated in the drawings are not necessarily drawn to scale, and the features of one embodiment may be employed with the other embodiments as the skilled artisan recognizes, even if not explicitly stated herein. Descriptions of well-known components and techniques may be omitted to avoid obscuring the invention. The examples used herein are intended merely to facilitate an understanding of ways in which the invention may be practiced and to further enable those skilled in the art to practice the invention. Accordingly, the examples and embodiments set forth herein should not be construed as limiting the scope of the invention, which is defined by the appended claims. Moreover, it is noted that like reference numerals represent similar parts throughout the several views of the drawings.
[0033] For illustrative purposes only, the invention will be described in conjunction with a Fourdrinier papermaking machine although the invention and concept could also be applied to hybrid and gap formers. The invention is implemented in the wet section of the Fourdrinier and includes a forming board section 10 , a hydrofoil section 20 , and a low-vacuum section 30 . High-vacuum section 40 does not include automatically adjustable height blades or automatically angle adjustable blades. It should be noted that a headbox is known and is therefore not shown in FIG. 1 . Referring now to FIG. 1 , a Fourdrinier comprises a forming fabric 105 , a breast roll 106 and couch roll 107 . The forming fabric is continuous and travels between the breast and couch rolls 106 , 107 . The stock which comprises pulp fibers is deposited from the headbox to the top surface of the forming fabric 105 at a paper dryness ranging from 0.1% to 1%. Immediately following the headbox, the forming fabric passes over a forming board section 10 which comprises a formline element 11 .
[0034] As shown in FIGS. 1 and 2 , the forming board section 10 includes formline element 11 which includes a fixed ceramic lead blade 12 and a plurality of trailing blades 13 , 14 . The blades 13 , 14 are arranged beneath the forming fabric or wire and are fixed atop either stationary or adjustable C-bar or T-bar which extend from one side of the Fourdrinier to the other. The support bars preferably comprise fiber reinforced composite. The stationary bars are fixed. In the preferred embodiment, the formline element 11 includes three adjustable trailing blades 13 which may be raised and lowered or the angle adjusted as shown in the respective figures with the use of respective drive 17 A. The drives are arranged at opposite ends of a support bar and fixed. The drives arranged at opposite ends of the support bar operate in concert to lower or raise a respective blade. It should be noted that the air, hydraulic and electrical lines for actuating the drives are not shown for ease in understanding the drawings. It should be understood that it is contemplated that various other drives, pistons or motors including electric and hydraulic ones and their associated supply lines may be employed to practice the invention. The adjustable blades 13 are raised or lowered to cause them to intersect the underside of the forming fabric 105 at a predetermined height to influence the alignment of the fibers within the paper web. Two fixed trailing blades 14 are arranged between the height adjustable blades 13 , as shown. In a preferred embodiment, the height of the adjustable blades may be changed to ensure that the paper fibers are aligned in a desired direction. The forming board lead blade 12 is arranged near the breast roll and is stationary. A plurality of forming board trailing blades is arranged in an alternating sequence of adjustable height blades 13 and stationary blades 14 . The forming board trailing blades preferably comprise ceramic.
[0035] During this stage, some water is drained from the stock and a very thin wet sheet is carried over to various other dewatering devices such as foil blades in hydrofoil section 20 , until a sheet paper dryness of around 1% to 1.5% is achieved. Following this, the paper dryness is increased by the foil blades in the Varioline and Vaculine in the low vacuum section 20 to a dryness level of 5%. Next, a paper dryness of 8% to 10% is achieved in the elements of the low-vacuum section 30 and the sheet is transferred to the high-vacuum section 40 to achieve a paper dryness of 18% or greater. Finally, the sheet is transferred over the couch roll where additional dryness level is achieved.
[0036] A Fourdrinier composed of the previously described equipment is fitted with a plurality of adjustable angle and height foil blades starting from the forming board section 10 and partially through the low-vacuum section 30 . As the stock travels with the forming fabric 105 , it encounters the adjustable angle and height foil blades at various points along the dewatering table to manipulate the paper web and orient more fibers in a desired direction. On the forming board section 10 and the hydrofoil or gravity section 20 , the adjustable angle foil blades generate a vacuum pulse that dewaters the stock slurry. The amount of drainage produced along each adjustable angle foil blade is determined by the angle setting of the foil blade which can be typically varied between +2 and −4 degrees. A higher angle will produce more drainage.
[0037] Also within the forming board section and hydrofoil or gravity section of the papermaking process, the stock encounters adjustable height foil blades. These blades also drain water from the stock slurry. The amount of water drained by the adjustable height foil blades is determined by their height setting in relation to the forming fabric. At a setting of −5 mm, they do not touch the fabric and do not drain any water. At a setting of 0 mm, they are in the same plane as the forming fabric and will drain water. As the adjustable height foil blades are lowered from the fabric, the amount of drainage increases up until a point at which the static and dynamic vacuum forces generated by the adjustable height foil blade are overcome by the tension forces of the forming fabric. When this occurs, the fabric breaks its seal with the adjustable height foil blade and no dewatering occurs. The setting at which this occurs will vary based on the drainage characteristics of the stock, the stock consistency, and the speed of the forming fabric. As can be understood, changing the height settings will directly influence the fiber orientation.
[0038] The wet slurry will leave the hydrofoil section 20 at a consistency of around 1.5% depending on the paper grade and speed. From here, it travels to the initial vacuum assisted foil units in the low-vacuum section 30 which are referred to as the Varioline elements. In addition to natural gravity drainage, these Varioline elements also use a dynamic and an external vacuum source to create a vacuum which is drawn onto the lower side of the forming fabric 105 . This further increases drainage within these units. The Varioline elements are equipped with a plurality of stationary and adjustable height foil blades. Similar to the previous section, as the foil blades are lowered from the forming fabric, the drainage rate increases as discussed above.
[0039] Following the Varioline table elements, another set of vacuum assisted units is encountered by the underside of the forming fabric 105 . These table elements are the Vaculine elements which are equipped with adjustable angle foil blades. Again, as the angle of the foil blades is increased, the drainage rate will increase until a consistency of 5% is achieved.
[0040] In addition to controlling drainage, the adjustable angle and height foil blades in the previously described drainage units also control turbulence within the wet slurry. This is accomplished through deflection of the forming fabric from its original plane as it travels along the top surface of the adjustable angle foil blades and adjustable height foil blades. This deflection creates a series of accelerations within the stock slurry that results in turbulence and shear within the stock slurry. This turbulence keeps the fibers fluidized and mobile within the wet slurry so that they can be orientated in the cross-machine or machine direction, depending on what the finish paper property strength requirements are.
[0041] For example, if machine direction fiber orientation is desired, the headbox jet speed is operated in a rush or drag mode to promote an initial strong machine direction alignment of the paper fibers. From here, the foil blade angles and height, along with the vacuum levels on the vacuum assisted dewatering units are adjusted to produce a high early drainage rate in the initial sheet dewatering zone (0.1% to 2% paper dryness) to immediately freeze the machine direction fiber orientation produced by the headbox.
[0042] In addition to this, the foil blade angles, heights and vacuum levels are adjusted to produce a high amount of turbulence in this paper dryness zone (0.1% to 2%). This keeps the fibers from entangling with each other and allows the headbox shear to become more effective in orientating fibers in the machine direction. After 2% paper dryness, the angle and height and vacuum levels are adjusted to gradually achieve a paper dryness of 5%. However, the foil angle and height are adjusted to achieve only moderate turbulence levels to prevent disruption of the machine direction fiber orientation achieved earlier in the sheet dewatering and forming process.
[0043] For cross-machine direction fiber alignment, the process is completely reversed. The headbox stock jet is adjusted to produce a speed difference close to zero (square mode) to promote the highest possible cross-machine direction fiber orientation. However, due to friction created within the headbox nozzle, a certain unavoidable degree of machine direction fiber alignment is still always present in the fiber slurry when it lands on the dewatering fabric that cannot be reversed through normal fourdrinier dewatering equipment.
[0044] To break this natural machine direction fiber orientation up and produce the most random fiber orientation and highest amount of cross-machine direction fiber orientation, the claimed invention is operated as follows. First, the foil blade angles and heights along with the vacuum levels of the vacuum assisted dewatering elements are adjusted to significantly retard drainage in the early sheet forming zone (0.1% to 2% dryness). This is completely opposite of the previously described process. In addition to this, the angle height of the foil blades are adjusted to produce a very high degree of turbulence to prevent fiber entanglement and generate the most random fiber orientation possible for the highest level of cross-machine direction fiber alignment. After a dryness of 2% is achieved, the foil angle and height is adjusted to maintain this high level of turbulence all the way until a paper dryness of 5% is achieved. A very gentle early drainage along with high turbulence all the way until a dryness of 5% is achieved will create the most random fiber network resulting in the highest amount of cross-machine direction fiber alignment.
[0045] After passing through the forming board section, the paper stock is moved along to pass through a hydrofoil or gravity section 20 equipped with Hydroline elements 21 . Each Hydroline element 21 comprises height adjustable blades 13 and angle adjustable blades 22 which are alternately arranged as shown in FIG. 3 . Depending on the paper grade, Hydrolines may also be fixed with all height or angle adjustable blades. The angle adjustable blades are controlled through an angle adjustment mechanism 25 , 27 as shown in FIG. 8A . Height adjustable blades are controlled through a height adjustment mechanism 18 , 21 as shown in FIG. 9B .
[0046] FIG. 4 depicts a vacuum assisted unit or Varioline table element 51 with stationary or angle adjustable foil blades and adjustable height blades and being part of the low-vacuum section. The Varioline element 51 comprises a dewatering blade 32 followed by height adjustable blades 13 . A deckle is arranged blades and may comprise a poly material. A drop leg 34 extends down from the Varioline for draining purposes.
[0047] FIG. 5 shows a Vaculine element 41 that is part of the low-vacuum section 30 . Vaculine elements 41 are arranged downstream from the last Varioline element 51 . Each Vaculine element includes a fixed blade 14 arranged on stationary T-bar 55 at the front and back ends as shown. Adjustable angle blades 22 are arranged in the Vaculine element. Adjustable deckles are interposed between the fixed blades 14 and the adjustable angle blades 22 as shown. A drop leg 34 extends downward for draining purposes.
[0048] FIGS. 6A , 6 B show a detailed view of an adjustable angle blade mounted on a C-channel. Blade 22 comprises a ceramic top 22 A having a yoke 22 B formed of fiberglass reinforced composite and having an offset front side as shown. The yoke 22 B is fitted atop an adjusting mechanism 25 . An underside of the angle adjusting mechanism 25 is secured within C-channel 76 via clamping bar 77 . Protective shield 79 is provided on the blade 22 to prevent items from being caught when the adjustment mechanism 25 is actuated. The C-channel is preferably formed from stainless steel and rests atop the frame of the Fourdrinier.
[0049] FIGS. 6C , 6 D show a detailed view of an adjustable angle blade mounted on a T-bar. In this instance, the mounting means is a T-bar 55 instead of the C-channel and clamping bar of FIGS. 6A , 6 B. The adjustment mechanism and remaining parts are the same and operate in similar fashion. The respective angles and their range are also the same.
[0050] FIGS. 7A , 7 B show a detailed view of an adjustable height blade mounted on a C-channel. Height adjustable blade 13 includes an upper end having a leading and trailing edge of ceramic 13 A which is fixed in a yoke 138 preferably formed of fiberglass reinforced composite. A height adjustment mechanism 18 is arranged within the yoke 13 B. An underside of the height adjusting mechanism 18 is secured within C-channel 76 via clamping bar 77 . Protective shield 79 is provided on the blade 13 to prevent items from being caught when the height adjustment mechanism 18 is actuated. The C-channel is preferably formed from stainless steel and rests atop the frame of the Fourdrinier. The height adjustment mechanism 18 includes an adjustable T-bar 21 which extends across the Fourdrinier frame and onto which the blade 13 is attached as shown FIG. 9A . In this manner, the drive 17 A raises and lowers the T-bar 21 to adjust the height of the blade 13 in relation to an underside of the forming fabric 105 .
[0051] FIGS. 7C , 7 D shows a detailed view of an adjustable height foil blade mounted on a T-bar. In this instance, the mounting means is a T-bar instead of the C-channel and clamping bar of FIGS. 7A , 7 B. The adjustment mechanism is the same and operates in similar fashion. The respective heights and their range are also the same.
[0052] FIGS. 8A , 8 B shows an angle adjustment mechanism 25 which is a control subassembly for an angle adjustable blade 22 . A rotating T-bar 27 is formed from fiber reinforced composite and is the same length as a substructure upon which it is mounted. The angle adjustment mechanism 25 is secured atop a C-channel. The drive 17 B is indexed to rotate blade 22 over the range of angles shown in FIGS. 6A-D . The blade 22 is attached to the top side of T-bar 27 which is arranged to rotate in a clockwise or counter clockwise direction. In this manner, the angle of the blade 22 relative to the underside of the forming fabric is controlled.
[0053] FIGS. 9A , 9 B shows a height adjustment mechanism 78 which is a control subassembly for the height adjustable blade 13 . Blade 13 rests atop a T-bar having a drive 17 A that automatically raises and lowers the blade 13 to a desired height.
[0054] Tables 1 and 2 show blade angle and height settings for a paper grade with machine direction fiber alignment and a grade with cross-machine direction fiber alignment. The tables show a variety of angle adjustable and height adjustable blades which may be utilized in the respective regions of the wet end of the Fourdrinier to achieve synergistic results. It should be noted that in this instance seven blades are shown in each section with the abbreviations “H” or “A” indicating that the blade is either height or angle adjustable respectively. Moreover, the gravity units 1-3 correspond to the hydrofoil sections and are three Hydroline elements. Low vacuum units 1-3 correspond to Varioline elements. Low vacuum units 4, 5 correspond to Vaculine elements.
[0000]
TABLE 1
Machine Direction Fiber Alignment
Low
Low
Low
Low
Low
Vac-
Vac-
Vac-
Vac-
Vac-
Form-
Gravity
Gravity
Gravity
uum
uum
uum
uum
uum
ing
Unit
Unit
Unit
Unit
Unit
Unit
Unit
Unit
Blade
Board
1
2
3
1
2
3
4
5
1
H
−0.25 mm
A
−1.5°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
2
A
−0.25°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
3
H
−0.25 mm
A
−1.5°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
4
A
−0.25°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
5
H
−0.25 mm
A
−1.5°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
6
A
−0.25°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
7
H
−0.25 mm
A
−1.5°
H
−0.5 mm
A
−1.5°
H
−0.5 mm
H
−0.5 mm
H
−0.5 mm
A
−0.75°
A
−0.0°
[0000]
TABLE 2
Cross-machine Direction Fiber Alignment
Low
Low
Low
Low
Low
Vac-
Vac-
Vac-
Vac-
Vac-
Form-
Gravity
Gravity
Gravity
uum
uum
uum
uum
uum
ing
Unit
Unit
Unit
Unit
Unit
Unit
Unit
Unit
Blade
Board
1
2
3
1
2
3
4
5
1
H
−0.0 mm
A
−0.0°
H
−0.0 mm
A
−0.5°
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
2
A
−0.0°
H
−0.0 mm
A
−0.25°
H
−0.0 mm
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
3
H
−0.0 mm
A
−0.0°
H
−0.0 mm
A
−0.5°
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
4
A
−0.0°
H
−0.0 mm
A
−0.25°
H
−0.0 mm
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
5
H
−0.0 mm
A
−0.0°
H
−0.0 mm
A
−0.5°
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
6
A
−0.0°
H
−0.0 mm
A
−0.25°
H
−0.0 mm
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
7
H
−0.0 mm
A
−0.0°
H
−0.0 mm
A
−0.5°
H
−1.0 mm
H
−1.25 mm
H
−1.5 mm
A
−1.5°
A
−2.0°
[0055] It is to be understood that the invention is not limited to the exact construction illustrated and described above, but that various changes and modifications may be made without departing from the spirit and the scope of the invention as defined in the following claims. While the invention has been described with respect to preferred embodiments, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in limiting sense. From the above disclosure of the general principles of the present invention and the preceding detailed description, those skilled in the art will readily comprehend the various modifications to which the present invention is susceptible. Therefore, the scope of the invention should be limited only by the following claims and equivalents thereof.
|
An improved method for producing paper from pulp includes a plurality of subassemblies arranged in the forming or wet section of a Fourdrinier. The Fourdrinier includes a dewatering table having a plurality of blades that are static and on-the run adjustable in height and/or angle to control orientation of paper fibers in the stock to create a superior quality of paper and improved paper strength characteristics. Gravity and vacuum assisted drainage elements are equipped with on-the-run adjustable angle and height dewatering foil blades starting from a paper dryness of 0.1% and extending all the way to 5% dryness. The result of this process and machine is to improve the paper quality, save fibers and chemicals and fulfill the required paper properties.
| 3
|
FIELD OF THE INVENTION
This invention relates to apparatus and processes for washing prosthetic and other implants which require extended or repeated washing to remove preservatives or liquid reagent treatment, or both.
BACKGROUND OF THE INVENTION
Xenogeneic tissue, implant tissue from species different than the implanted species, is useful for replacing human organs damaged by pathological or physical injury. Xenografts are used for replacing heart valves, tendons, skin, blood vessels, ligaments, etc.
Xenografts are treated by several processes for cross-linking the predominate collagen to render the xenografts less susceptible to degradative mechanisms of the human system. Xenografts are preserved in sterile solutions, usually a dilute solution of glutaraldehyde or formaldehyde following treatment, during shipment and awaiting implanatation. While the apparatus and methods of this invention are not so limited, the washing of heart valve prostheses will be described to illustrate and exemplify the invention. A typical tissue heart valve prosthesis is made of a porcine heart or of membrane tissue mounted on a stent. The tissue is treated with various reagents to cross-link the collogen, alter the characteristics of the tissue, etc. and is preserved in a glutaraldehyde or formaldehyde or other solution which contains a preservative and/or bacteriostatic compound. For descriptive purposes, glutaraldehyde solutions will be discussed as exemplary, though the particular nature of the solution is not critical to the invention. It is extremely important that all of the glutaraldehyde, formaldehyde or other preservative solutions be removed from the valve before it is implanted in the patient. Some chemical treatments create the risk that some toxic responses will be encountered in sensitive individuals, even after general washing of the xenograft prior to implantation. Frolova, M. A.; Barbarash, L. S.; Gudkova, R. G. ; Carpinskaya, B. M., The Effect of Various Preservation Methods on Immunogenicity and Antigenic Composition of Xenogeneic Valve Tissue of the Heart, Byull. Eksp. Biol. Med., Volume No. 3, 1973, pp. 83-86.
The washing step has been tedious, time consuming and must be accomplished immediately before surgery. The general methods of rinsing the xenograft prior to implantation have not substantially decreased the risk of toxic response by completely removing the preservative. The present invention is designed to provide a system for complete washing of valve and graft tissues with a maximum of efficiency and a minimum of inconvenience and time.
SUMMARY OF THE INVENTION
The invention is a system for washing heart valve prosthesis, xenografts and other implants which require extended or repeated washing to remove a preservative and/or to pre-treat the prosthesis immediately before implantation.
The system typically includes a number of disposable containers of saline solution, or other wash solution. Sterile polyethylene or other polymeric containers are readily available and are conveniently used in this invention. Flow of wash solution from the containers controlled by a valve or a series of valves through a sterile filter and then through the wash chamber containing the prosthesis thoroughly washes the prosthesis many times and removes all soluble constituents of the preservative medium. The effluent from the wash chamber passes through a reaction chamber, controlled by suitable valves, which comprises a detection device for determining the presence or absence of preservatives in the effluent wash solution, thus permitting the operator to be certain that the xenograft has been thoroughly washed and that all preservative has been removed. The detection device may include any of several chemical and instrumental analytical systems and apparatus, such as, for example, a photometer, membrane electrode, polarimeter, oxidation-reduction cell, or indicator solution. The specific method for detecting the absence of presence of the preservatives is not critical. For example, an indicator for aldehydes may be metered into a reaction chamber, providing a color change based on the presence of aldehydes. Another sterile filter may be provided in the effluent line as the effluent wash solution is drained to a suitable waste disposable system. These filters assure the continued sterility of the system. The sterile filters can be checked to assure that no bacteria or other organisms have entered into the system.
The flow in the wash chamber is preferrably directed to flow over all of the surfaces of the heart valve or graft which is to be washed. The heart valve or other tissue prosthesis can be washed with very little attention, and with a high degree of confidence that the washing is complete.
The wash chamber is preferrably designed as a shipping and storage package functioning to preserve as well as wash the heart valve prosthesis. In a preferred form the wash chamber comprises a funnel with specific prosthesis supports designed to support the particular prosthesis in a configuration which will permit the fluid to wash all surfaces and a cap having means configured to direct the flow of the wash solution over the prosthesis. In a preferred form, a filter cloth surrounds the prosthesis and breaks down any jets of wash solution and difuses the flow over the surfaces of the prosthesis. The cap and funnel are constructed and configured to provide a relatively high velocity, low instantaneous volume fluid flow around the valve and through the sewing ring.
The invention is, in its preferred configuration, an integral package functioning as a storage and wash chamber, which may include a built-in recirculating pump to increase the efficiency of the washing and/or treating of the prosthesis. The heart valve prosthesis is placed within the chamber, which is filled with a suitable preservative solution. Seals close the top and bottom conduits of the chamber, which are configured to be connected to tubing, valves, etc. to complete the system. The chamber thus formed by the funnel and cap is enclosed in a heat sealable polyethylene or other polymeric material pouch to provide physical protection, and to serve as a tamper indicator and dust/lint protector and to maintain sterility. The pouch is then, typically, placed in an expanded polystyrene shell for shock protection and to moderate temperature extremes during shipping.
The prosthesis is prepared for implantation by removing the cap seals, draining the storage solution, and connecting the wash chamber to tubes to which are connected to allow the flow of saline solution through the chamber and over the prosthesis. In the preferred embodiment, a built-in recirculationg pump, fully prepared to run and supplied with batteries, may be turned on immediately without further preparation. The heart valve prosthesis is maintained in its proper washing configuration in the wash chamber to prevent damage before implantation. The prosthesis is then ready to be implanted without risk of a toxic reaction due to the presence of preservatives. The wash solution may perform the additional function of coating or treating the prosthesis with any desired reagent immediately before the prosthesis is implanted. Some or all of the wash solution may contain the treating reagent. For example, the final wash phases of the process may very desirably include the step of flowing a solution carrying epithelial cells for coating the prosthesis with the epithelial cells immediately before the prosthesis is implanted in the patient.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic diagram of the xenograft washing system of this invention.
FIG. 2 is an exploded side view of the wash chamber of this invention.
FIG. 3 is a partially cut away side view of the packaged wash chamber of this invention.
FIG. 4 is a side view, partially cut away and in partial cross-section showing the wash chamber of the invention unitarily associated with a recirculating pump.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention is described using as an example a porcine heart valve prosthesis, with the understanding that any prosthetic device which requires washing before use is contemplated within the scope of the invention.
Referring to FIG. 1, the system of the invention comprises one or more disposable containers 11, 12 and 13 of sterile wash solution, typically saline, one or more of which contain one or more treating reagents. For example, container 13 may typically contain suspended epithelial cells for coating the prosthesis. In general, reference will be made to "ash solutions" with the understanding that the solutions may be reagent solutions as well. The containers are designed to be suspended from a typical hospital hanger. Valves 14, 15 and 16 control the flow from the respective containers, permitting the use of one or more containers seriatim until a complete wash is accomplished. A master flow rate control valve 17 permits the operator to adjust the rate of flow through the chamber. A sterile filter 18 is desirably provided to provide additional assurance that the fluid entering the wash chamber 19 is perfectly sterile. If sterility is assured, and if particular types of reagents are to be included in some or all of the wash solution, the filter may be bypassed or omitted. For example, a valve 17a may open a bypass conduit to the wash chamber. A porcine heart valve 20 is mounted in the wash chamber on suitable supports to assure that it is in the proper configuration for use and to assure that the fluid flow will be uniform over the surface of the prosthesis being washed.
While the invention is illustrated as washing a porcine heart valve, the invention is equally applicable to washing and/or coating or treating other prosthetic devices, e. g. veins, arteries, and other tissue taken from pigs, other animals, or humans, all of which are known to be useful for implantation in humans. Human umbilical cords, for example, have been used as arterial grafts after fixation in glutaraldehyde. Similarly porcine and bovine arteries, and veins, have also been suggested for use as arterial grafts.
The effluent from the wash chamber passes, in a preferred embodiment, through a filter 21 and a ball-check or other non-return check valve 22 to assure that no liquid can be forced or sucked back into the heart valve chamber. Valves 23a nd 23b on the inlet and outlet of a reaction chamber 24 control flow through and permit isolation of the reaction chamber 24. An indicator containing solution is provided in the indicator container 25 and metered through a valve 26 into the reaction chamber 24. There are a number of indicators which may be used to permit detection of the presence or amount of various reagents. For example, where removal of glutaraldehyde is important, as is generally the case, several indicators react with aldehyde to provide a color reaction which is proportional to the amount of aldehyde present. Aldehydes will react, for example, with 2,4-dinitrophenylhydrazine to form an insoluble yellow or red solid. Aldehydes give a positive reaction with Tollens' reagent. Tollens' reagent contains the silver ammonia ion. Oxidation of the aldehyde is accompanied by reduction of the silver ion to free silver in the form of a mirror under proper conditions. Aldehydes are oxidized by oxidizing agents such as chromic anhydride and aqueous sulfuric acid. The clear orange solution formed by the combination of chromic anhydride and aqueous sulfuric acid turns blue-green and becomes opaque with the addition of aldehyde. A highly sensitive test for aldehydes is the Schiff test, in which an aldehyde reacts with the fuchsin-aldehyde reagent to form a characteristic magenta color. Typically a negative reaction with the above indicators is shown by no color change. The chamber 24 preferably includes transparent walls to permit visual detection of colored species or silver in the above examples. Instrumental detection of, for example, redox potential may also be used.
While the previous example depicts an indicator chamber and reaction chamber as well as a indicator solution to determine the presence of preservatives, other effective devices such as a polarimeter, oxidation-reduction cell, membrane electrode, or other means can be used to determine the presence of preservatives on or within the heart valve prosthesis.
As shown in greater detail in FIG. 2 the wash chamber is in the form of a heart valve support and container comprising a removable cap 27, connected to a funnel 28. The cap is provided with protuberances 29 and 29A which are received and rotated in the slots 30 and 30A to form a bayonet lock. A threaded or other type of connection can be used also, but the bayonet type interlocking mechanism is convenient, secure and easily connected and opened. The cap has finger grips 31 to facilitate the locking and unlocking of the cap with the funnel. The heart valve prosthesis 20 is placed in the large end of the funnel 32 on supports to assure the proper configuration of the valve and permit reasonably uniform flow of fluid over the valve. The particular support will be configured, dimensioned and constructed according to the configuration of the particular prosthesis being shipped, stored and washed. A filter cloth 33 optionally surrounds the prosthesis 20, breaking down any fast jets of wash solution and assuring a diffuse flow of solution over all surfaces of the prosthesis. The cap, which is the inlet portion to the wash chamber, is designed to cause the wash solution to flow in a relatively high velocity flow, with low volume over all surfaces of the prosthesis, thus providing a continuing source of fresh wash solution to assure that the concentration differential between the solution on and in the tissue and the wash solution is maximum and thus maximize the migration of preservative from the tissue to the wash solution.
A high velocity, relatively thin layer and low volume of the wash solution is formed by the inner walls of the funnel around the valve. Tube connectors 34, on the funnel, and 35 on the cap are configured, constructed and adapted to be connected to tubes from the containers saline wash solution.
FIG. 3 depicts the wash chamber, which also serves to contain the prosthesis and protect it during shippment and storage, as part of an integral package protected against extremes of temperature and shock. The heart valve prosthesis 20 is placed wash chamber and covered by storage preservative solution, indicated at 36. Cap seals 37 and 38 are placed on the connecting devices 34 and 35 to maintain the storage solution in the heart valve rinser. The rinser is placed in a heat sealable polyethylene pouch 39. The pouch is sealed to serve as a tamper indicator and dust/lint protector and to maintain sterility. The pouch and rinser are placed in a expanded polystyrene shell 40 which prevents rapid and extreme changes in temperature during temporary shipment and as a protection against shock and physical damage. The expanded polystyrene shell is then placed in a corrugated carton 41 for shipment and storage.
Reference is now made to FIG. 4 in connection with FIGS. 2 and 3. A preferred embodiment of this invention which includes a built-in recirculation system is depicted in FIG. 4. The wash chamber in FIG. 4 is identical to that shown in FIGS. 2 and 3 with the addition of inlet and outlet conduits for recirculation. Cap 127 and funnel 128 interlock using a boss 129 in a bayonet connector, have fluid conduit connectors 134 and 135 and caps 137 and 138 all as described above respecting the corresponding elements 27, 28, 29, 34, 35, 37, and 38, except as described below. The funnel 128 is provided with a conduit 152 which provides fluid communication into a pump chamber 154 and back through a conduit 156, a portion of which 156a is formed as part of the cap 127, into the wash chamber. Alternatively, the conduit 156 may bypass the cap 127 and connect directly back into the funnel 128. An impeller 160 is mounted in the pump chamber 154 and is connected to a motor 162 driven by a battery 164, or a plurality of batteries, the entire pump drive assembly being packaged in a housing 166. A slide switch 168 is mounted in the housing for turning the motor on and off. Any reliable switch may be used. As is the case in the previous embodiments, the wash chamber, including in this case the built in recirculation pump, is enclosed in an airtight envelope 170 which, in turn, is packaged against shock and physical damage by packing 172 and a case 174 which may be of the type previously described or of any other suitable type.
The system of this invention is most conveniently shipped together with all components and reagents in two, or more, packages marked to identify a complete system. The wash chamber and prosthesis contained therein is typically shipped in a separate container, because of the need to have various sizes and types of prosthesis on hand. Thus, for example, a complete system would include in one container of the type shown in FIGS. 3 or 4 the implant prosthesis in a wash chamber and in another container one or more, typically three, containers of wash solution, the valves, tubing, chambers, filters and reagents necessary to complete a system as schematically depicted in FIG. 1. All of the components are typically pre-sterilized and sealed in tamper proof or tamper indicator packages, or in packages which permit sterilization by the hospital.
In or adjacent the operating room, the system is assembled as indicated in FIG. 1, the solution from the first container is caused to flow by gravity or pumping over the prosthesis. Periodic checks, at different periods depending upon the prosthesis and nature and concentration of the preservative solution, are made using the indicator means described to monitor the preservative content of the effluent of the wash chamber. As needed, the wash solution from the various containers is caused to flow over the prosthesis until the effluent tests absolutely free of the preservative, or the level is low enough to assure that no adverse physiological reaction will occur. In some instances, the configuration of a prosthesis may be constant enough to provide an impirical basis for determining that a complete wash is accomplished when a predetermined volume of wash solution has been caused to flow over the prosthesis.
Higher washing and/or treating efficiency is provided using the recirculation pump, especially during washing. One of the containers, e. g. container 13 may contain epilethial cells or other treating cells and/or reagents, which will be cause to flow over the prosthesis after washing is complete or essentially complete for pre-treating the prosthesis by coating, reaction or otherwise.
Industrial Application
This invention finds application in the surgical arts.
|
A packaged prosthesis and a system and method for washing prosthetic and other implants with a biologically compatible wash solution prior to implantation, which allows for complete washing of valve and graft tissue to remove preservatives used to store the tissue grafts and or treat the same, having containers containing the wash solution, a sterile filter in fluid communication with these containers, a valve to the sterile filter to control the flow of wash solution from the containers to the sterile filter and a wash chamber, in fluid communication with the sterile filter, for positioning the prosthesis or tissue implant to permit wash solution to flow freely over and wash the same are disclosed.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
The present invention claims priority to U.S. Provisional Application Ser. No. 60/475,558 filed Jun. 3, 2003.
TECHNICAL FIELD
The present invention relates to hydrogen gas sensors and, more particularly, to hydrogen gas sensors and switches that utilize metal nanowires.
BACKGROUND INFORMATION
Like any fuel, hydrogen stores large amounts of energy, and handling hydrogen requires safety precautions. As the use of hydrogen fuel becomes more common, there will be an increased need for reliable hydrogen sensors. Hydrogen is now used in the transportation, petrochemical, food processing, microchip, and spacecraft industries. Each of these industries needs reliable hydrogen sensors for many applications, for example, pinpointing leaks to prevent the possibility of explosions in production equipment, transport tanks, and storage tanks. Advances in fuel cell technology will provide numerous future applications for hydrogen sensors.
Hydrogen sensors, in some instances, could be used to warn of an imminent equipment failure. Electrical transformers and other electrical equipment are often filled with insulating oil to provide electrical insulation between energized parts. The presence of hydrogen in the insulating oil can indicate a failure or potential explosion. Hydrogen sensors could be utilized both under the insulating oil and in the air immediately above the insulating oil. Therefore, closely monitoring hydrogen levels in and around equipment containing insulating oil could be an effective tool in predicting and preventing equipment failure.
As fuel cell technology advances, fuel cells will see greater use as power sources for both vehicles and homes. Since hydrogen can be a highly explosive gas, each fuel cell system needs hydrogen detectors to sense and alarm in the event of a hydrogen leak. Hydrogen detectors can also be placed inside a fuel cell to monitor the health of the fuel cell. Hydrogen sensor packages are also needed to monitor hydrogen concentration in the feed gas to fuel cells for process control.
Hydrogen sensor packages in fuel cells require high sensitivity. Such sensor packages should have a wide measurement range spanning from below 1% up to 100% hydrogen. The measurement range is dependent on which fuel cell technology is used and the status of the fuel cell. Detectors are needed also to monitor for leaks in the delivery system. For transportation and other portable applications, hydrogen detectors operating in ambient air are needed to ensure the safety of hydrogen/air mixtures and to detect hydrogen leaks before they become a hazard. At high hydrogen concentration levels, issues associated with the potentially deteriorating effect on the oxygen pump operation must be addressed. Finally, hydrogen sensors must be highly selective in monitoring hydrogen in ambient air.
There are many commercially available hydrogen sensors, however, most of them are either very expensive or do not have a wide operating temperature range. Additionally, most sensors sold today have heaters included with the sensor to maintain elevated operating temperatures, requiring high power consumption that is undesirable for portable applications.
Favier et al. pioneered the use of palladium nanowires in 2001 by producing a demonstration hydrogen detector. The disclosure of Favier et al. can be read in an article published in Science, Vol. 293, Sep. 21, 2001. Hydrogen sensors prepared by this method have incredible properties due to the nature of the chemical/mechanical/electrical characteristics of the nanotechnology of palladium nanowires. The hydrogen sensors operate by measuring the conductivity of metal nanowires arrayed in parallel. In the presence of hydrogen gas, the conductivity of the metal nanowires increases.
The alpha-to-beta phase transition in the nanowire material is the mechanism for operation of these sensors. There is first a chemical absorption of hydrogen by the palladium nanocrystals of the nanowire. This causes expansion of the lattice by as much as 5-10%, causing the palladium nanocrystals that were initially isolated from each other to touch and form an excellent low-resistance wire.
However, there are many drawbacks to systems as produced and disclosed by Favier et al. A lack of complete characterization of the palladium nanowires has limited the understanding of those devices. Also, the Favier et al. method and apparatus utilizes nanowires that are electrochemically prepared by electrodepositon onto a stepped, conductive surface such as graphite. This presents a problem because nanowires prepared on conductive surfaces are required to be transferred off of the conductive surface so that the conductivity of the nanowire array can be measured more readily. Such transfers of nanowires cause degradation of hydrogen sensing at higher temperatures. In summary, the major issues with pure palladium nanowires prepared on step edges of graphite are: (1) unpredictable formation of palladium nanowires; (2) narrow temperature range of operation; and (3) narrow range of sensitivity to hydrogen concentration.
As a result, there is a need in the art for an apparatus and method for (1) predictably forming palladium and palladium alloy nanowires; (2) increasing the temperature operating range of sensors; and (3) increasing the range of hydrogen concentrations that can be measured.
SUMMARY OF THE INVENTION
The present invention is directed to an improved method and apparatus for sensing hydrogen gas. An embodiment comprises the steps of depositing an insulating layer onto a silicon substrate, depositing a metal layer on the top surface of the insulating layer, and depositing a plurality of nanoparticles onto the side-wall of the metal layer. In an embodiment, the metal layer may be removed.
Another embodiment of the present invention is directed to a hydrogen sensing apparatus comprising nanoparticles deposited on a substrate to form one or more nanoparticle paths which conduct electricity in the presence of hydrogen and wherein the nanoparticles were formed in close proximity to the substrate and not transferred off of a conductive substrate.
Another embodiment of the present invention is directed to a method of sensing hydrogen including depositing a first layer of material onto a second layer of material, depositing a metal layer on the second layer of material, depositing a third layer of material on the metal layer, removing a portion of the metal layer to expose one or more side-walls of the metal layer, depositing nanoparticles on the side-walls of the metal layer, and sensing a change of resistivity of the nanoparticles when they are exposed to hydrogen.
An embodiment of the present invention is directed to a palladium-silver alloy nanowire technology that eliminates the (1) unpredictable formation of palladium nanowires; (2) narrow temperature range of operation; and (3) narrow range of sensitivity to hydrogen concentration. A basis of the present invention is the ability to co-deposit palladium and palladium-silver alloy nanoparticles or nanowires electrochemically on a patterned surface without the need for a transfer process.
The present invention operates by measuring the resistance of many metal nanowires arrayed in parallel in the presence of hydrogen gas. The present invention may also operate by, in the presence of hydrogen, measuring the resistance of nanowires deposited as a film. The nanowires or nanofilm contain gaps that function as open switches in the absence of hydrogen. In the presence of hydrogen, the gaps close and behave like closed switches. Therefore, the resistance across an array of palladium or palladium alloy nanowires or nanofilm is high in the absence of hydrogen and low in the presence of hydrogen.
The nanowires or nanofilm are typically composed of palladium and its alloys. One of ordinary skill recognizes that any other metal or metal alloy having a stable metal hydride phase such as copper, gold, nickel, platinum and the like may also be used. Herein the use of the term “path” is meant to encompass nanowires, nanofilm, and/or any potentially electrically conductive path.
In the prior art, nanowires were electrochemically prepared by electrodepositon onto a stepped surface such as graphite. The nanowires were then transferred off of the graphite onto a polystyrene or cyanoacrylate film. The transfer process contributed to a decrease in sensitivity and operating range for hydrogen sensors. It is an object of the present invention to increase sensitivity and operating range of the hydrogen sensors by dispensing with the need to transfer nanowires during fabrication.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
FIG. 1 is an image from a scanning electron microscope (SEM) of a nanoparticle thin film;
FIG. 2 is an SEM image of 300 nm palladium nanowires prepared by side-wall-electroplating technique;
FIG. 3 is a graph of hydrogen sensor responses at varying hydrogen concentrations at 70° C.;
FIG. 4 is a graph of hydrogen sensor responses at varying hydrogen concentrations at 70° C.;
FIG. 5 a is a schematic representation of one embodiment of the present invention;
FIG. 5 b is a graph of hydrogen sensor responses at 100° C. with hydrogen concentrations of 0.5%, 1.5%, and 2%;
FIG. 5 c is a graph of hydrogen sensor responses during 5 cycles of testing at 1% hydrogen concentration at 120° C.;
FIG. 6 a is a schematic representation of one embodiment of the present invention;
FIG. 6 b is a graph of responses for the hydrogen sensor from FIG. 6 a at room temperature at varying levels of hydrogen as shown;
FIG. 6 c is a graph of responses for the hydrogen sensor from FIG. 6 a at 70° C. at varying levels of hydrogen as shown;
FIG. 6 d is a graph of responses for the hydrogen sensor from FIG. 6 a at room temperature at varying levels of hydrogen as shown;
FIG. 7 a is a schematic representation of another embodiment of the present invention;
FIG. 7 b is a graph of responses for the hydrogen sensor from FIG. 7 a at room temperature at varying levels of hydrogen as shown;
FIG. 7 c is a graph of responses for the hydrogen sensor from FIG. 7 a at 120° at varying levels of hydrogen as shown;
FIG. 8 a is a schematic representation of an early stage of fabrication of an embodiment of the present invention;
FIG. 8 b is a schematic representation of an intermediate stage of fabrication of an embodiment of the present invention;
FIG. 8 c is a schematic representation of a final stage of fabrication of an embodiment of the present invention;
FIG. 8 d is a schematic representation of an embodiment of the present invention configured into an array of nanowires;
FIG. 8 e is a graph of test results from an embodiment of the present invention tested at varying hydrogen levels and 103° C., 136° C. and 178° C.;
FIG. 9 is a schematic representation of an embodiment of the present invention;
FIG. 10 a is an illustration of hydrogen sensors used for automobile applications;
FIG. 10 b is an illustration of hydrogen sensors within a fuel cell;
FIG. 10 c is an illustration of hydrogen sensors used for transformer applications; and
FIG. 10 d is an illustration of hydrogen sensors used for home applications.
DETAILED DESCRIPTION
In the following description, numerous specific details are set forth such as specific alloy combinations, etc. to provide a thorough understanding of the present invention. However, it will be obvious to those skilled in the art that the present invention may be practiced without such specific details. Some details have been omitted in as much as such details are not necessary to obtain a complete understanding of the present invention and are within the skills of persons of ordinary skill in the relevant art.
Refer now to the drawings wherein depicted elements are not necessarily shown to scale and wherein like or similar elements are designated by the same reference numeral through the several views.
The present invention is directed to an improved apparatus and method for sensing hydrogen gas. The addition of silver to the palladium nanowires significantly increases the operating temperature range of the sensor. The incorporation of silver with palladium also addresses the issue of sensitivity of the nanowires to different levels of hydrogen concentrations. Pure palladium nanowires typically do not provide enough sensitivity to allow detection over a large range of hydrogen concentrations. At room temperature, pure palladium nanowires are able to detect a concentration of about 2% hydrogen. At higher temperatures, pure palladium wires require a higher concentration of hydrogen for detection. However, the incorporation of silver in palladium nanowires provides a greater range of detection suitable to make hydrogen sensors.
The substrate for an embodiment can be any insulating surface such as polymer, glass, silicon, or silicon nitride. A thin layer of titanium is deposited onto the substrate to form a conductive area for electroplating. A photoresist pattern is prepared on the top of the substrate by lithography. Palladium or palladium-silver alloy nanoparticles/nanowires are then electroplated on the exposed titanium surface. The palladium electroplating bath contains 1 mM PdCl 2 , 0.1 M HCl in water. The palladium-silver electroplating bath contains 0.8 mM PdCl 2 , 0.2 mM AgNO 3 , 0.1 M HCl, 0.1 M NaNO 3 , and 2 M NaCl in deionized water. The nanoparticles/nanowires are deposited at −50 mV vs SCE for 600 sec with one second large overpotential pulse (−500 mV vs SCE). FIG. 1 shows an image of a nanoparticle thin film that consists of nanoparticles with a 100 nm diameter. FIG. 2 shows an image of 300 nm palladium nanowires prepared by side wall technique.
FIG. 3 and FIG. 4 show the response of a palladium-silver alloy hydrogen sensor at 70° C. for varying hydrogen concentrations over time. Note that the devices are essentially OFF when no hydrogen is present and palladium alloy-nanocrystals in the device act as an “open circuit” with very-high resistance. When the device is exposed to hydrogen, the palladium alloy-nanocrystals in the device touch each other through expansion of the lattice. This causes any nanogaps in the wires to close (ON state) and the nanowires behave as a “short circuit” with very-low resistance. The sensors have a highly desirable characteristic in that the sensors require essentially zero power in the absence of hydrogen. The sensor acts like an open circuit in the absence of hydrogen and only draws a small amount of power when an alarm condition occurs. This is the ideal situation for a good hydrogen detector: OFF in the absence of hydrogen, and ON only when hydrogen is present.
Turning to FIG. 5 a , a particular embodiment of making a hydrogen sensor involves evaporating a 1000 Å layer 302 of titanium onto a polymide film 300 such as Kapton. One of ordinary skill in the art will recognize that any insulating material such as glass or silicon may be substituted for Kapton. Next, a photoresist (not shown) is patterned on the titanium layer 302 in a well-known manner. A layer 304 of nanoparticles of palladium-silver alloy are then electroplated onto the surface. The device is heated to 500° C. for 2 hours in air to oxidize the titanium layer. FIG. 5 b displays test results for this embodiment at 100° C. In this test, an exemplary sensor of the instant embodiment was tested for 3 cycles with hydrogen concentrations of 0.5%, 1.5%, and 2%. FIG. 5 c displays results for tests at 120° C. with 1% hydrogen concentrations. FIG. 5 c illustrates that the sensor did not degrade after 5 cycling tests.
Another embodiment of the present invention is depicted schematically in FIG. 6 a . In this embodiment, a 5000 Å layer 602 of SiNx is deposited on a silicon substrate 600 . A layer 604 of 1000 Å thick titanium is then deposited on layer 602 . Using lithography, a pattern (not shown) is created on the substrate. A thin film 606 of palladium-silver nanoparticles is electroplated to layer 604 . In one example of the instant embodiment, the palladium-silver alloy was electroplated at 300 μA for 1 second and 20 μA for 600 seconds. Next, oxidizing the titanium 604 forms TiO 2 . In one example, the titanium was exposed to 500° C. air overnight. Following oxidation of the titanium, another layer 608 of palladium-silver is deposited to layer 606 . In one example, palladium-silver was electroplated at 300 μA for 1 second and 20 μA for 200 seconds.
FIGS. 6 b - 6 d illustrate results achieved by testing the exemplary embodiment as depicted in FIG. 6 a . FIG. 6 b illustrates test results performed at room temperature. The device was first tested at room temperature with hydrogen concentrations ranging from 0.5% to 4%. The voltage applied was 0.1V. The current was about 3E-6A with no hydrogen present. The current rose to 7E -6A at 0.5% hydrogen and 1E-5A at 1% hydrogen. The response was slowly saturated at around 3% hydrogen concentration with a current of 1.2E-5A, about 400% of the current at OFF state.
FIG. 6 c illustrates test results performed at 70° C. for the exemplary embodiment as depicted in FIG. 6 a . At 120° C., the sensor did not respond to hydrogen. The results shown in FIG. 6 c were achieved after slowly reducing the temperature from 120° C. to 70° C. FIG. 6 c illustrates that the sensor was essentially non-operational when the temperature was raised to 120° C., but the sensor regained its operation when the temperature was reduced to 70° C.
FIG. 6 d illustrates test results for the embodiment depicted in FIG. 6 a after cooling the device from 70° C. to room temperature. The device responded to hydrogen with similar magnitude as the previous test at room temperature, illustrated in FIG. 6 b . In the OFF state, the device had a current of about 1.5E-6A . In the ON state, the current was about 7E -6A at 4% hydrogen. This result showed about 400% change in magnitude between OFF and ON states. The difference in current of the OFF state before and after high temperature testing might indicate some degradation, but the relative changed in resistance (400%) was about the same.
The embodiment depicted in FIG. 6 a provides a way to prepare a hydrogen sensor without using the transfer method. However, unlike using Kapton, the tested device did not work at 120° C. In fact, the sensitivity of the sensor decreased as the temperature increased. Nevertheless, the sensor showed good sensitivity at room temperature with more stable and less noisy response curves.
Another embodiment of the present invention is shown schematically in FIG. 7 a . FIG. 7 a shows a silicon substrate 700 deposited with 5000 Å of SiNx, forming layer 702 . Next, 200 Å of titanium is deposited to form layer 704 . A layer 706 of palladium-silver is electroplated to titanium layer 704 . In an example of the instant embodiment, palladium-silver was electroplated at 300 μA for 1 second and 20 μA for 600 seconds. Test results of an example of the instant embodiment are illustrated in FIG. 7 b . The results in FIG. 7 b were achieved at room temperature. A second experiment performed at 120° C. yielded the results shown in FIG. 7 c . Although at 120° C. the change between OFF state to ON state was not very large, the device from this embodiment was able to detect hydrogen at 0.5% concentration both at room temperature and 120° C.
Another embodiment of the present invention is depicted schematically in FIGS. 8 a - 8 e . In this embodiment, SiO 2 is deposited on a silicon substrate 800 to form a 5000 Å layer 802 of SiO 2 One of ordinary skill in the art recognizes that SiNx or other suitable materials may be substituted for SiO 2 . Titanium 200 Å thick is deposited to form layer 804 . Next, the photoresist 806 is deposited on the substrate and patterned by photolithography leaving the assembly substantially as depicted in FIG. 8 b , with layer 804 having two side-walls. Nanowires 808 made from palladium-silver alloys are then electroplated onto the side-walls of the titanium 804 . In one example of the instant embodiment, palladium-silver was electroplated using a side-wall plating technique at 300 μA for 1 second and 20 μA for 600 seconds. Since the sidewall of the metal is the only place exposed to the electrolytic bath, the palladium-silver will be deposited on the sidewall only and form the nanowires at the edge of the metal lines. Next, the remaining titanium 804 is etched away, leaving the assembly as shown in FIG. 8 c . Alternatively, the titanium 804 could be oxidized at high temperature or left on the substrate. The sensor is functional without removing the metal layer, but has a low S/N ratio. The removal of the metal layer provides higher S/N ratio.
The side-wall plating technique for an embodiment as shown in FIG. 8( c ) and operational at high temperatures can be accomplished as follows: the substrate can be used as a working electrode in a three-electrode plating system with a saturated calomel electrode (SCE) as the reference electrode and platinum wire as the counter electrode. Using conventional electrochemical deposition/plating, the three electrodes can be immersed in a palladium silver alloy plating solution bath solution consisting of 2.5 mM of PdCl2, 0.5 mM of AgNO 3 , 0.05 M of NaNO 3 , 0.05 M of HCl, and 2 M (20 g in 100 mL) of NaCl in water. A standard electrochemical program, namely chronopotentiometry can be used for this process. For formation of the nanowires on the substrate, the electrochemical plating conditions can be as follows: using a pure palladium plating bath, apply −300 μA for 10 sec, then apply −20 μA for 450 sec. After electroplating, the substrate can be immersed in acetone, followed by IPA and water to remove the photoresist on the surface.
The side-wall plating technique for an embodiment as shown in FIG. 8( c ) and operational at room temperature can be accomplished as follows: the substrate can be used as a working electrode in a three-electrode plating system with a saturated calomel electrode (SCE) as the reference electrode and platinum wire as the counter electrode. Using conventional electrochemical deposition/plating, the three electrodes can be immersed in a pure palladium plating bath consisting of 1 mM of PdCl 2 and 0.1 M HCl in water. A standard electrochemical program, namely chronopotentiometry can be used for this process. For formation of the nanowires on the substrate, the electrochemical plating conditions can be as follows: using pure palladium plating bath, apply −300 μA for 10 sec, then apply −20 μA for 450 sec. After electroplating, the substrate can be immersed in acetone, followed by IPA and water to remove the photoresist on the surface.
FIG. 8 d depicts an embodiment created by patterning the substrate using photolithography to electroplate multiple nanowires 808 to the side-walls of titanium strips 804 . FIG. 8( d ) is made in the similar fashion as outlined in 8 ( a ) to 8 ( c ); however, FIG. 8( d ) shows multiple nanowires arranged in an array. A hydrogen sensor is utilized by connecting conductors to the ends of the array of nanowires which electrically connects the nanowires in parallel. In an embodiment, silver paste is applied to the ends of the array of nanowires and separate wires are connected to the silver paste on each end. A voltage is then applied across the parallel nanowires, and the resultant current is measured to determine whether there is hydrogen present. Using palladium-silver alloy nanowires, the current is higher in the presence of hydrogen than in the absence of hydrogen.
The particular embodiment as described in FIG. 8 d can be fabricated as follows: 5000 Å SiO 2 , item 802 , is deposited on a 4 inch silicon wafer, item 800 , using a E-beam evaporator followed by a layer of 200 Å titanium, item 804 . The substrate is then coated with a photoresist hexamethylenedisilane (HMDS) for 30 seconds at 700 RPM followed by a positive photoresist for 90 seconds at 3000 RPM. The substrate is then exposed under UV light with a homemade H-Sensor 5 mm line mask (not shown) for 25 sec and further developed by photoresist developer diluted for 40 seconds. The substrate is then rinsed with water for 30 minutes, dried using a blow drier, and heated in an oven for 10 minutes at 120° C. The titanium layer not covered by the photo resist is then etched away by a titanium etchant, exposing the sidewall of the titanium layer over the entire substrate. The pattern is exposed under UV with homemade mask (not shown) for 25 seconds after proper alignment of the sensor pattern. The substrate is then developed by 400 K developer diluted for 40 seconds. The substrate is then rinsed with water for 30 minutes, dried using a blow drier, and heated in an oven for 10 minutes at 120° C.
The sidewall plating technique is then used to electroplate the nanoparticles 808 onto the substrate. After electroplating, the substrate is immersed in acetone followed by IPA and water to remove the photoresist from the surface. In an embodiment, the nanowires 808 are separated from the titanium 804 without removing them from 802 .
FIG. 8 e shows the results from testing an example of the embodiment as depicted in FIG. 8 c . The test began at room temperature. The temperature was increased to 103° C., then 136° C., and then 178° C. As the temperature increased, the current increased due to the larger thermal expansion coefficient of palladium-silver compared to SiNx. The palladium-silver nanowires 808 expanded faster than the substrate and the resistance lowered. With the test chamber at 103° C., the sensor was tested with hydrogen concentrations of 0.25%, 1.0%, and 4.0%. As FIG. 8 e shows, the sensor responded to each concentration level. The device was functional even at 178° C.
FIG. 9 a - 9 b depicts another embodiment of the present invention. The embodiment of FIG. 9 a - 9 b produces response curves typical of other embodiments described herein, but the embodiment in FIG. 9 a - 9 b is suitable for fabricating hydrogen sensors to be operable both in ambient air and under oil, such as transformer oil.
The embodiment of FIG. 9 a - 9 b can be fabricated using photolithography as follows: First, a 5000 Å layer 912 of silicon nitride is deposited on a 4 inch silicon wafer 900 using a E-beam evaporator followed by a layer 902 of 200 Å titanium. The substrate is then coated with a photoresist hexamethylenedisilane (HMDS) for 30 seconds at 700 RPM followed by a positive photoresist for 90 seconds at 3000 RPM. The substrate is then exposed under UV light with homemade H-Sensor 5 mm line mask (not shown) for 25 sec and further developed by photoresist developer diluted for 40 seconds. The substrate is then rinsed with water for 30 minutes, dried using a blow drier, and heated in an oven for 10 minutes at 120° C. A layer 904 of 100 Å chromium and 300 Å gold, item 906 , is deposited using E-Beam. In an embodiment, the resistance of the substrate can be measured to be less than 10 ohms. The photoresist is lifted off using appropriate stripper followed by heating in oven for 30 minutes at 90° C. and subsequent drying.
The substrate is then coated with a photo resist 908 for 30 seconds at 700 RPM followed by positive photoresist for 90 seconds at 3000 RPM. The pattern is exposed under UV with homemade mask (not shown) for 25 seconds after proper alignment of the sensor pattern. The substrate is then developed by photoresist developer diluted for 40 seconds. The substrate is then rinsed with water for 30 min, dried using a blow drier, and heated in an oven for 10 minutes at 120° C. A plating technique is then used to electroplate the nanoparticles 910 onto the substrate. Note, in an embodiment the sidewall plating technique is not used because the titanium is not etched in this process. After electroplating, the substrate was immersed in acetone, followed by IPA and water to remove the photoresist on the surface.
FIGS. 10 a - 10 d show various applications for the present invention. FIG. 10 a depicts an application for utilizing hydrogen sensors to monitor hydrogen levels inside a vehicle and within a fuel cell. Sensors in the vehicle cabin monitor to ensure that dangerous concentrations of hydrogen do not create an unsafe condition for drivers and passengers. Sensors within the fuel cell ensure proper operation and health of the fuel cell. FIG. 10 b represents a fuel cell used to monitor the health of the fuel cell. The hydrogen sensor is placed to ensure proper hydrogen levels in the intake and to monitor the hydrogen level in the exhaust.
Similarly, FIG. 10 d depicts an application for monitoring hydrogen concentration in and around a home utilizing a fuel cell. Hydrogen sensors in the home monitor for dangerous levels of hydrogen to protect occupants by preventing explosive buildups of hydrogen.
FIG. 10 c depicts yet another application for hydrogen sensors in power equipment. As discussed previously, power transformers and switching equipment are often filled with insulating oil. A breakdown or contamination of the insulating oil can cause short circuits and lead to dangerous explosions and fires. Some potential failures are predicted by monitoring for buildups of hydrogen and other gases in the transformer oil. FIG. 10 c shows a hydrogen sensor placed under the insulating oil of a transformer. Another sensor could be placed above the oil to monitor hydrogen levels. One of ordinary skill in the art recognizes that hydrogen sensors may also be placed in any application where a buildup of hydrogen signals a dangerous condition.
The present invention relates to using palladium-silver alloy thin film (or array, network) and nano/meso wires as an active element for hydrogen sensing applications. Embodiments of the present invention can detect 0.25% hydrogen in nitrogen. With the present invention, by preparing a very thin layer of metal (for example, titanium) or oxidizing a titanium layer to TiO 2 and preparing conductive palladium or palladium-silver nanostructures on the less conductive titanium or TiO 2 surface, there is no need for the transfer process which caused degradation of the sensor at high temperature. Test results show that palladium or palladium-silver nanoparticles (or nanowires) on titanium (or TiO 2 ) can be used to detect very low concentration (0.25%) of hydrogen at very high temperature (178° C.).
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
|
A hydrogen sensor and/or switch fabricated from an array of nanowires or a nanoparticle thick film composed of metal or metal alloys. The sensor and/or switch demonstrates a wide operating temperature range and shortened response time due to fabrication materials and methods. The nanowires or nanoparticle thick films demonstrate an increase in conductivity in the presence of hydrogen.
| 6
|
BACKGROUND OF THE INVENTION
This invention relates to a semiconductor memory device using a ferroelectric material.
From the point of view of write-in and read-out, memory devices may be divided into the RAM (random access memory) type which allows data to be written in and read out from any address and the ROM (read only memory) type which allows data only to be read therefrom. In other words, data can be written into a RAM and can be read therefrom and for this reason, the speeds of reading out and writing in data are usually set about equal to each other. As for a ROM, data can be read therefrom whenever they are needed but they cannot be written in, or may be written in but the speed of writing in data is set very much slower than the speed of reading them out. For this reason, a RAM is usually used for storing data which must be updated frequently, while a ROM is usually used for storing a program which does not have to be rewritten frequently.
Examples of a magnetic memory device include disk memories such as hard disks and floppy disks. Although they may be classified as a RAM because data can be freely written in and read out, they can also function as a ROM if a write-inhibiting means is provided so as to be used only for reading out data. In other words, a single memory device can sometimes be used both as a RAM and a ROM. As for optical memory devices such as CD-ROMs, they are used only for reading out data.
As for semiconductor memory devices, DRAMs and SRAMs may be cited as examples of RAMs while examples of ROM include mask ROMs, fuse-type bipolar PROMs (programmable read only memories) and diode destructible PROMs. Examples of a non-volatile semiconductor device include EPROMs (erasable PROMs) and EEPROMs (electrically erasable PROMs). DRAMs and SRAMs are not provided with any non-volatile characteristics like ROMs and cannot physically prevent write-in. On the other hand, aforementioned kinds of semiconductor ROMs cannot allow data to be freely written in and hence cannot serve as a RAM. In summary, unlike disk memories as an example of magnetic memory devices, there has not been developed yet a technology for making a semiconductor memory device to serve both as a RAM and, with the help of a write-inhibiting means, also as a ROM.
Recently, ferroelectric memory devices are being developed as an example semiconductor memory devices. Ferroelectric memories function to store data by means of residual polarization of a ferroelectric material and not only have non-volatility but also are capable of having data written in and read out at a high speed like DRAMs. In other words, ferroelectric memories can function as RAMs but they cannot serve as a ROM since they cannot inhibit write-in.
One of the technological problems involved in the development of ferroelectric memory devices has related to the so-called "imprint characteristic." This is the problem, for example, of the phenomenon that, if a data item such as "0" is stored in a memory cell for a long time such as several years and if an attempt is made thereafter to write "1" in this memory cell, the cell will find it difficult to store "1" but will return to the condition of storing "0." It is known that this phenomenon occurs when voltage pulses of a same polarity are successively applied or when heat is applied under a polarized condition. For this reason, it has been a common practice to apply voltage pulses continuously or heat in order to test the imprint characteristic by means of such a load.
Such an "imprint condition" at which it becomes difficult to write in a data item into a memory cell is now understood to be caused when the hysteresis characteristic of the ferroelectric material is deformed or shifted. FIGS. 8A, 8B and 8C show how the hysteresis curve becomes deformed from an initial condition shown in FIG. 8A to FIG. 8B and then to FIG. 8C.
When the hysteresis curve was as shown in FIG. 8A, for example, let us assume, as described in Japanese Patent Publication Tokkai 8-36888, that two voltage levels V 1 and V 2 are taken corresponding to a positive polarization condition and a negative polarization condition in order to distinguish data "0" and "1" and that a reference voltage V ref (not shown) is set between V 1 and V 2 such that a detected voltage V d at the time of detection is compared with this reference voltage V ref and the stored data item is identified as "1" or "0" respectively if V d >V ref and V d <V ref .
As the hysteresis curve becomes deformed, as shown in FIGS. 8B and 8C, however, the difference between V 1 and V 2 becomes smaller and their size relationship may even become reversed, as shown in FIG. 8C. In such a situation, since voltage V 1 corresponding to data item "1" is smaller than the reference voltage V ref , even if it is attempted to write "1" where it was "0", the stored data item may not necessarily be recognized as "0". In other words, the memory cell seems to go back to the initial condition before the rewriting is effected, and this is the so-called imprint condition.
It has indeed been ascertained that the so-called imprint condition does not mean that the memory condition of a memory device has irreversibly affixed but that the memory device goes back to its initial condition even if voltage pulses of the polarity corresponding to a data item opposite to the stored data item are repeated applied.
The aforementioned imprint characteristic has been considered as a kind of deterioration in the characteristics of a memory device. From a different point of view, however, this property that the memory condition is kept unchanged as before even if an attempt is made to write in a new data item may be considered to be similar to the function of inhibiting write-in, say, into a disk memory of a magnetic memory device, as explained above.
It is therefore an object of this invention to affirmatively make use of the imprint characteristic in a memory device such that a semiconductor memory device, which already has the functions of a RAM, can also function as a ROM.
SUMMARY OF THE INVENTION
A semiconductor memory device embodying this invention, with which the above and other objects can be accomplished, may be characterized as comprising not only a plurality of memory cells with a ferroelectric material so as to remain in a data-storing condition by the residual polarization of this ferroelectric material, but also an imprint controlling means for controlling the imprint condition of the ferroelectric material of at least one of these memory cells. This imprint controlling means comprises a heat-applying means for applying heat to the ferroelectric material of the memory cell and/or a voltage-applying means for applying a pulsed voltage of the same polarity to the memory cell continuously for a specified length of time. This voltage-applying means serves to accelerate the imprint condition of the ferroelectric material by applying to the memory cell voltage pulses of the same polarity as that which indicates the stored data item of the memory cell and to cancel the imprint condition by applying to the memory cell voltage pulses of the polarity which is opposite to that which indicates the stored data item. The heat-applying means serves to apply heat to the ferroelectric material so as to accelerate the imprint condition of the ferroelectric material or its cancellation.
The semiconductor memory device further comprises a detecting means for detecting the hysteresis characteristic of the ferroelectric material of the memory cell, and the imprint control means serves to operate from the initial moment when it begins to operate until this detecting means a hysteresis characteristic which indicates the imprint condition and further continuously for an extra length of time which is approximately the same as the first period.
A method of this invention for controlling the imprint condition of a semiconductor memory device as described above may be characterized as comprising the steps of continuously applying to the memory cell, holding a data item in an imprint condition, voltage pulses of polarity opposite to that which indicates the stored data item of the memory cell for a specified length of time and applying heat so as to accelerate the cancellation of the imprint condition such that the imprint condition will be canceled. In this method, the imprint condition is caused by applying heat so as to accelerate the imprint condition and/or by continuously applying voltage pulses of the same polarity as that which indicates the stored data item of the memory cell for a specified length of time.
In summary, a semiconductor memory device of this invention causes an imprint condition in a memory cell through its imprint control means so as to prevent data from being written in and to cancel the generated imprint condition so that a new data item can be written in. In other words, the switch-over between the functions of a RAM and a ROM is carried out by the imprint control means. The method of control according to this invention is characterized by the step of applying both heat and voltage pulses of a selected polarity so as to cancel the imprint condition of a data-storing memory cell such that the imprint condition can be easily canceled.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. In the drawings:
FIG. 1A is a plan view of a semiconductor memory device according to a first embodiment of this invention and FIG. 1B is its sectional view taken along line 1B--1B in FIG. 1A;
FIG. 2A is a plan view of a semiconductor memory device according to a second embodiment of this invention and FIG. 2B is its sectional view taken along line 2B--2B in FIG. 2A;
FIG. 3A is a plan view of a semiconductor memory device according to a third embodiment of this invention and FIG. 3B is its sectional view taken along line 3B--3B in FIG. 3A;
FIG. 4A is a sectional view of a memory cell and FIG. 4B is an equivalent circuit diagram of the memory cell;
FIGS. 5A and 5B are graphs of a voltage pulses;
FIG. 6 is a circuit diagram of a detection circuit;
FIGS. 7A and 7B are flow charts for the generation and cancellation of an imprint condition according to a method of this invention; and
FIGS. 8A, 8B and 8C are hysteresis curves showing the generation of an imprint condition.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1A and 1B show a semiconductor memory device according to a first embodiment of this invention. In general, expression "semiconductor memory device" is used to indicate a device as a whole, including not only memory cells but also data processing means for processing data in the memory cells. In the description of examples which follows, however, only the portions which characterize the invention will be mainly explained and the other portions may be ignored. It is still to be understood that within the context of this invention, expression "semiconductor memory device" include not only memory cells but also systems which include memory cells.
In FIGS. 1A and 1B, numeral 1 indicates a memory part formed, say, on a silicon substrate by a conventional semiconductor process such as an epitaxial method, patterning and injection of impurities. The cell structure of the memory part 1 may be, for example, as shown in FIG. 4A, having an equivalent circuit diagram shown in FIG. 4B. Explained more in detail, the memory part 1 includes a selection transistor TR which is a MOSFET and a memory capacitor C containing a ferroelectric material, the source, the gate and the drain of the selection transistor TR being connected respectively to a bit line BL, an word line WL and one of the electrodes of the memory capacitor C. The other electrode of the memory capacitor C is connected to a plate line PL. As a signal is received by the selection transistor TR through the word line WL, the bit line BL and the memory capacitor C are connected such that a data item can be written into or read out of the memory capacitor C.
As shown in FIG. 4A, the selection transistor TR is formed by forming an N-type source 101 and drain 102 on a P-type silicon substrate 100 and depositing a layer of polysilicon gate 103 on the N-channel portion therebetween. An insulating layer 104 comprising a silicon oxide film is deposited thereon, and a memory capacitor C having a ferroelectric membrane 105 of PZT sandwiched between a lower electrode 106 and an upper electrode 107 is formed thereon. The upper electrode 107 of the memory capacitor C is connected to the drain 102 of the selection transistor TR through a conductive layer 108 which may comprise Al.
Many memory cells, as described above, are formed in the memory part 1 of FIG. 1. The memory part 1 itself is formed as an island on the silicon substrate, surrounded by a heat-emitting part 2. As a current is passed through electrodes 3 formed on the surface of this heat-emitting part 2, heat is emitted from the heat-emitting part 2 and is applied to the memory part 1. In summary, the example shown in FIG. 1 is characterized as using the heat-emitting part 2 as the imprint means and also as containing this heat-emitting part 2 within the device. As a practical example, the memory may be brought into an imprint condition by applying heat for several hours to the memory part 1 at 150-200° C.
Alternatively, the memory may be brought into an imprint condition by applying voltage pulses as shown in FIG. 5A or 5B for several hours (about 10 7 times) continuously from the bit line BL shown in FIG. 4B to thereby continuously write in a same data item. In this case, pulses with negative voltage (as shown in FIG. 5B) are applied if the ferroelectric material of the memory capacitor C is in a negative polarization condition and pulses with positive voltage (as shown in FIG. 5A) are applied if the ferroelectric material of the memory capacitor C is in a positive polarization condition. In other words, data having the same polarity as the polarization condition of the ferroelectric material of the memory capacitor C must be written in. An imprint condition can be efficiently generated under a heated condition of about 150° C. by applying voltage pulses for only several minutes. In other words, although an imprint condition can be generated by applying only heat or only voltage pulses but there is a multiplicative effect such that an imprint condition can be generated very quickly if both heat and voltage pulses are applied at the same time.
When a memory device is in an imprint condition, it serves as a ROM because the memory contents of the memory cells are not affected even if it is attempted to write in data which are different from the imprinted data.
If it is desired to use a memory device in an imprint condition again as a RAM into which different data can be written, one has only to cancel this imprint condition, say, by continuously applying voltage pulses having polarity opposite from that of the imprinted data (as shown in FIG. 5A or 5B) while causing a current to flow to the heat-emitting part 2 to raise the temperature of the memory part. In the case of PZT, the imprint condition can be canceled at 150-200° C.
Such a method for controlling the imprint condition of a memory device can be effective not only for canceling an imprint condition by applying voltage pulses and heat as described above but also in the case of an imprint condition brought about after data have been in storage for a long period of time such as several years. In such a situation, the memory device in an imprint condition is set in a control device provided with means for applying heat and voltage pulses as described above to cancel the imprint condition of the memory device and then new data are written in into the rejuvenated memory device.
In order to detect the generation and/or cancellation of an imprint condition, one or more detection capacitors may be contained in the memory part 1. It is preferable to have several such detection capacitors distributed throughout in order to improve the accuracy of detection. The detection capacitors are structured similarly to the memory capacitors of the memory cells and since they are placed in the same environment as the memory capacitors, they go into an imprint condition and their imprint conditions are canceled nearly as do the memory capacitors. Thus, the condition of a memory capacitor can be monitored by detecting the characteristics of a detection capacitor.
The hysteresis characteristics of a detection capacitor Cd can be detected, for example, by means of a detection device shown in FIG. 6, comprising a so-called Sawyer-Tower circuit, wherein capacitor Cs with a much larger capacitance than the detection capacitor Cd is used. If an input voltage V in , given by V in =Vsinωt, for example, is be applied, a hysteresis curve as shown in FIG. 8 is obtained on a CRT.
The routine for the generation and cancellation of an imprint condition, as described above, is summarized in a flow chart shown in FIGS. 7A and 7B. For generating an imprint condition, data are initially written in a memory device from a data processing device such as a CPU (Step S1) and then the memory cells with data not to be overwritten are identified (Step S2). Next, parameters Tw for indicating the time for write-in and t for counting time are reset to zero (Step S3) and the application of heat and voltage pulses and the write-in of data are started (Step S4). After a specified time t1 has elapsed (Yes in Step S5), t1 is added to Tw and t is reset (Step S6). Next, the hysteresis curve of the capacitor Cd is detected by the detecting apparatus described above to check whether the voltage level V 1 has become lower than the voltage level V 2 as explained with reference to FIGS. 8A-8C (Step S7). If V 1 remains to be higher than V 2 , the routine goes back to Step S4 to continue the write-in process. If the deformation of the hysteresis curve has sufficiently advanced and V 1 is found to be lower than V 2 , the routine proceeds to Step S8 wherein application of heat and voltage pulses is started as in Step S4 but the counting down of time is started at this time (Step S9) and the process is stopped when the counter counts down from Tw to zero (YES in Step S10). With reference to this flow chart, the application of heat and voltage pulses is continued for a period which is approximately the same as the time between the start of application until an imprint condition is detected (that is V 1 <V 2 is detected). This is because the memory device may go back from the imprint condition if the process is terminated immediately after the imprint condition has been reached. It is also to be noted, as explained above, that although both heat and voltage pulses are applied according to the flow chart, this is not a requirement according to this invention because an imprint condition can be generated by the application of heat alone or voltage pulses alone. Moreover, although the flow chart shows that the detection of the hysteresis characteristics of the detection capacitor Cd is carried out at intervals of t1, the detection may be carried out continuously or only after the imprint condition has been approached. Similarly, the period of time for the continued application of heat and/or voltage pulses may be further increased.
FIG. 7B shows a cancellation flow for showing the process for canceling an imprint condition. After the memory cells where cancellation should be effected are identified (Step S11), application of heat and voltage pulses as well as write-in of data with opposite polarity are started (Step S12). The detection device detects the hysteresis characteristics of the detection capacitor Cd to check whether V 1 and V 2 have returned to their initial levels (Step S13). If V 1 and V 2 have not returned to their initial values (NO in Step S13), the program goes back to Step S12 to resume the application of heat and voltage pulses. If V 1 and V 2 are found to have returned to their initial values (YES in Step S13), the cancellation process is then terminated. The remarks made above with reference to FIG. 7A are also applicable to the cancellation flow, that is, application of heat alone or voltage pulses alone may be sufficient and the hysteresis characteristics of the detection capacitor Cd may be carried out continuously or at intervals.
By appropriately combining an imprint flow such as shown in FIG. 7A and a cancellation flow such as shown in FIG. 7B, a memory device serving as a RAM can be converted into a ROM and then back to a RAM whenever a switch-over is required. Moreover, such processes may be repeated for any number of times without affecting the characteristics of the ferroelectric material adversely to any significant degree.
Although the invention has been described above with reference to only one embodiment shown in FIGS. 1A and 1B, but this is not intended to limit the scope of the invention. Many modifications and variations are possible within the scope of the invention. For example, FIGS. 2A and 2B show another semiconductor memory device according to a second embodiment of this invention characterized as not having the heat-emitting means contained in the substrate but having it attached from outside. In FIGS. 2A and 2B, numeral 4 indicates a silicon substrate having a memory part formed thereon as shown in FIGS. 1A and 1B. A frame 5, made of a copper alloy or nickel alloy material, is intimately attached to the substrate 4, serving as a heat-emitting body itself when a current is introduced thereinto through its connector part 6. In summary, heat is applied to the memory part on the substrate 4 by supplying a current to the frame 5. This embodiment is the same as the first embodiment in other respects such as the manner of applying voltage pulses.
FIGS. 3A and 3B show still another semiconductor memory device according to a third embodiment of the invention, characterized as applying heat only to a portion of the memory part, unlike the first and second embodiments of the invention wherein heat is applied to the whole of the memory part. As shown in FIG. 3B, a silicon oxide layer 9 is formed above the memory part 1, and a conductor layer 8 is formed with Al on the silicon oxide layer 9 to be connected to electrodes 7. Portions 6 (shaded in FIG. 3A) of the silicon oxide layer 9 corresponding to memory cells, which are portions of the memory part 1, are connected to the conductor layer 8 so as to function as heat-emitting parts. These heat-emitting parts 6 may comprise a material such as polysilicon or aluminum or may be formed as "well" parts produced by the diffusion of impurities, and are connected to the electrodes 7 through wires so as to emit heat when a current is passed therethrough and to apply heat to selected portions of the memory cells intended to be brought into an imprint condition. This embodiment is useful when memory cells to be converted into ROMs are preliminarily determined.
Although FIGS. 3A and 3B show an example whereby heat-emitting parts are formed above the memory part but this is not intended to limit the scope of the invention. The heat-emitting parts of this kind may equally well be formed below the memory part. This can be done, for example, by forming a polysilicon or aluminum layer, say, by patterning, below the memory part.
Advantages gained by the present invention include the following:
(1) Since data stored in memory cells can be placed in an imprint condition, they can be effectively protected by erroneous rewriting operations;
(2) Since data which have once been put in an imprint condition can be rewritten by means of a refresh operation, and hence data can be effectively corrected without exchanging the memory device as a whole;
(3) An imprint condition which naturally occurred after a long period of storage can be easily canceled and hence the memory device can be used again, this effectively improving the effective lifetime of the memory device; and
(4) If the heat-emitting means is included in the semiconductor memory device, this serves to save electric power and the device does not become bulky even if such means are attached externally.
|
A semiconductor memory device with a plurality of memory cells each having a ferroelectric material for storing a data item by its residual polarization is made usable selectably both as a RAM and as a ROM by controlling the so-called "imprint condition" of the ferroelectric material. When some of the memory cells are going to be used to a ROM or when the memory cells in an imprint condition are going to be used a RAM, heat and/or voltage pulses with an appropriate polarity are applied to the data-storing ferroelectric material to change its hysteresis characteristics.
| 6
|
This invention relates to a method and construction of manufacturing a cistern from component arcuate blocks at a building cite.
More specifically, this invention relates to a method and construction of manufacturing a cistern using preformed structurally rigid blocks such as concrete blocks which are hollow in construction and when placed in a cylindrical mode, are capable of receiving circular reinforcing rings which are coupled together with hooked rods and form a rigid monolithic construction when concrete is poured into the hollow openings of the preformed blocks.
BACKGROUND OF THE INVENTION
Cisterns are conventionally and commercially manufactured at a plant in one large monolithic structure normally requiring transportation by means of a large truck or the like to the location at which the cistern is to be installed. This transportation exposes the cistern to the hazards of breakage or damage while at the same time requiring heavy equipment for purposes of loading and unloading. Moreover, where such cisterns are cast as a one-piece unit, problems of stresses arise which sometimes result in inherent weaknesses. Certain proposals have been made for purposes of fabricating cisterns from sub-units or sub-assemblies which are transported as such to the location where they are to be installed. These techniques for various reasons have never found large commercial application.
PRIOR ART
There are numerous patents in the prior art which illustrate the construction of monolithic structures using circular blocks which are reinforced. Such patents include the patent to Dochnal, U.S. Pat. No. 1,277,556. Hollow building blocks have also been disclosed in the patent to Steward, U.S. Pat. No. 1,485,309. Other patents showing building block construction using hollow blocks with and without reinforcing means include U.S. Pat. Nos. 1,050,130 to Harvey; 3,386,217 to Couture; 1,727,546 to Knapen; 1,154,219 to Straight; 2,198,399 to Tefft; 777,073 to Brownson; 2,153,913 to Blackwell; 767,398 to Ferguson; 798,850 to Weber; 894,122 to Dougherty; UK Patent No. 2,062,062 to Rassias et al and French Patent No. 967,968 to Dargelas.
None of the above patents taken singly or in combination include all of the inventive features such as the use of the wedge-shaped openings including wedges and hooked rods which join annular reinforcing rings contained between the blocks together nor suggest any of the methods of the construction of this invention.
DETAILED DESCRIPTION OF THE INVENTION
It is therefore an object of the invention to provide a new and improved technique for the manufacture of cisterns and the like.
It is a further object of the invention to provide new and improved techniques whereby special and improved concrete blocks are provided which are capable of being formed into a monolithic structure constituting a cistern.
Yet another object of the invention is to provide improved means for the fabrication of a monolithic cistern construction while at the same time providing in such construction the specialized wedge-shaped openings available in conventional cisterns to provide for drainage therefrom while limiting the entry of dirt and other foreign materials into the cistern construction.
In achieving the above and other of the objects of the invention, there is proposed a cistern construction consisting of a plurality of superposed layers of arcuate concrete blocks having communicating openings extending through and between said layers, a bonding material such as mortar being charged into these openings in order to bond the layers into a monolithic structure having a generally cylindrical form.
As a feature of the invention, wedge-shaped openings are provided in and radially disposed with respect to the blocks, these wedge-shaped openings accommodating wedges which are removed after the mortar has set.
According to another feature of the invention, there are employed metal reinforcing rings extending through the respective layers of blocks in generally concentric relationship with the cylindrical form. Moreover, reinforcing rods are provided which extend through the layers in generally axial disposition relative to the reinforcing rings. In accordance with the invention, the aforesaid openings are supplemented by juxtaposed dove-tail shaped openings which are intended to provide for an effective gripping between the mortar and the various blocks.
Other objects and features of the present invention will become apparent from the following detailed description considered in connection with the accompanying drawings, which disclose several embodiments of the invention. It is to be understood that the drawings are to be used for the purpose of illustration only, and not as a definition of the limits of the invention.
In the drawings, wherein similar reference characters denote similar elements throughout the several views:
FIG. 1 is a perspective view of a cistern prepared in accordance with the invention;
FIG. 2 is a top plan view of a concrete block employed in the cistern of FIG. 1;
FIG. 3 is a side view of the concrete block of FIG. 2;
FIG. 4 is a cross-sectional view, taken along line IV--IV of FIG. 3; and
FIG. 5 illustrates a modification of one of the elements illustrated in FIG. 4.
DETAILED DESCRIPTION OF THE DRAWINGS
Referring to FIG. 1, there is shown a cistern 10 having a generally cylindrical form and consisting of a plurality of layers of which layers 12, 14, 16, 18, 20 and 22 are shown by way of example. These layers are superposed upon one another and are each formed of a plurality of blocks such as, for example, block 24. Each block 24, as will be described in greater detail hereinafter, is an arcuate segment susceptible of being combined with a plurality of like blocks to form a circular tier. The blocks of one layer are preferably staggered (in relationship to polar coordinates) with respect to the blocks of the next superposed layer. The blocks of alternate layers are preferably aligned with one another.
As is readily seen in FIG. 1, the cistern is provided with a multitude of openings 26 which are of wedge-shape and which are, per se, conventional. These openings are radially disposed relative to the cylindrical form of cistern and flare outwardly so that drainage from the interior 28 of the cistern is facilitated while entry of the surrounding dirt is minimized due to the tapered walls of the openings.
It will be noted that openings 26 are generally provided in the upper faces of the respective blocks in which these openings are formed. Thus, the side and lower walls of the openings are defined by the block in which the openings are provided, whereas the upper or closing wall of each opening is provided by the bottom wall or face of the next superposed block or blocks.
The arrangement which has been described with respect to openings 26, applies to each of the layers except uppermost layer 22 in which the wedge-shaped openings are provided in the bottom faces of the respective blocks. Actually, these latter blocks are identical in shape and form to the blocks of the lower layers. However, the blocks in the uppermost layer are inverted in order to avoid having upwardly opening wedge-shaped passages in the top edge of the cistern.
An illustrative block of the type employed in the cistern of FIG. 1 appears in detail in FIGS. 2-4. Referring first to FIG. 2, block 24 consists of an outer face 30 and an inner face 32, both of which are arcuately shaped and concentric with one another. These faces are similarly concentric with the axis of the cistern constructed from the related blocks.
Block 24 is also provided with end faces 34 and 36. These faces are preferably planar, and are also preferably tapered so as to be radially disposed with respect to the finished cylindrical form.
Block 24 is provided with a vertical opening 38 extending completely therethrough from the top face of the block to the bottom face thereof, said faces being indicated at 40 and 42 in FIG. 2.
Opening 32 is generally of arcuate shape extending between end faces 34 and 36 of the block but being spaced from the latter. As a feature of the invention, there is provided adjacent ends 44 and 46 of said vertical opening supplemental openings 48, 50, 52 and 54. These latter openings are dove-tail shaped openings and are intended to provide a most effective gripping of the mortar as will be explained hereinafter.
Further openings 56 and 58 are provided in the ends of the block and communicate vertical opening 38 with the block ends. As is seen more particularly in FIG. 4, these latter openings do not extend completely through the block in a vertical sense, but have rounded bottoms 60 which are spaced from bottom face 42 of block 24 (see FIG. 4).
Centrally located in each block 24 is a wedge-shaped opening 62 having a sloping bottom wall or face 64 and two tapered side faces 66 and 68. This wedge-shaped opening 26 is freely open at the top of the block and is intended to accommodate a wedge to substantially fill the space, as will be subsequently explained.
Blocks 24 are preferably fabricated of concrete, but other similar materials having suitable structural strength can be substituted if found convenient. The blocks are preferably of a size which renders them portable so that they can be manually loaded and unloaded from the transportation vehicle employed. It will therefore be readily appreciated that these blocks can be manufactured at a suitable plant provided for their fabrication and then transported unassemblied to the location at which the cistern is to be installed. These products can then be combined into cistern form and processed as will be hereinafter described, whereupon a complete cistern will be formed having the strength of a monolithic structure.
In order to provide a suitable physical strength for the resulting structure, as each layer of blocks is installed, a steel reinforcing ring 70 is inserted at the top of each layer, this ring extends through openings 56 and 58, below bottoms 64 of the various wedge-shaped openings 26. Ring 70, which can also be fabricated of any other metal or material having suitable structural strength, is supported on bottoms 60 of the various openings 56 and 58. These rings will be generally disposed in concentric relationship with the axis of the cistern being manufactured and a plurality of such rings will be employed, one for each layer of blocks except the uppermost layer.
In addition to the metal reinforcing rings 70, there are also provided a plurality of vertical reinforcing rods 72, each provided with a hooked upper extremity 74 which is preferably hooked over the uppermost ring 70 and suspended therefrom in depending relationship. At least one such reinforcing rod is preferably employed with each vertical alignment of openings 38, but two or more of such vertical reinforcing rods can also be employed as required.
When rings 70 and rods 72 have been installed in superposed layers, the next step in the construction of the cistern is the insertion of wedges 76 into the wedge-shaped openings 26. Wedges 76 are preferably fabricated of wood or a like inexpensive material capable of being used repeatedly and capable of withstanding mallet blows as will hereinafter be explained. Wedges 76 are moreover preferably lubricated with a heavy oil or the like, or with a conventional material capable of inhibiting the setting of the immediately surrounding mortar. Such materials are well known in the art and require no explanation in this text.
After the wedges are installed, and assuming that the reinforcing rings and rods have already been positioned, mortar is then charged through the uppermost of the vertical openings 38 in the assembly and is allowed to descend through the network of communicating openings which have been formed until the entire honeycomb has been filled with mortar which extends into the dove-tail openings described above. The mortar will pass through the various openings 38 and through communicating openings 56 and 58 so that the mortar in combination with the concrete blocks will form a monolithic structure through which will extend the rings 70 and rods 72.
After a suitable curing time, the mortar will have set and openings 38, 56 and 58 will have been completely filled with the cured mortar. At this time, blocks 76 are hammered out of the wedge-shaped openings 26 whereupon these openings will be permanently available for the drainage of fluid from within the cistern. Thus, the wedge-shape has two important aspects to it, notably that of facilitating the removal of wedges 76, while at the same time providing for the tendency of unidirectional movement of materials therethrough since drainage from inside of the cistern will be facilitated whereas the movement of dirt and other such materials into the cistern will be impeded due to the sloped walls of these openings.
While the wedges are removed and can be subsequently used in the fabrication of further cisterns, rings 70 and rods 72 remain in place thereby contributing to the physical strength of the resulting cistern and providing further surfaces on which the mortar may attach. The result is an extremely strong construction which is as durable, if not more so, than previously known cisterns which are made in entirety at a plant provided for such purpose.
While openings 56 and 58 have been illustrated in rectilinear coaxial alignment, it is possible to arrange these openings in arcuate concentric relationship provided that the cost of manufacture will not be too greatly increased thereby. Similarly, the dove-tail shaped openings which have been illustrated can be distributed with greater or lesser frequency through the concrete blocks according to the needs of the construction.
While wedge-shaped openings have been illustrated in each of the layers of blocks, it might be possible to eliminate these in alternate of the layers or to provide additional wedge-shaped openings if increased drainage is necessary. Similarly, while the inverted arrangement of blocks at the top of the cistern is to be preferred, this layer can be eliminated if, for any particular use, the presence of upwardly opening wedge-shaped slots is not objectionable.
While it is not found generally necessary to supplement the force of gravity for purposes of spreading the mortar throughout the system of communicating openings in the cistern, it should be noted that it is possible in certain instances to employ vibrating equipment as is conventional in the art to provide for insuring against voids or the like when the mortar is inserted. Usually, however, it will be possible to provide the mortar in such consistency that its flow throughout the honeycomb of openings will be complete without such auxiliary treatment which can therefore be omitted.
It will be appreciated that the mortar represents one type of bonding material including, by way of example, cement and cementitious products, the chief requirement for such material being that it have suitable structural strength so that the various blocks can be readily held together.
There will now be obvious to those skilled in the art many modifications and variations of the construction and techniques set forth hereinabove. These modifications and variations will not depart from the scope of the invention if defined by the following claims. One such modification appears in FIG. 5 wherein rod 72 of FIG. 4 is replaced by individual rods 80 extending between adjacent layers (e.g. rings 82 and 84) and provided with upper and lower hooks 86 and 88.
|
A cistern made of layers of arcuate blocks provided with openings in which reinforcing rings and rods are deposited, the openings being arranged such that mortar can be spread throughout the structure to form a monolithic construction. Wedge-shaped openings are formed in the blocks in radial disposition and removable wedges are placed therein to form permanent openings in the construction, the wedges being removed after the mortar has set. Metal circular rings are also placed on each leg or block and each of the rings are coupled together by vertical depending rods before the cement is forced through the hollow openings of the layers of arcuate blocks.
| 4
|
FIELD OF THE INVENTION
[0001] The present invention provides a flechette cartridge having flechettes contained therein which, when fired, are accelerated without spin being imparted thereto. In particular, a flechette cartridge is provided containing flechettes which are accelerated within the cartridge case without spin imparted thereto, and which do not engage the barrel rifling, thus allowing flechettes to stabilize quickly and avoiding an excessive spread pattern during a firing event.
BACKGROUND OF THE INVENTION
[0002] Conventional flechette rounds, such as the M1001, contain approximately 113 flechettes, each flechette weighing 18 grains. The flechettes contained within such conventional rounds reach average velocities of approximately 790 ft/sec. Such velocities are satisfactory. The M1001 uses a heavy projectile body to carry the flechette payload down the barrel. The projectile body uses a slip band obturator to minimize spinning the projectile body and flechette payload in the barrel rifling.
[0003] Conventional payload carriers are stripped from the flechette payload by propellant gases and a spring, which are deficient in stripping the payload carriers from the flechette payloads. Further, the payload carrier is formed of a heavy metal body, which undesirably functions as a parasitic mass. This means of stripping the flechette payload carriers results in undesired dispersion characteristics. The relatively heavy metal body results in reduced muzzle velocities and reduced kinetic energy, reducing the effectiveness of the flechettes.
[0004] It is an object of the present invention to provide a flechette cartridge which maximizes the muzzle velocity of the flechettes by minimizing the parasitic mass associated with the flechette carrier. It is a further object of the present invention to provide a robust means for reliably stripping the flechette carrier.
SUMMARY OF THE INVENTION
[0005] In order to achieve the object of the present invention as described above, the present inventor earnestly endeavored to develop a flechette cartridge capable of launching flechettes in a concentrated, predictable spread pattern at a relatively high muzzle velocity. Accordingly, in a first embodiment of the present invention, a flechette cartridge is provided comprising:
[0006] (a) a cartridge case having:
(i) a base having a primer cavity disposed therethrough; (ii) a cartridge case body having an outer circumference adjacent the base, and an inner circumference opposite the outer circumference, said inner circumference defining a smooth-bored cartridge barrel, the smooth-bored barrel having a open mouth at one end thereof; (iv) a high pressure chamber disposed adjacent the primer cavity; and (v) a low pressure chamber disposed adjacent the high pressure chamber;
[0011] (b) a primer disposed within the primer cavity;
[0012] (c) a propellant charge disposed within the high pressure chamber;
[0013] (d) a sub caliber payload cup slidably disposed within the smooth-bored cartridge barrel, adjacent the low pressure chamber, the sub caliber payload cup having:
(i) a payload cup body having an outer base, an outer circumference adjacent the outer base, an inner circumference opposite the outer circumference, and an inner base opposite the outer base; and (ii) flechette retaining means for retaining flechettes, disposed within the inner circumference; and (iii) a plurality of flechettes retained within the flechette retaining means.
[0017] In a second embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, wherein the payload cup body further comprises a metal disk disposed therein, within the inner circumference of the payload cup body, adjacent the inner base. This metal disk prevents the flechettes from digging into the payload cup body upon firing.
[0018] In a third embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, wherein the payload cup further comprises a payload cup stripping means in communication with the cartridge case at a first end, and with the payload cup at an end opposite the first end,
[0019] wherein, when the flechette cartridge is fired, the payload cup is propelled from the smooth bored cartridge barrel and, at a predetermined distance from the smooth bored cartridge barrel, the payload cup stripping means acts upon the payload cup to strip the payload cup from the flechettes. The flechette retaining means generally disintegrates upon being exposed to the high velocity airstream, allowing the flechettes to fly unimpeded to the target.
[0020] In a fourth embodiment of the present invention, the flechette cartridge of the third embodiment is provided, wherein the payload cup stripping means is comprised of a line or string.
[0021] In a fifth embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, wherein a barrel ridge is formed on the smooth-bored cartridge barrel, and a payload cup ridge is formed on the payload cup, adjacent the outer base thereof. Upon firing, the payload cup ridge and barrel ridge are caused to impact one another, thereby decelerating the payload cup.
[0022] In a sixth embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, comprising a plurality of sub caliber payload cups disposed within the smooth-bored barrel, with separator disks disposed therebetween.
[0023] In a seventh embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, further comprising an ogive cap removably disposed on the cartridge case adjacent the open mouth of the smooth bored barrel.
[0024] In an eighth embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, further comprising a metal disk disposed within the cartridge barrel between the low pressure chamber and the payload.
[0025] In a ninth embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, wherein an empty volume is present within the cartridge barrel between the payload cup and the open mouth of the smooth-bored barrel. Longer cartridge barrel lengths allow for gentler payload accelerations, with lower required peak propellant pressures.
[0026] In a tenth embodiment of the present invention, the flechette cartridge of the first embodiment above is provided, further comprising a closure disk disposed within the cartridge barrel, adjacent the flechettes and flechette retaining means of the sub caliber payload cup.
[0027] In an eleventh embodiment of the present invention, the flechette cartridge of the first embodiment is provided, comprising a plurality of sub caliber payload cups.
[0028] In a twelfth embodiment of the present invention, a flechette cartridge is provided comprising:
[0029] (a) a cartridge case having:
(i) a base having a primer cavity disposed therethrough; (ii) a cartridge case body having an outer circumference adjacent the base, and an inner circumference opposite the outer circumference, said inner circumference defining a smooth-bored cartridge barrel, the smooth-bored barrel having a open mouth at one end thereof;
[0032] (b) a primer disposed within the primer cavity;
[0033] (c) a propellant charge disposed within the cartridge case body;
[0034] (d) a sub caliber payload cup slidably disposed within the smooth-bored cartridge barrel, the sub caliber payload cup having:
(i) a payload cup body having an outer base, an outer circumference adjacent the outer base, an inner circumference opposite the outer circumference, and an inner base opposite the outer base; and (ii) flechette retaining means for retaining flechettes, disposed within the inner circumference; and (iii) a plurality of flechettes retained within the flechette retaining means.
BRIEF DESCRIPTION OF THE DRAWING
[0038] FIG. 1 is a cross sectional view of the flechette cartridge of the present invention.
[0039] FIG. 2 is a cross-sectional view of the flechette cartridge of the present invention, as shown in FIG. 1 , further illustrating the payload cup stripping means 33 .
[0040] FIG. 3 is a partially cut away perspective view of the flechette cartridge of the present invention, having a plurality of sub caliber payload cups disposed therein.
[0041] FIG. 4 is a cross sectional view of the flechette cartridge, illustrating the frictional payload cup stripping means.
DETAILED DESCRIPTION OF THE INVENTION
[0042] As illustrated in FIGS. 1 and 2 , the present invention provides a flechette cartridge 1 comprising a cartridge case 3 having a base 5 and cartridge case body 7 . A primer cavity 9 is disposed through said base 5 . The cartridge case 3 is comprised of a cartridge case body 9 having an outer circumference 11 adjacent the base 5 , and an inner circumference 13 opposite the outer circumference 11 . The inner circumference 13 defines a smooth-bored cartridge barrel 15 , the smooth-bored barrel 15 having an open mouth 17 disposed at one end thereof.
[0043] A primer 19 is disposed with the primer cavity 9 , and high pressure chamber 21 is disposed adjacent the primer cavity 9 . A low pressure chamber 23 is disposed adjacent the high pressure chamber 21 . A propellant charge 25 is disposed within the high pressure chamber 21 . When fired, the weapon firing pin strikes the primer 19 , and the primer 19 ignites, subsequently igniting the propellant charge 25 .
[0044] A sub caliber payload cup 27 is disposed within the smooth-bored cartridge barrel 15 , adjacent the low pressure chamber 23 . Alternatively, a single propellant chamber can be used, wherein the propellant is ignited and propels the payload cup down the barrel, venting at the muzzle. The sub caliber payload cup 27 is comprised of a flechette retaining means 29 for retaining flechettes, and for sealing propellant case within the cartridge barrel, and a plurality of flechettes 31 retained therein. The flechette retaining means 29 is, generally, formed of a plastic or composite material, but may be formed of a metallic material, and has a structure containing numerous protrusions therein for frictionally retaining the flechettes 31 .
[0045] As called for in the eighth embodiment of the present invention herein, and as illustrated in FIG. 1 , the low velocity flechette cartridge 1 may further comprise a metal disk 43 disposed within the smooth-bored cartridge barrel 15 between the low pressure chamber 23 and the sub caliber payload cup 27 . This metal disk 43 acts to separate and evenly disperse the pressure produced by the propellant gases, so as to prevent damage to the flechettes and the flechette retaining means during firing.
[0046] Preferably, the sub caliber payload cup 21 further comprises a payload cup stripping means 33 , as illustrated in FIG. 2 . The payload cup stripping means 33 , generally comprised of a string or line, as called for the in the fourth embodiment above, to attach the sub caliber payload cup 27 to the cartridge case 3 , is in communication with the cartridge case 3 at a first end 35 , and with the payload cup 21 at an end 37 (i.e., a second end) opposite the first end 35 . When the flechette cartridge 1 is fired, the payload cup 33 is propelled from the smooth bored cartridge barrel 15 and, at a predetermined distance from the smooth bored cartridge barrel 15 (which is dependent upon the length of the payload cup stripping means 33 ), the payload cup stripping means acts 33 upon the sub caliber payload cup 27 (by restraining same) to strip the flechette retaining means 29 from the flechettes 31 , allowing only the flechettes 31 to continue direct forward travel. Thus, the sub caliber payload cup 27 is prevented from traveling with the flechettes 31 to the target.
[0047] The line or string is preferably designed to break near the attachment point inside the cartridge case 3 (i.e., at or adjacent to the first end 35 ), to eliminate having the string remaining in the barrel after firing. This is accomplished by creating a weak point, such as a knot, near attachment point of the line or string to the cartridge case 3 . The process of breaking the string or line extracts sufficient kinetic energy from the flechette payload cup 33 to reliably strip the payload cup 33 from the flechettes 31 .
[0048] As called for in the fourth embodiment of the present invention, the flechette cartridge 1 , as illustrated in FIG. 3 , may comprise a plurality of sub caliber payload cups 27 and 28 , disposed within the smooth-bored cartridge barrel 15 , with separator disk 39 disposed therebetween. This separator disk 39 prevents the flechettes within the rearwardly disposed sub caliber payload cup 27 from digging into the base of the forwardly disposed sub caliber payload cup 28 during a firing event.
[0049] As illustrated in FIG. 3 , the flechette cartridge 1 may further comprise an ogive cap 41 , removably disposed on the cartridge case 3 adjacent the open mouth 17 of the smooth-bored cartridge barrel 15 . This ogive cap 41 merely prevents intrusion of foreign objects and/or moisture from entering the barrel 15 prior to firing. The ogive cap 41 is forcibly ejected from the cartridge case 3 during firing, and expelled from the weapon barrel.
[0050] As illustrated in FIG. 1 and FIG. 2 , when the flechette cartridge 1 does not include an ogive cap 41 , means for protecting the sub caliber payload are needed. Accordingly, the flechette cartridge 1 may further comprise a closure disk 51 , as illustrated in FIG. 1 , disposed within the smooth-bored cartridge barrel 15 , adjacent the flechettes 31 and the flechette retaining means 29 of the sub caliber payload cup 27 . This closure disk 51 performs essentially the same task as the ogive cap 41 , i.e., prevents intrusion of foreign objects and/or moisture from damaging the payload.
[0051] As illustrated in FIG. 1 , in a preferable embodiment, the flechette cartridge 1 preferably comprises an empty volume equaling or exceeding the volume of the payload cup is present within the smooth-bored cartridge barrel 15 between the sub caliber payload cup 21 and the open mouth 17 of the smooth-bored cartridge barrel 15 . This empty volume within the smooth-bored cartridge barrel 15 acts as an internal cartridge barrel, to launch the payload, rather than utilizing the weapon barrel (which can be damaged by the flechette payload and/or cause a decrease in accuracy thereof). Longer cartridge barrel lengths allow for gentler payload accelerations, with lower required peak propellant pressures.
[0052] In a preferred embodiment, as illustrated in FIG. 4 , in order to decelerate the payload cup upon firing, a barrel ridge 45 is formed on the smooth-bored cartridge barrel 15 . In addition, a payload cup ridge 47 is formed on the sub caliber payload cup 27 adjacent the base thereof. When the sub caliber payload cup 27 is fired, the payload cup 27 travels down the cartridge barrel 15 . At a certain point, the payload cup ridge 47 impacts the barrel ridge 45 . This impact produces a negative effect on the acceleration of the payload cup 27 , causing deceleration thereof.
[0053] Although specific embodiments of the present invention have been disclosed, those having ordinary skill in the art will understand that changes can be made to the specific embodiments without departing from the spirit and scope of the invention. The scope of the invention is not to be restricted, therefore, to the specific embodiments. Furthermore, it is intended that the appended claims cover any and all such applications, modifications, and embodiments within the scope of the present invention.
|
A flechette cartridge is provided, containing a plurality of flechettes, capable of firing the flechettes in a concentrated and accurate spread pattern upon firing. In particular, both low and high velocity flechette cartridges are provided, which accurately disperse flechettes in a concentrated spread pattern. The flechette cartridge minimizes the parasitic launch mass to maximize flechette payload, flechette velocity and kinetic energy, and to maximize target effects. The flechette cartridge provides a robust means for reliably stripping the flechette payload cup.
| 5
|
FIELD OF THE INVENTION
This invention relates to the preparation of lacquer. More particularly it relates to a process for preparing a cold-set lacquer.
BACKGROUND OF THE INVENTION
Paints based on aqueous polymer dispersions are widely used since they have two decisive advantages compared to paints based on film formers dissolved in organic solvents: they are not combustible; and they can be handled without causing any health hazard.
The aqueous polymer dispersions may be prepared by emulsifying the desired polymerizable monomer (e.g. acrylates such as ethyl acrylate; methacrylates such as methyl methacrylate; styrene; vinyl chloride; acrylonitrile; etc.) in water. Polymerization is initiated by addition of a water-soluble polymerization initiator, typically a per-compound.
An emulsifier is used in order to emulsify the water-insoluble monomer in the aqueous reaction mixture. However the emulsifier commonly has a harmful effect in that it may render the finished coating water-sensitive.
The prior art has heretofore attempted to obviate this disadvantage. Thus the amount of emulsifier has been reduced as far as possible; but only a relatively slight improvement in water-resistance has thereby been achieved. Other attempts to obtain dispersions from which water-proof coatings can be made have included the use of certain additives or special operating procedures.
For example W. German DT-OS No. 2,365,619 discloses that water resistance can be improved by addition of 1-10 w % (based on monomer) of a hydrocarbon or hydrocarbon mixture during or after emulsion polymerization.
W. German DT-OS No. 2,410,822 describes a process according to which emulsifier-free dispersions can be obtained containing only a small amount of polyvinyl alcohol as a protective colloid. The monomers are polymerized in a mixture of water, a water-miscible organic solvent, and a water-soluble, high molecular weight compound (containing hydroxyl, carboxyl, carboxylic amide, and/or ether groups), followed by precipitation of the polymers. The disadvantage of this process is that the organic solvent then must be at least partially removed by distillation under conditions such that the resin remains in the water as a disperse phase i.e., the dispersion must not be destroyed.
W. German DT-OS No. 1,795,757 discloses a cold crosslinkable acrylic resin dispersion prepared from (i) acrylates, and optionally other monomers, and (ii) halogenated acrylic esters or halogenated methacrylic esters. Because of the presence of the reactive halogen atoms, the copolymers can be vulcanized with various systems. These resins are however unsuitable as paints; and this specification does not discuss the problem of producing, from aqueous acrylic dispersions, a waterproof glossy coating.
The idea that an improvement in the gloss can be achieved by adding water-soluble resins to paint dispersions has been disclosed by K. Haman: Development Tendencies in the Lacquer Field, Farbe und Lack 907, Vol. 81 (1975). It is found that addition of a water-dilutable acid polyester to an aqueous acrylic resin dispersion permits attainment of coatings of improved gloss compared with coating obtained by use of the same acrylate dispersion without addition of polyester. However the water-resistance was unsatisfactory after subsequent cross-linking. When the acid polyester resin was replaced by a neutral, water-dilutable hydroxy polyether resin, no improvement in water-resistance of the matte coating was noted.
It is an object of this invention to provide a glossy water-proof paint based on an aqueous acrylic resin dispersion and a process for preparing the same. Other objects will be apparent to those skilled in the art.
STATEMENT OF THE INVENTION
In accordance with certain of its aspects, the novel process of this invention for preparing a cold-set lacquer for a glossy, water-proof coating may comprise
forming a reaction mixture containing an aqueous emulsion including (i) emulsifier, (ii) acrylate monomers, and (iii) cold-cross-linkable co-monomers,
adding polymerization initiator to said reaction mixture;
heating said mixture until the polymerization reaction starts;
adding to said mixture, at a temperature of from about 75° to 80° C., an aqueous pre-emulsion including further (i) emulsifier, (ii) acrylate monomers, and (iii) cold-cross-linkable comonomers;
a total of 1 to 10 percent by weight of cold-cross-linkable comonomers, based on the total amount of acrylate monomers, being employed;
and further polymerization initiator;
and adding after completion of polymerization to the resultant polymer dispersion from 3 to 15 percent by weight, based on the solids content of the polymer dispersion, of a polyaminoamide colloidally soluble in water.
DESCRIPTION OF THE INVENTION
Acrylate monomers which may be used in practice of the process of this invention may typically include the following:
(i) n-butyl acrylate, ethylhexyl acrylate, or other monomers which particularly contribute plasticizing properties;
(ii) isobutyl methacrylate, methyl methacrylate, methyl ethacrylate, acrylonitrile, or other monomers which particularly contribute adhesive properties to the final composition;
(iii) acrylic amides such as acrylamide se, methacrylamide, N-methylol ether of acrylamide, N-methylol ether of methacrylamide, etc.
(iv) hydroxyalkyl methacrylate such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc;
(v) acrylic acid se; etc.
Acrylamide, acrylic acid, and hydroxyalkyl methacrylates (such as 2-hydroxypropyl methacrylate) are particularly desirable in that they favourably influence subsequent cross-linking of the product.
It should be noted that the paints prepared in practice of this invention may not be water-resistant immediately upon application; but after the cold, cross-linking polymer systems have been in place for about one week, they are found to be water-resistant. Maximum values of water-resistance may be reached after about three weeks.
Cold, cross-linkable comonomers which may be copolymerized with the acrylate monomer, in practice of the process of this invention include those which have a reactive radical or group such as hydroxyl, amino, chloroacetoxy, etc. Illustrative of preferred comonomers may be N-methylol acrylamide, hydroxypropyl methacrylate, or chloroacetoxyalkyl acrylates such as
chloroacetoxyethyl acrylate
chloroacetoxypropyl acrylates
chloroacetoxybutyl acrylates
chloroacetoxyethyl methacrylate
chloroacetoxypropyl methacrylates
chloroacetoxybutyl methacrylates
Polymerizable monomers having chloroacetoxy groups may be preferred - typically those listed in the listing supra.
A particularly preferred co-monomer may be 2-chloroacetoxyethyl methacrylate.
The co-monomer may be added to the reaction mixture neat or in a solution in e.g. the acrylate monomer. A preferred charge may contain 10-100 parts of 2-chloroacetoxyethyl methacrylate in 100-1000 parts of butyl acrylates. Preferably the co-monomers, e.g. 2-chloroacetoxyethyl methacrylate and hydroxypropyl methacrylate may be present in an amount of 10-35, say 32.5 parts per 200-700 parts, say 348 parts of acrylate monomer, based on the solids content.
In a typical embodiment for example, the reaction mixture may contain:
(i) acrylate monomer:acrylonitrile: 75-125 parts, preferably 90-100 parts, say 95 parts;
isobutyl methacrylate: 100-250 parts, preferably 100-150 parts, say 125 parts; and
n-butyl acrylate: 75-125 parts, preferably 90-100 parts, say 95 parts;
(ii) cold, cross-linkable comonomer chloroacetoxyethyl acrylate: 2.5-50 parts, preferably 10-40 parts, say 30 parts.
The reaction mixture may also contain 1-30, preferably 5-20, say 14 parts of emulsifier. The preferred emulsifier may be anionic or non-ionic. A mixture of anionic emulsifier and non-ionic emulsifier may be employed. Illustrative emulsifiers may include: soaps of higher fatty acids; fatty alcohol sulfonates such as sodium dodecyl sulfonate; ethoxylated compositions such as the ethylene oxide adduct of octylphenol or the ethylene oxide adduct of nonyl phenol. A specific preferred emulsifier may be sodium dodecyl sulfonate.
The polymerization initiator which may be employed may be 0.5-5 parts, preferably 1-4 parts, say 3 parts of a percompound. Typical are peroxides and persulfates such as ammonium persulfate, potassium persulfate, hydrogen peroxide, etc.
The polymerization reaction is performed in a manner known per se. In the first stage, the emulsifier(s) and the water-soluble acrylate monomer (by this term there is meant herein acrylic acid and acrylamide) as well as a part of the initiator are dissolved in water and a part of the water-soluble acrylate monomers and cross-linkable monomers added whilst thoroughly stirring. The reaction mixture is heated until polymerization begins which takes place at a temperature of about 75° to 80° C. An aqueous pre-emulsion containing the remaining acrylate monomers, cross-linkable monomers, and initiator is added so slowly whilst stirring that the temperature of about 80° C. is not exceeded.
Preferably after completion of polymerization, i.e., after about 3-5 hours total time, typically after about three hours from the initial addition of components to the reaction vessel, there is added a colloidal solution of a polyaminoamide colloid to the reaction mixture.
The polyaminoamides which may be used in practice of the process of the invention may typically include resinous products which are colloidally soluble in water and formed by reacting a dimerized or trimerized unsaturated fatty acid and (iii) a polyalkylene polyamine.
There are preferably used the polyaminoamides which have been introduced onto the market by the firm of Schering under the trademark Versamid 125 and Versamid 140. These are the reaction products of dimerized linoleic acid with polyalkylene amines. These products have the following properties:
______________________________________Versamid 125 140______________________________________Specific gravity 0.98 0.98Amine number.sup.1) 290-320 350-400Acid number.sup.2) approx. 2 approx. 1Colour numberaccording to Gardner max. 12 max. 12Viscosity, poise at 25° C 400-1000 100-300______________________________________ .sup.1) mg KOH which are equivalent to 1 g of Versamid .sup.2) mg KOH which are required for the neutralisation of Versamid
The noted polyaminoamides may be added to the polymerization product in the reaction mixture after completion of polymerization in amount of 0.3-7.5 parts, preferably 2.4-7.2 parts, say 4.8 parts which corresponds to 3-15 wt.%, preferably 5-15 wt.%, say 5 wt.% of the dry weight of the copolymer.
The polyaminoamide may be added in the form of a colloidal solution containing 40-60 wt.%, preferably 45-55 wt.%, say 50 wt.% of polyaminoamide in aqueous medium, preferably water.
Other components, such as pigment, filler, opacifier, dyestuffs, etc. may be added to the composition.
It is a feature of this invention that the lacquers so prepared may be applied to form a coating typically 50-65 microns in thickness. Such coatings, when tested for pendulum impact hardness in accordance with Test DIN 53,157 are found to be outstanding. Their Gardner Gloss (as tested by DIN 67,350) and their water resistance are also found to be superior. The water resistance commonly increases substantially as the coating is allowed to set after application.
DETERMINATION OF THE WATER RESISTANCE
One drop of distilled water is placed on a lacquer-coated plate, a little hat placed thereover and the plate left for 60 minutes at 20° C. The appearance of the coat is then evaluated visually.
In order to summarize the broad range of the amounts of the several components, the preferred range, and a typical value, these numbers are hereinafter tabulated.
______________________________________Component Range Preferred Typical______________________________________Acrylate Monomer 100-1000 200-700 348Cold cross-linkable 1- 100 2- 70 35co-monomerEmulsifier 1-30 5-20 14Initiator 0.5-5 1-4 3Aqueous Component 50-500 100-300 200Pigments etc. 10-100 20-70 60______________________________________
DESCRIPTION OF PREFERRED EMBODIMENT
Practice of this invention may be observed from the following wherein, as elsewhere, all parts are parts by weight unless otherwise stated.
EXAMPLE I*
In this control example there is added to 100 parts of water, whilst stirring,
Emulsifier
6 parts of a 50 wt.%--50 wt.% mixture of sodium dodecylsulfonate as an anionic emulsifier and of ethylene oxide adduct of nonylphenol as a non-ionic emulsifier, and
Water-Soluble Acrylates
5.5 parts of acrylamide
5.6 parts of acrylic acid
Polymerization Initiator
1.7 parts of potassium persulfate
To this mixture is added, with agitation,
Acrylate Monomer
37.5 parts of isobutyl methacrylate
23.8 parts of butyl acrylate
20.0 parts of acrylnitrile
Cold Cross-linkable Comonomer
12.5 parts of hydroxypropyl methacrylate
10.0 parts of a 50 wt.% solution of chloroacetoxyethyl acrylate
This reaction mixture is heated under a gentle stream of nitrogen. The polymerization starts when the temperature is about 75° C.
At this point, there is added to the reaction mixture over a period of about one hour a "pre-emulsion" containing
Acrylate Monomers
112.5 parts of isobutyl methacrylate
73.8 parts of butyl acrylate
60.0 parts of acrylonitrile
Cold-Cross-linkable Comonomer
2.5 parts of hydroxypropyl methacrylate
30.0 parts of a 50 wt.% solution of chloroacetoxyethyl acrylate
Emulsifier and Initiator
100.0 parts of water
8.0 parts of a 50 wt.%--50 wt.% mixture of sodium dodecylsulfate and ethylene oxide adduct of nonyl phenol
1.3 parts of potassium persulfate.
The pre-emulsion is added so slowly that the temperature does not rise above 80° C.
At the end of this period, there is obtained an aqueous dispersion of finely-divided solids having a solids content of 60 wt.%.
There is then added to 100 parts of the dispersion (with vigorous stirring), the following pigment mixture:
60 parts of titanium dioxide (rutile type);
0.1 parts of "Byk-073" (Byk Gulden) anti-foaming agent;
0.5 parts of "Pigmentverteiler A" (BASF) pigment distributing agent;
40 parts of water.
The product dispersion so obtained is useful (as a control) in preparing a cold-set lacquer for a glossy water-proof coating.
All the following examples are carried out in the same manner except as specifically set forth hereinafter.
EXAMPLE II*
In this control example, the procedure of Example I is followed except that there is added to the pigment mixture:
12 parts of a 50 percent aqueous solution of a hydroxy polyester which is neutralised with trimethylamine. The hydroxy polyester is the "Versuchsprodukt 940" of DEUTSCHE TEXACO AKTIENGESELLSCHAFT. It is built up from the polyols neopentylglycol, hexanediol, and trimethylpropane and the dicarboxylic acids 2-ethylhexane dicarboxylic acid and phthalic acid and is brought up to an acid number of about 50 with trimellitic acid. The hydroxyl number is about 5.0.
EXAMPLE III*
In this control example, the procedure of example I is followed except that there is added to the pigment mixture:
6 parts of a hydroxylpolyether (Desmophen 550 U of Bayer, a hydroxyl group-containing, branched polyether having a hydroxyl content of 11.5 percent, an acid number of less than 0.5 and a viscosity at 25° C. of 650 ± 100 cps.), and
6 parts of water.
EXAMPLE IV
In this example, carried out according to the process of this invention, there is added to the pigment mixture the following:
5.2 parts of water, and
4.8 parts of the polyaminoamide "Versamid 140" (as described above)
EXAMPLE V
In this example, carried out according to the process of this invention, there is added directly into the acrylate dispersion of example I immediately preceding the addition thereto of the pigment mixture, a pre-dispersion of the following:
5.2 parts of water, and
4.8 parts of the polyaminoamide "Versamid 140")
EXAMPLE VI
In this Example, carried out according to the process of this invention, the procedure of experimental Example V is followed except that the pre-dispersion, added immediately prior to the addition of the pigment mixture, contains the following:
2.6 parts of water
2.4 parts of the same polyaminoamide used in Example V.
EXAMPLE VII
In this Example, carried out according to the process of this invention, the procedure of experimental Example V is followed except that the pre-dispersion, added immediately prior to the addition of the pigment mixture, contains the following:
7.8 parts of water
7.2 parts of the same polyaminoamide used in Example V.
EXAMPLE VIII*
In this control Example, the procedure of Example V is followed except that the cold, cross-linkable co-monomer (chloroacetoxyethyl acrylate) is omitted and, immediately preceding addition of the pigment mixture, there is added:
5.2 parts of water
4.8 parts of the polyaminoamide used in Example V.
Also tested (and listed as Example IX) is a commercially available cold-set lacquer for glossy water-proof coatings sold as an aqueous acrylate dispersion by the firm of Dr. Kurt Herberts under the trademark "Tacholit".
Results are tabulated in the Table which follows:
In the table, the following abbreviations are used:
C -- chloroacetoxyethyl methacrylate
S -- polyester
E -- polyether
P -- polyaminoamide
D -- days
W -- weeks
In the case of Water Resistance, the numerical designations have the following significance:
0 -- destroyed
1 -- markedly swollen
2 -- slightly swollen
3 -- unchanged
No entry in the Composition columns, means that a component is not present. The numbers in the composition columns represent wt.% additive, based on the total of composition.
From the paints obtained in Examples I-VIII, which contained a weight ratio of copolymer solids to titanium dioxide of 1:1, coatings were prepared of thickness of 50-65 microns. The coatings were tested for:
(i) pendulum impact hardness, in accordance with test DIN 53, 157,
(ii) Gardner gloss
in accordance with test DIN 67 530.
(iii) Water Resistance.
TABLE______________________________________ Pendulum WaterComposition Hardness Glossy ResistanceExample C S E P 3D 7D 4W 20° 45° 3D 7D 4W______________________________________I* 5 52 60 64 12 48 0 0 0 II* 5 5 46 51 60 29 65 0 0 0 III* 5 5 28 30 41 3 35 0 0 0 IV 5 8 45 46 61 7 42 2 2 3 V 5 8 49 60 65 20 69 2 2 3 VI 5 4 45 58 60 26 57 1 2 3 VII 5 12 47 56 63 8 47 2 2 3 VIII* 5 8 27 36 45 14 59 0 1 1 IX* 36 43 54 3 30 0 0 1______________________________________ *Control examples
From the above table it is apparent that the most satisfactory results are attained in experimental Examples IV-VII in which the polyaminoamide is present. The lacquers in accordance with the invention have about the same and in some cases even better hardness and gloss than the lacquers of the comparative examples and are, in addition, water-resistant: in other words, they have the desired combination of properties.
More importantly, it will be noted that the water resistance of the samples of experimental examples IV-VII rises after 4 weeks of curing, at ambient conditions prior to water-testing, to the desired level of 3 i.e., the sample is unchanged during testing, if it is allowed to stand for four weeks prior to testing.
Although this invention has been illustrated by reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made which clearly fall within the scope of this invention.
|
Cold-set lacquers are prepared by emulsifying acrylate monomers with 1 to 10 percent by weight of a cold cross-linkable comonomer in water, polymerizing, and adding to the resultant polymer dispersion, a dispersion of 3 to 15 percent by weight, based on the solids content of the polymer dispersion, of a water-soluble polyamino-amide and, optionally, usual additives. The lacquers give coatings which have good gloss and hardness and are at the same time water-resistant.
| 2
|
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. patent application Ser. No. 10/605,263, filed Sep. 18, 2003, now U.S. Pat. No. 7,523,534, issued Apr. 28, 2009, and further claims the benefit of U.S. Provisional Patent Application Nos. 60/319,560, filed Sep. 18, 2002 and 60/319,655, filed Oct. 29, 2002.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a disposable, reclosable lid having a closure tab for selectively closing a drink opening of the reclosable lid. More specifically, the invention relates to an apparatus and method for automatically assembling the closure tab to the lid.
2. Description of the Related Art
Disposable lids have long been used for closing the top of a beverage container, especially for beverages that are purchased “to go,” such as from a fast-food restaurant, for example. The disposable lids used with containers for heated drinks such as coffees and the like are often provided with a closure tab that the user can manipulate to selectively close a drink opening in the lid, thus permitting the user to drink the heated beverage when desired while otherwise keeping the drink opening closed to reduce the convective cooling of the beverage and reducing the spilling of the beverage as it moves in response to the user moving the cup.
Disposable lids of this nature are typically made by thermoforming a suitable plastic, such as High Impact Polystyrene (HIPS). The thermoforming process has the advantage of being able to produce high-quality, low-cost lids at high volumes as compared to other manufacturing techniques such as injection molding, which can make more complex shapes than thermoforming but generally has lower production rates and higher tooling costs.
For most thermoformed, reclosable lids, the tab closure is integrally formed as part of the cover, thus requiring the user to tear back the tab closure from the cover when initially opening the reclosable lid. Tear guides of some sort are normally formed on the lid to aid the user in tearing back the tab closure. After the tab closure is torn along the tear guides a discontinuity remains between the lid and the tab closure at the tear guides even when the tab closure is closed. The beverage can seep out through the discontinuity as the beverage is sloshed while the container is moved by the user, resulting in a suitable but imperfect seal.
Therefore, there is a desire to have a disposable, reclosable lid with the cost and production benefits of the thermoforming process while providing a better seal between the tab closure and the lid than is currently obtainable with thermoformed lids having an integral tab closure.
SUMMARY OF THE INVENTION
The invention addresses the disadvantages of the prior art by providing a method and apparatus for assembling a first thermoformed workpiece, such as a tab closure, to a second thermoformed workpiece, such as a lid, without the need to temporarily store either workpiece. In the context of a tab and lid operation, the apparatus and method for assembling the tab closure to the lid are automated and integrated into the traditional thermoforming lid manufacturing process thereby maintaining the cost benefit and production volume attributable to thermoformed lids.
In one aspect, the invention relates to an automated manufacturing line for making a composite thermoformed article from first and second thermoformed workpieces by automatically assembling the first thermoformed workpiece to the second thermoformed workpiece. The automated manufacturing line comprises a thermoforming station for thermoforming the first and second thermoformed workpieces in a plastic sheet, a trim station for trimming at least the first thermoformed workpiece from the plastic sheet; and an assembly station for assembling the first thermoformed workpiece onto the second thermoformed workpiece to form the composite article.
The assembly station can assemble the first thermoformed workpiece to the second thermoformed workpiece in a number of methods, including: press-fitting, snap-fitting, bonding, or ultrasonically welding.
The assembly station can comprise a carrier that moves between a first position, where it picks the first thermoformed workpiece, and a second position, where it assembles the first thermoformed workpiece to the second thermoformed workpiece. A suction device can be added to the carrier to pick the first thermoformed workpiece as it is trimmed from the sheet and hold the first thermoformed workpiece as it is carried to the second thermoformed workpiece. Additionally, a force reliever can be added to the carrier to control the amount of force applied by the carrier to the first and second thermoformed workpieces as they are assembled.
The carrier can comprise a reciprocating arm on an end of which the suction device is mounted. The force reliever can be used to mount the suction device to the end of the arm. The reciprocating arm reciprocates between a pick-up position that corresponds to the first position, and an assembly position that corresponds to the second position. The direction of reciprocation is preferably either parallel or transverse to the machine direction as defined by the movement of the plastic sheet through the assembly station.
Multiple carriers, whether in the form of reciprocating arms or not, can be arranged in at least two sets, wherein when one of the at least two sets is in the first position, the other of the at least two sets is in the second position providing for the contemporaneous pick-up of a first thermoformed workpiece while a previously picked-up first thermoformed workpiece is being assembled to the second thermoformed workpiece.
The trim station can comprise a first punch and die set for trimming the first thermoformed workpiece from the plastic sheet. In this configuration, the die comprises an inlet opening in which the punch is received to trim the first thermoformed workpiece from the plastic sheet when the plastic sheet is positioned between the punch and die, and an outlet opening into which the reciprocating arm extends to pick up the first thermoformed workpiece when the reciprocating arm is in the pick-up position.
A moveable platform can be provided for carrying the reciprocating arm and which is moveable between a first position where the reciprocating arm is positioned within the die outlet, and a second position where the reciprocating arm is positioned outside of the die outlet.
In another aspect, the invention relates to an apparatus for automatically forming a composite article by assembling first and second workpieces thermoformed in a common plastic sheet comprising a plurality of the first and second work pieces, where the assembly station comprises: a trimmer for trimming at least one of the first workpieces from the plastic sheet; and a carrier moveable between a first position, where the carrier picks up one of the first workpieces, and a second position, where the carrier assembles the first workpiece to one of the second workpieces in the plastic sheet.
The carrier preferably moves directly between the first and second positions, eliminating the need to temporarily store the first workpiece prior to assembly to the one of the second workpieces. The carrier preferably assembles the first workpiece to the one of the second workpieces by press-fitting the first and second thermoformed work pieces.
The invention also relates to a method for automatically assembling a first thermoformed workpiece to a second thermoformed workpiece from a plastic sheet comprising a plurality of the first thermoformed workpieces and a plurality of the second thermoformed workpieces to form a composite thermoformed article. The method comprises: trimming at least one of the first thermoformed workpieces from the plastic sheet to form at least one trimmed first thermoformed workpiece; immediately after trimming, carrying the trimmed first thermoformed workpiece to a corresponding second thermoformed workpiece; and assembling the trimmed first thermoformed workpiece to the corresponding second thermoformed workpiece to form a composite thermoformed article.
The assembling of the trimmed first thermoformed workpiece to the corresponding second thermoformed workpiece can comprise one of press-fitting, snap-fitting, bonding, or ultrasonically welding.
The carrying of the trimmed first thermoformed workpiece can comprise picking up the trimmed thermoformed workpiece by suction. The carrying of the trimmed first thermoformed workpiece further can also comprise stopping the suction or overpowering the suction with pressure, at the completion of the assembly of the trimmed first thermoformed workpiece to the corresponding second thermoformed workpiece. The method can additionally comprise limiting the force applied to the trimmed first thermoformed workpiece and the corresponding second thermoformed workpiece as the trimmed first thermoformed workpiece is assembled to the corresponding second thermoformed workpiece.
The trimming step can comprise the trimming of multiple first thermoformed workpieces to form multiple trimmed first thermoformed workpieces, and the assembling step can comprise assembling each of the multiple first thermoformed workpieces to a corresponding second thermoformed workpiece to form multiple composite thermoformed articles.
The trimming can be done by trimming multiple first thermoformed workpieces. The trimming of multiple first thermoformed workpieces can comprise trimming a subset of the total number of first thermoformed workpieces from the plastic sheet. The first thermoformed workpieces forming the subset can be trimmed simultaneously from the plastic sheet. Similarly, the first thermoformed workpieces forming the subset can be simultaneously assembled to corresponding second thermoformed workpieces.
The method can further comprise thermoforming the first and second thermoformed workpieces in a repeating pattern of a predetermined unit. Preferably, the subset is an integer multiple of the predetermined unit. The predetermined unit is one of a row or a column.
The first and second workpieces can be arranged in alternating rows or columns on the plastic sheet. In such a configuration, a preferred sequence of assembly comprises the first thermoformed workpiece being trimmed from one of the alternating rows or columns and assembled onto the second thermoformed workpieces in the adjacent row or column.
The thermoforming can also include the first workpiece being a thermoformed closure tab having first and second projections connected by a flexible strap, the second workpiece being a thermoformed lid having a body recess and a drink opening, wherein the snap-fitting comprises inserting the first projection into the body recess and inserting the second projection into the drink opening.
However the first thermoformed workpieces are assembled to the second thermoformed workpieces, one additional step can include the trimming of the composite thermoformed articles from the plastic sheet.
In a variation, the method for automatically assembling a first thermoformed workpiece to a second thermoformed workpiece from a plastic sheet comprising a plurality of the first thermoformed workpieces and a plurality of the second thermoformed workpieces to form a composite thermoformed article, comprising: trimming at least one of the first thermoformed workpieces from the plastic sheet to form at least one trimmed first thermoformed workpiece; carrying the trimmed first thermoformed workpiece to a corresponding second thermoformed workpiece; and press-fitting the trimmed first thermoformed workpiece to the corresponding second thermoformed workpiece to form a composite thermoformed article.
The method can also comprise the thermoforming of the first and second thermoformed workpieces in the plastic sheet such that one of the first and second workpieces has a projection and the other has a recess, and the press-fitting comprising inserting the projection into the recess. With this configuration, the press-fitting can comprise snap-fitting the projection into the recess. The projection has a portion of greater size than a portion of the recess to effect the snap fit. The first and second thermoformed workpieces can have multiple corresponding pairs of projections and recesses. The method can further comprise thermoforming the sheet from a web of plastic.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a schematic illustration of a first embodiment of a manufacturing line for thermoforming and assembling lids in accordance with the invention and which comprises a thermoforming station, an opening forming station, an assembly station, and a trimming station.
FIG. 2 is a plan view of a portion of a web of thermoformed material containing lids and corresponding tab closures suitable for use in the first embodiment.
FIG. 3 is a top perspective view of a suitable lid and tab for use in the invention after they have been removed from the web.
FIG. 4 is a bottom view of the lid and tab of FIG. 3 .
FIG. 5 is a top view of a forming tool for the first embodiment and which is used in the thermoforming station to form the lid and tab closure in the web.
FIG. 6 is a partial perspective view of the forming tool for the lid and tab closure as is shown in FIG. 5 .
FIG. 7 is a front view of a punch tool assembly for the assembly station of the first embodiment and which is used to punch the tab closure from the thermoformed web and to support the lid as the tab closure is assembled thereto.
FIG. 8 is a partial perspective view of the punch tool assembly used in the first embodiment and illustrating a punch for punching the tab closure from the thermoformed sheet and a support element for supporting the lid on the thermoformed sheet when the tab is assembled thereto.
FIG. 9 is a front view of a die assembly for the assembly station of the first embodiment that cooperates with the punch tool assembly of FIGS. 7 and 8 for punching the tab closure from the thermoformed sheet and comprises a row of access openings corresponding to the row of support elements and a row of die openings corresponding to the row of punches.
FIG. 10 is a sectional view taken along line 10 - 10 of FIG. 9 and illustrating a cross section of the access opening and the die opening.
FIG. 11 is a partial perspective view of a tab assembly mechanism for the first embodiment including multiple tab assembly devices, each having reciprocating arms for carrying the tab closure from the web into alignment with the lid.
FIG. 12 is a side view of one of the tab assembly devices of FIG. 11 and illustrating the reciprocating arms, each having tab receiver assemblies connected to each end thereof by a force relief device and for selecting a punched tab closure from the thermoformed sheet and assembling the punched tab to the lid.
FIG. 13 is a top-front perspective view of one of the reciprocating arms and illustrating in greater detail the connection of the tab receiver assemblies to the arm by the force relief device.
FIG. 14 is a top-rear perspective view of the reciprocating arm of FIG. 13 .
FIG. 15 is a partially sectioned, enlarged perspective view of the tab receiver assemblies and the force relief device of FIGS. 13 and 14 .
FIG. 16 is a schematic illustrating one possible control scheme for controlling the timing and indexing for the various components of the lid manufacturing line.
FIG. 17 is a partial sectional view of the first embodiment assembly station wherein the punch tool assembly is nearing a back stroke limit, the lower arm is prepared for picking up a tab closure, and the upper arm is carrying a tab for assembly to the lid.
FIG. 18 is a partial sectional view identical to FIG. 17 except the tab assembly device is now advanced to an over-stroke position for cleaning out any tab closures that may not have been picked up during the last cycle.
FIG. 19 is a partial sectional view identical to FIGS. 17 and 18 except that the punch tool assembly is shown in a forward stroke limit position where the punch has trimmed a tab closure from the web, and the tab assembly device is shown in an assembly position where the upper arm mounts a tab closure to a lid and the lower arm picks up the trimmed tab closure.
FIG. 20 is an alternative configuration of the manufacturing line shown in FIG. 1 , with the opening forming station, the assembly station, and the trimming station all combined into a single station.
FIG. 21 is a plan view of a portion of a web of thermoformed material containing lids and the corresponding tab closures suitable for use in a second embodiment of the invention.
FIG. 22 is a partial front view of the punch tool assembly for the second embodiment having a tab punch used to punch the tab closure from the thermoformed web, a lid support assembly to support the lid as the tab closure is assembled thereto, and a lid punch assembly for punching an assembled lid and tab from the thermoformed sheet.
FIG. 23 is a partial perspective view of the punch tool assembly of FIG. 22 .
FIG. 24 is a front view of a die shoe for the second embodiment that cooperates with the punch tool assembly of FIGS. 22 and 23 for punching the closure tab and assembled lid from the thermoformed sheet and comprising a first row of alternating access openings corresponding to the row of lid support assemblies and die openings corresponding to the row of tab punches, and a second row of die openings corresponding to the row of lid punch assemblies.
FIG. 25 is a sectional view taken along line 25 - 25 of FIG. 24 and illustrating a cross section of the die openings.
FIG. 26 is a partial perspective view of the tab assembly mechanism for the second embodiment including multiple tab assembly devices, each having reciprocating arms for laterally carrying a tab closure from the web into alignment with a lid.
FIG. 27 is an exploded view of one of the tab assembly devices of FIG. 26 showing the reciprocating receiver arms and a drive assembly for moving the arms between the tab die openings and the access openings.
FIG. 28 is a front elevational view of one of the tab assembly devices of FIG. 26 showing the relative operable positions of the reciprocating arms.
FIG. 29 is a partial sectional view of the second embodiment assembly station shown when the punch tool assembly is nearing a back stroke limit and the tab assembly device is in a back stroke limit.
FIG. 29A is a partial sectional view illustrating the relative positions of the punch tool assembly, web, die shoe, and tab assembly device when viewed from above the section shown in FIG. 29 .
FIG. 30 is a partial sectional view identical to FIG. 29 except the tab assembly device is now advanced to an over-stroke position for cleaning out any tab closures that may not have been picked up during the last cycle.
FIG. 30A is a partial sectional view illustrating the relative positions of the punch tool assembly, web, die shoe, and tab assembly device when viewed from above the section shown in FIG. 30 .
FIG. 31 is a partial sectional view identical to FIGS. 29 and 30 except that the punch tool assembly is shown in a forward-stroke limit position where the tab closure punch has trimmed a tab closure from the web, the tab assembly device is shown in an assembly position where a first reciprocating arm mounts a tab closure to a lid and a second reciprocating arm picks up the trimmed tab closure, and the lid punch has trimmed the assembled lid from the web.
FIG. 31A is a partial sectional view illustrating the relative positions of the punch tool assembly, web, die shoe, and tab assembly device when viewed from above the section shown in FIG. 30 .
FIG. 32 is a perspective view of an alternative lid support assembly having a reduced area to ease the removal of the lid while still supporting the lid during the assembly of the tab closure.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 schematically represents a first embodiment automated lid manufacturing line 10 according to the invention. The lid manufacturing line 10 comprises a thermoforming station 12 , an opening forming station 14 , an assembly station 16 , and a lid trimming station 18 through which a plastic web 20 passes. An overview of the general operation of the lid manufacturing line 10 will be useful in understanding the details of the invention. The thermoforming station 12 forms a tab and lid in the plastic web 20 . As the plastic web 20 continues through the various stations of the manufacturing line 10 , openings, such as drink openings and vent openings, for example, are punched in the tab closure and lid at the opening forming station 14 . The tab is removed from the plastic web 20 and assembled to the lid at the assembly station 16 . The lid with the assembled tab is then transferred from the assembly station 16 to the lid trimming station 18 , where the assembled lid is trimmed from the web to complete the manufacture of the reclosable lid.
FIG. 2 illustrates an example of a portion of a suitable plastic web 20 that has passed through the thermoforming station 12 resulting in lids 30 and tab closures 32 being formed in the plastic web 20 and arranged in alternating and aligned rows comprising five lids and five tab closures. The web is preferably made from a suitable plastic, an example of which is HIPS.
An illustrative lid 30 and tab closure 32 are shown in greater detail in FIGS. 3 and 4 . The lid 30 comprises a cup mounting ring 34 from which extends a peripheral wall 36 , which terminates in an upper surface 38 in which is formed a drink opening recess 41 in the form of a punched-out hole in the bottom of a recessed well. The upper surface 38 of the peripheral wall 36 transitions into a top surface 40 , which is generally parallel to the mounting ring 34 . A D-shaped well forming a reservoir 42 is formed in the top surface 40 along with a channel 44 . A locking recess 46 extends from the top surface 40 and into the peripheral wall 36 , where it terminates in opposing inwardly extending fingers 48 .
The tab closure 32 comprises a mounting portion 49 including a D-shaped mounting plug 50 and a tab portion 51 including a sealing plug 52 . A hinge in the form of a channel 54 is formed adjacent the mounting plug 50 and permits the sealing plug 52 to be pivoted relative to the mounting plug 50 . The mounting plug 50 is preferably sized to be pressed into the reservoir 42 of the lid 30 . Similarly, the sealing plug 52 is sized to be pressed into the drink opening recess 41 .
The affixing of the mounting plug 50 and the sealing plug 52 is preferably accomplished by providing the mounting plug 50 , sealing plug 52 , reservoir 42 , and drink opening recess 41 with a slight draft or taper to their sidewalls. The reservoir 42 and drink opening recess 41 preferably have a negative draft such that the sidewall extends back under the top surface 40 and upper surface 38 , respectively. The mounting plug 50 and sealing plug 52 also have a negative draft. It is also preferred that the lower peripheral edge of the mounting plug 50 and sealing plug 52 have a slightly greater periphery than the upper edges of the reservoir 42 and the drink opening recess 41 , which in combination with the negative draft, permit the mounting plug 50 and sealing plug 52 to be pressed into the reservoir 42 and drink opening recess 41 to mount the tab closure 32 to the top surface 40 of the lid 30 by snap-fitting a portion of the tab closure 32 into the lid 30 .
It should be noted that for purposes of this application the term “press-fit” refers to any type of connection where two parts are connected by at least a portion of one of the parts being received within the other and the resulting interaction between the parts, whether it be frictional, mechanical or another coupling type, results in their coupling, whether it be permanent or temporary. The term “snap-fit” is used to denote a subset of press-fit where there is at least a mechanical coupling.
When the tab closure 32 is mounted to the lid 30 , the drink opening recess 41 is selectively opened and closed by the user selectively pulling or pressing on the tab portion 51 to unsnap or snap-fit the sealing plug 52 within the drink opening recess 41 . If it is desirable to fix the tab closure 32 in an opened position, the user merely needs to pivot the tab portion 51 about the hinge 54 into the locking recess 46 until the edges of the tab portion 51 pass by the locking fingers 48 . The inherent resiliency of the tab closure 32 permits the side edges of the tab portion 51 to deflect beneath the locking fingers 48 , which will hold the tab portion 51 in the opened position until unlatched by the user.
It is important to note that the lid 30 and tab closure 32 illustrated in the patent application are only one of any type of lid and tab closure structures that can be assembled according to the invention. The lid 30 and tab closure 32 are therefore merely illustrative and aid in explaining the invention and are not in any manner limiting to the invention.
While the connecting of the tab closure 32 to the lid 30 is described as pressing a portion of the tab closure 32 into a portion of the lid 30 , the lid 30 could just as easily be pressed onto the tab closure 32 . As a matter of convenience and simplicity, the connection of the tab closure 32 to the lid 30 is described herein as the tab closure 32 being pressed into the lid 30 , with it being understood the description just as easily applies to the pressing of the lid 30 onto the tab closure 32 .
It should also be noted that the illustrative lid 30 and tab closure 32 are shaped to result in a snap-fit connection. However, the invention is not limited to such a snap-fit connection. Any suitable connection can be used with the invention, for example: press-fit, friction-fit, ultrasonic welding, or adhesion.
The invention is also not limited to assembling tabs to lids. The invention is equally applicable to the assembly of other components and is most suitable for assembling an article comprising multiple pieces formed in a web, at least one of which is removed from the web and assembled to one of the other pieces.
FIG. 5 illustrates a top view of the thermoforming station 12 and multiple lid and tab closure forms 62 , 64 about which the web 20 is shaped to form the lids 30 and tab closures 32 . The forms 62 , 64 are arranged in the same alternating rows as the web 20 of FIG. 2 . To form the lids 30 and tab closures 32 in the web 20 , the web 20 is heated and laid on top of the forms 62 , 64 . A vacuum is applied to the lower surface of the web 20 to draw the web 20 against the forms 62 , 64 , while pressurized air is then imparted to the top of the web 20 to force the web 20 to take the shape of the forms 62 , 64 . Subsequently, the web 20 is lifted up off the forms 62 , 64 and advanced.
The structure and operation of the thermoforming station 12 are generally well known in the art and further description is not necessary. An example of a suitable forming station is an IRAD Model 44 sold by Irwin Research and Development, Yakima, Wash.
It should be noted that the number of forms per row is not limiting on the invention. For purposes of this description five forms are shown for each row. However, any desired number of forms can be used for each row.
Referring now to FIG. 6 , a corresponding pair of lid and tab closure forms 62 , 64 are shown in greater detail. The forms 62 , 64 conform to the shape of the lid 30 and tab closure 32 as previously described. Therefore, they will only be briefly described.
The lid form 62 comprises multiple surfaces against which the web 20 is formed. The surfaces include a mounting ring surface 74 , a peripheral wall surface 76 , a lid form upper surface 78 , a top surface 80 , a drink opening surface 81 , a reservoir surface 82 , a channel surface 84 , and a locking recess surface 86 . Similarly, the tab closure form 64 comprises a raised upper surface 88 in which is formed a mounting plug surface 90 , a sealing plug surface 92 , and a hinge surface 94 . The sealing plug surface 92 is formed in a raised portion 93 whose upper surface will form the tab portion 51 . Similarly, the raised upper surface 88 will form the mounting portion 49 once the tab closure 32 is trimmed from the web 20 .
Once the lids 30 and tab closures 32 are formed in the web 20 , the web 20 is ultimately advanced to the opening forming station 14 where the drink and vent openings are created in the lids 30 and tab closures 32 . The opening forming station 14 is well known to one of ordinary skill in the art and will not be described in detail. For purposes of the invention, it is only necessary to understand that the opening forming station 14 removes the material in the drink opening recess 41 to form a drink opening therethrough. Similarly, the opening forming station 14 also creates a vent opening in the bottom of the reservoir 42 and another vent opening in the bottom of the mounting plug 50 to create a vent opening extending through the lid 30 and the tab closure 32 when the tab closure 32 is mounted to the lid 30 .
A suitable opening forming station 14 is an IRAD Model 44 sold by Irwin Research and Development, Yakima, Wash., and uses a punch and die structure to create the openings. It is also within the scope of the invention for the openings to be formed by the thermoforming station 12 .
FIGS. 7-13 illustrate the details of the assembly station 16 where the tab closures 32 are removed from the web 20 and snap-fitted to the lids 30 . Beginning with FIG. 7 , the assembly station 16 comprises an assembly to trim the tab closures 32 from the web 20 . The trim assembly is in the form of a punch tool assembly 100 from which extends a row of tab punch assemblies 102 for separating the tab closures 32 from the web 20 and a row of lid support assemblies 104 for supporting the lid 30 when the tab closure 32 is mounted to the lid 30 .
Referring to FIGS. 7 and 8 , each tab punch assembly 102 comprises a base 106 on which is mounted a tab punch 108 . The tab punch 108 has a punch upper surface 110 that conforms to and corresponds to the surface of the tab closure 32 that faces the lid 30 . The punch upper surface 110 includes a mounting portion surface 112 and a tab portion surface 114 on which are supported the mounting portion 49 and the tab portion 51 , respectively. A mounting plug recess 116 , a sealing plug recess 118 , and a hinge recess 120 are formed in the punch upper surface 110 and are sized and located to receive the mounting plug 50 , sealing plug 52 , and hinge 54 , respectively, when the punch 108 contacts the web 20 to assure that the mounting plug 50 , sealing plug 52 , and hinge 54 are not deformed by the punching process.
The lid support assemblies 104 comprise a base 126 on which is mounted a support element 128 having an exterior surface 130 that generally conforms to the inner surface of the lid 30 . The exterior surface 130 comprises a peripheral wall support 132 , an upper surface support 134 , a top surface support 136 , a reservoir support 138 , and a drink opening support 140 . With this structure, the peripheral wall 36 , the upper surface 38 , and the top surface 40 of the lid 30 are supported along with the reservoir 42 and the drink opening 41 while the mounting plug 50 and sealing plug 52 are snap-fitted within the reservoir 42 and drink opening 41 , respectively.
FIG. 9 illustrates a die assembly 150 that cooperates with the punch tool assembly 100 to trim the tab closures 32 from the web 20 while permitting subsequent mounting of the trimmed tab closures 32 to the lids 30 . The die assembly 150 comprises a die shoe 152 in which are formed two rows of access openings 154 . The number of access openings 154 in each row corresponds to the number of lids 30 and tab closures 32 in the web 20 . A tab die 156 is mounted to the die shoe 152 at each of the openings 154 of the lower row. Each tab die 156 includes a die opening 158 that is sized to receive the tab punch 108 and which is partially surrounded by a support element 160 , which functions similar to the support element 128 of the punch tool assembly 100 in that the support element 160 supports the portion of the web 20 surrounding the area from which the tab closure 32 is to be punched.
Although the preferred form of the invention is described in the context of punching one tab closure 32 while affixing an already punched tab closure 32 to a lid 30 , additional punch tool assemblies 100 , die assemblies 150 , and tab assembly mechanisms 190 , which will be discussed in detail hereinafter, can be added to provide for the simultaneous punching and assembly of multiple tab closures 32 to multiple lids 30 . For example, additional punch tool assemblies 100 , die assemblies 150 , and tab assembly mechanisms 190 could be added to permit the simultaneous punching and assembly of tab closures 32 for a portion of the web 20 that corresponds to the number of rows of tab closures 32 and lids 30 formed by the thermoforming station 12 in a single forming operation. With such a configuration, the web 20 would be advanced or indexed in sequence with the thermoforming station 12 .
Referring to FIG. 10 , the interior shape of the access opening 154 and the die opening 158 are shown. Initially, the die opening 158 has a reduced height as it extends through the support element 160 . When the die opening 158 reaches the main portion of the tab die 156 , there is a slight increase in the height of the die opening. The die opening 158 then opens into the lower access opening 154 extending through the die shoe 152 .
The punch tool assembly 100 is mounted for relative movement to the die assembly 150 . When the web 20 is disposed between the punch tool assembly 100 and the die assembly 150 , the punches 102 and support elements 104 are aligned to be received within the die opening 158 and the upper row of access openings 154 , respectively. Upon movement of the punch tool assembly 100 toward the die assembly 150 , the tab punch 108 is received within the die opening 158 to trim the tab closures 32 from the web 20 and the support elements 128 support the back of the lid 30 for assembly of a tab closure 32 onto the lid 30 .
The particular manner in which the punch tool assembly 100 is moved relative to the die assembly 150 is not germane to the invention and will not be described in detail. One of ordinary skill in the art will understand that there are many ways in which the movement of the punch tool assembly 100 can be accomplished.
FIG. 11 illustrates the tab assembly mechanism 190 that functions as a carrier to pick up the punched tab closure 32 and assemble it to the lid 30 . The tab assembly mechanism 190 comprises multiple tab assembly devices 192 . Although FIG. 11 only illustrates three tab assembly devices 192 , a tab assembly device 192 is provided for each column of alternating lids 30 and tab closures 32 on the web 20 . Thus, for the web 20 , as illustrated, five tab assembly devices 192 would be used.
Referring to FIGS. 11 and 12 , each tab assembly device 192 comprises a central beam 196 that is fixedly mounted to a base 198 , which is movably mounted on parallel rails 200 for permitting the tab assembly devices 192 to reciprocate relative to the die assembly 150 . A pair of receiver arms 204 are connected to common shafts 206 , which are journaled in the central beam 196 , by crank arms 208 . One end of the crank arms 208 is fixedly mounted to the shafts 206 and the other end of the crank arms 208 is pivotally mounted to the receiver arms 204 .
A spur gear 210 is mounted to one of the shafts 206 and is used instead of a crank arm 208 to connect one end of one of the receiver arms 204 to the shaft 206 . The spur gear 210 is meshed with a drive gear 212 that is mounted to a drive shaft 214 journaled in the end of the central beam 196 .
Rotation of the drive shaft 214 thereby simultaneously rotates the drive gears 212 for all of the tab assembly devices 192 and results in the simultaneous rotation of the spur gears 210 to effect the reciprocal movement of the receiver arms 204 . Since the receiver arms 204 are connected to the central beam 196 by crank arms 208 , the rotation of the spur gear 210 effectively reciprocates the receiver arms 204 between a lower position that is aligned with the die openings 158 and an upper position that is aligned with the upper row of access openings 154 . It is preferred that a servomotor 216 (shown in phantom in FIG. 11 ) is connected to the drive shaft 214 to reciprocally rotate the drive shaft 214 to effect the reciprocation of the receiver arms 204 between the lower and upper positions.
Referring to FIGS. 13-15 specifically, and FIGS. 11 and 12 generally, a tab receiver 220 is mounted at the very tip of the receiver arm 204 by a force reliever 260 , which permits the tab receiver 220 to move relative to the receiver arm 204 if the tab receiver 220 is impacted by a large enough force. Each tab receiver 220 comprises a main body 222 having a lower surface 224 in which is provided a fluid port 240 to which an air line 254 ( FIG. 16 ) is connected. The body 222 also has an upper surface 226 that conforms to the upper surface of the tab closure 32 . The upper surface 226 comprises a tab portion 228 that corresponds to the tab portion 51 of the tab closure 32 and a mounting plug portion 230 that corresponds to the mounting portion 49 of the tab closure 32 .
A tab suction inlet 232 is located in the tab portion 228 and is shaped to be received within the sealing plug 52 of the tab closure 32 . Similarly, a mounting plug suction inlet 234 is located in the mounting portion 230 and is shaped to be received within the mounting plug 50 of the tab closure 32 . Each suction inlet 232 and mounting plug inlet 234 comprise air passages 236 , 238 , respectively, which are piped to the suction port 240 to thereby fluidly couple the air line 254 to the suction inlets 232 , 234 for drawing a suction against the mounting plug 50 and sealing plug 52 when the sealing plug 52 and mounting plug 50 are picked up to hold the tab closure 32 against the tab receiver 220 . Additionally, air can be injected into the air line 254 and exhausted through the suction ports 232 , 234 .
The force reliever 260 comprises a platform 261 that is fixedly connected to the receiver arm 204 by screws 262 extending through the arm and into a side edge of the platform 261 . The platform 261 comprises spaced guide pin openings 264 , between which is provided an air line passage 266 through which the air line 254 passes when it is mounted to the suction port 240 . The guide pin openings 264 comprise a frustoconical countersink portion 268 and a constant diameter portion 270 .
Mounting pins 272 comprising a frustoconical mounting pin head 274 and a constant diameter shaft 276 are sized to be received within the guide pin openings 264 , such that the guide mounting pin heads 274 nest with the countersink portion 268 of the guide pin opening 264 and the ends of the mounting pin shaft 276 extend through the constant diameter portion 270 of the guide pin opening 264 and contact the tab receiver 220 . A coil spring 278 is mounted over each shaft 276 and extends between the tab receiver 220 and the platform 261 , such that one end of the spring abuts the lower surface 224 of the tab receiver and the other end abuts the platform 261 . A screw 280 is received through the mounting pins 272 and threaded into the tab receiver 220 to fix the mounting pins 272 to the tab receiver 220 .
The function of the force reliever 260 is to relieve any force imparted to the tab receiver 220 by contact with the tab punch 108 during the punching of the tab closure 32 from the web 20 and the picking up of the punched tab closure 32 by the tab receiver 220 . If contact occurs between the tab punch 108 and the tab receiver 220 , the springs 278 will compress, and the tab receiver 220 will slide toward the platform 261 , thus resulting in the corresponding movement of the shafts 276 within the guide pin openings 264 to relieve the force and prevent damage to the tab receiver 220 and other components of the tab assembly mechanism 190 . As the shafts 276 slide relative to the platform 261 , the mounting pin heads 274 are unseated from the countersink portion 268 of the guide pin openings 264 .
Upon the relative separation between the tab receiver 220 and the tab punch 108 , the springs 278 bias the tab receiver 220 away from the platform 261 and return the mounting pins 272 to their prior position. Upon their return, the mounting pin heads 274 nest within the countersink portion 268 , which functions to center and align the mounting pins 272 relative to the guide pin openings 264 . Additionally, the counter sink portion 268 reduces the likelihood that the shaft 276 will bind as it slides within the constant diameter portion 270 .
FIG. 16 is a schematic representation of one possible method for controlling and synchronizing the various operations of the punch tool assembly 100 and tab assembly mechanism 190 (not shown in FIG. 16 ), with the rest of the lid manufacturing line 10 . It is preferred that two controllers, a tab assembly controller 250 and a tab punch tool controller 251 , are provided to operably control the operation and synchronization of the tab assembly mechanism 190 and the punch tool assembly 100 , respectively. The tab assembly controller 250 and tab punch tool controller 251 are connected by a data link 253 , which permits the transfer of data, such as timing or position data, as need be between the controllers 250 , 251 .
The tab assembly controller 250 is operably connected to a vacuum source 252 that is connected by air lines 254 to the suction port 240 of each of the tab receivers 220 on the end of the arms 204 . The air lines 254 preferably comprise a fitting portion that connects to the tab receiver 220 and a flexible hose portion that connects the fitting portion to the vacuum source 252 . The tab assembly controller 250 also connects the air lines 254 to a compressed air supply 255 .
Thus, the tab assembly controller 250 is able to control the application of the vacuum or pressurized air to the tab receivers 220 to hold the tab closures 32 after they are trimmed from the web 20 or to blow out any tab closure 32 left in the die assembly 150 . The tab assembly controller 250 is also operably coupled to a base actuator 256 for reciprocating the base 198 of the tab assembly mechanism 190 relative to the die shoe 152 of the die assembly 150 . The tab assembly controller 250 is further connected to the servomotor 216 to effect the reciprocation of the drive shaft 214 and thereby reciprocate the receiver arms 204 between the lower and upper positions. Thus, the tab assembly controller 250 controls the operation of the various components of the tab assembly mechanism 190 to effect the picking up of a punched tab closure 32 , moving the picked up tab closure 32 into alignment with a lid 30 , and mounting the tab closure 32 to the lid 30 .
The tab punch tool controller 251 is operably coupled to an actuator 258 to reciprocate the punch tool assembly 100 relative to the die shoe 152 of the die assembly 150 . The tab punch tool controller 251 also controls the indexing and advancement of the web 20 through the assembly station 16 . Thus, the tab punch tool controller 251 controls the advancement of the web 20 to an indexed position where the punch tool assembly 100 is advanced to punch the tab closure 32 from the web 20 , where it can then be picked up by the tab assembly mechanism 190 .
The type of actuator 256 , 258 can be any suitable actuator, such as, for example, hydraulic cylinders, pneumatic cylinders, mechanical drives, and electrical motors. Also, it is within the scope of the invention for the tab assembly mechanism 190 to be mechanically operated, instead of using the servo 216 , actuator 256 , and even controller 250 . Under such an implementation, suitable mechanical connections or linkages can couple the tab assembly mechanism 190 to the punch tool assembly 100 , wherein the movement of the punch tool assembly 100 generates the desired synchronized movement of the tab assembly mechanism 190 , including both the reciprocation of the base 198 and the arms 204 . The vacuum source 252 could be operated by the tab punch tool controller 251 or directly by a position sensor, such as a limit switch.
It is also within the scope of the invention for the multiple controllers 250 , 251 to be replaced by a single controller that controls the operation and timing of the various elements of the tab assembly station 10 as need be relative to the plastic web 20 to effect the punching of the tab closure 32 from the plastic web 20 , the pickup of the punched tab 32 , and the assembly of the punched tab 32 to the lid 30 .
Referring to FIGS. 16-19 , the operation of the assembly station 16 is generally described. For purposes of the description, it is presumed that the operation is begun when the punch tool assembly 100 is near its back stroke, the upper and lower receiver arms are in the upper and lower positions, respectively, lower receiver arm 204 is not carrying a tab closure 32 , and upper receiver arm 204 is currently carrying a tab closure 32 that was picked up in the prior cycle. From this position, the tab punch tool controller 251 continues the steady-state reciprocation of the punch tool assembly 100 and advances the plastic web 20 to index the next rows of lids 30 and tab closures 32 into alignment with the access openings 154 . The tab assembly controller 250 then initiates the base actuator 256 to advance the tab assembly mechanism 190 toward the die assembly 150 . The rate of advancement of the tab assembly mechanism 190 is greater than the substantially constant stroke rate of the punch tool assembly 100 , which is beginning to move forward from its back stroke position toward the die assembly 150 .
Referring to FIG. 18 , the faster speed of the base 198 as it moves on the rails 200 results in the tab receivers 220 extending into and through the die opening 158 beyond the support element 160 into a position that is referred to as an over-stroke position. At this point in the cycle, the tab assembly controller 250 turns on the vacuum source 252 . The purpose of the over-stroke position is to ensure that no tab closures 32 were left in the die opening 158 from the prior cycles. If desired, the tab assembly controller 250 can cause a burst of pressurized air to be exhausted from the tab suction inlet 232 and mounting plug inlet 234 to blow out any tab closures 32 .
The tab assembly controller 250 then reverses the direction of movement for the base 198 of the tab assembly mechanism 190 to withdraw the tab receivers 220 from the die opening 158 into a standby position. In the standby position, the base 198 of the tab assembly mechanism 190 is preferably stopped on the rails 200 at a position where the tab receivers 220 are located at the furthest insertion depth reached by the tab punch assembly 102 to permit abutting contact between the tab receiver 220 and the tab punch 108 to improve the likelihood of a successful pickup of the tab closure 32 by the tab receiver 220 . If, for any reason, the tab receivers 220 are located beyond the forward stroke limit of the tab punch 108 , the force reliever 260 will permit the tab receiver 220 to move in response to contact with the tab punch 108 without damage while still permitting the tab receiver 220 to pick up the tab closure 32 .
Referring to FIG. 19 , with the tab receivers 220 in the standby position, the controller 251 continues the steady advance of the punch tool assembly 100 until the punch tool assembly 100 reaches its forward stroke limit. As the punch tool assembly 100 moves towards the forward stroke limit, the lid support 104 is received within the lid 30 , which by now is aligned relative to the upper access opening 154 . Similarly, the tab punch assembly 102 initiates contact with the web 20 . The continued advancement of the punch tool assembly 100 to its forward stroke limit results in the tab punch assembly 102 extending into the die opening 158 thereby trimming the tab closure 32 from the web 20 while the area surrounding the now-punched tab closure 32 is supported by the support element 160 .
As the punch tool assembly 100 reaches its forward stroke limit, the tab receiver 220 , with the vacuum on, is awaiting the arrival of the tab closure 32 punched from the web 20 . As the tab punch 108 reaches the forward stroke limit, the tab closure 32 is pulled by the vacuum against the tab receiver 220 . In addition to the picking up and retaining of the tab closure 32 , the advancement of the base 198 of the tab assembly mechanism 190 as the punch tool assembly 100 reaches its forward stroke limit also causes the tab receiver 220 of the receiver arm 204 in the upper position to press the tab closure 32 that it is currently carrying against the lid 30 currently supported by the lid support 104 . Since the tab receiver 220 is holding the tab closure 32 such that the mounting plug 50 and sealing plug 52 are aligned with the reservoir 42 and drink opening 41 , respectively, the pressing of the tab closure 32 against the lids 30 results in the mounting plug 50 and sealing plug 52 being snap-fit within the reservoir 42 and drink opening 41 , respectively, to mount the tab closure 32 to the lid 30 , with the tab closure 32 being in the closed position.
An additional benefit of the force reliever 260 is that the tab assembly pressing force can be controlled by selecting the spring force of the springs 278 . In other words, the tab receiver 220 carrying the tab closure 32 for mounting to the lid, presses the tab closure 32 against the lid 30 . The force used to press the tab closure 32 against the lid 30 can be controlled by selecting the spring force of the springs 278 .
Once the punch tool assembly 100 begins moving from the forward stroke limit toward the back stroke limit, the base 198 of the tab assembly mechanism 190 is moved to its back stroke position. As the base 198 is being moved to its back-stroke position, the tab assembly controller 250 initiates the actuation of the servomotor 216 to move the receiver arms 204 from their current position to their opposite position. In other words, the receiver arm 204 currently in the lower position is moved to the upper position and the receiver arm 204 currently in the upper position is moved to the lower position. To avoid any potential contact between the receiver arms 204 and the die shoe 152 of the die assembly 150 , the actuation of the servomotor 216 preferably does not occur until the tab receivers 220 are completely withdrawn from the access openings 154 in the die shoe 152 .
The punch tool controller 251 preferably continues the steady-state reciprocation of the punch tool assembly 100 while the tab assembly controller 250 continues the syncopated movement of the tab assembly mechanism 190 . Thus, the pickup of the tab closure 32 by the tab receiver 220 in the lower position and the snap-fitting of the tab closure 32 to the lids 30 by the tab receiver 220 in the upper position are performed on a continuous basis. This series of steps is continuously repeated as need be as long as the plastic web 20 is supplied to the assembly station 16 .
After the tab closures 32 are assembled to the lids 30 , the plastic web 20 is advanced to the lid trimming station 18 where the now assembled lid 30 and tab closure 32 combinations are trimmed from the plastic web 20 by a punch and die in a well-known manner, which is similar to the trimming of the tab closure 32 from the plastic web 20 . Therefore, the lid trimming station 18 will not be described in detail. A suitable trimming station 18 is an IRAD Model 44 sold by Irwin Research and Development, Yakima, Wash., and uses a punch and die structure to trim the assembled lids 30 from the web 20 .
In general, operation of the assembly station 16 can be thought of as a machine-direction assembly process where, as the plastic web 20 is advanced by indexing the web 20 relative to the various stations 12 - 18 , the tab closures 32 are trimmed from one row of a pair of rows comprising a row of tab closures 32 and an adjacent row of lids 30 . The trimmed tab closures 32 are mounted to the lids 30 in the next paired rows of tab closures 32 and lids 30 . In other words, the trimmed tab closures 32 are not mounted to the lids 30 in the first immediately adjacent row, but are mounted to the lids 30 in the second immediately adjacent row.
While this particular assembly sequence is preferred, it should not be considered limiting on the invention. Other sequences are possible. For example, the tab closures 32 could be mounted to the immediately adjacent row of lids 30 by the tab punch tool controller 251 holding the punch tool assembly 100 at the forward stroke limit while the receiver arm 204 is moved from the lower position to the upper position to mount the tab closures 32 to the lid 30 . In such a configuration, the tab assembly device 192 would only need one receiver arm 204 . The disadvantage of such an assembly is that it would run slower than the preferred embodiment.
Another possible variation is that many of the individual stations 12 - 18 of the manufacturing line 10 can be combined into a single station. For example, FIG. 20 illustrates a configuration where the opening forming station 14 , the assembly station 16 , and the lid trimming station 18 are combined into a single station. Since all three of these stations 14 - 18 typically use a punch and die structure to perform the opening forming, tab closure punching, and lid trimming functions, combining them will not present any insurmountable technical hurdles.
An additional variation worth mentioning is that the tab assembly mechanism 190 could also incorporate an ultrasonic welder that would be used to affix the tab closure 32 to the lid 30 . In such a configuration, the tab receiver 220 could still be used to hold and position the tab closure 32 relative to the lid 30 for the ultrasonic welder. In fact, the ultrasonic welder could be incorporated into a portion of the tab receiver 220 . Similarly, the tab assembly mechanism 190 could incorporate an adhesive application for gluing the tab closure 32 to the lid 30 .
It is also within the scope of the invention for the tab closures 32 to be assembled to the lids 30 in a direction transverse to the machine direction. In such a configuration, the lids 30 and tab closures 32 would be arranged in columns instead of rows as illustrated in FIG. 2 . The tab assembly devices 192 would need to be rotated approximately ninety degrees such that their movement between the lower and upper positions would now become a movement between a left and a right position. With this configuration, the tab closure 32 from one column is assembled to the lid 30 in an adjacent column. The disadvantage of this configuration as compared to the first embodiment is that fewer lids 30 can be assembled for a given web 20 width. For most lid manufacturing lines 10 , there is a practical limit on the width of the web 20 . Therefore, from a production output standpoint, it is more beneficial to assemble as many lids 30 for a given web 20 width as possible.
The stroke sequence and distances are also not limiting. For example, if clogging of the tab closures 32 within the die opening 158 is not an issue, then the tab receivers 220 need not be moved into the over-stroke position. Instead, they can be immediately moved to the standby position.
FIGS. 21-31 illustrate a second embodiment tab assembly line in accordance with the combined assembly station 16 and final trim station 18 shown in FIG. 20 and where the tabs are laterally or horizontally assembled to the lids. Since the substantive differences between the first and second embodiments are found in the assembly station, only the new assembly station will be described in detail, with it being understood that the description of the other stations for the first embodiment are applicable to the second embodiment.
FIG. 21 illustrates a portion of a plastic web 320 suitable for use with the second embodiment. Lids 330 and tab closures 332 are formed in the plastic web 320 and arranged in alternating and aligned columns comprising four tab columns and four lid columns. The lids 330 are identical to the lids 30 and the tab closures 332 are identical to the tab closures 32 except that they are rotated ninety degrees and arranged into columns instead of rows, which is a function of the horizontal assembly.
As with the first embodiment, the plastic web 320 is preferably made from a suitable plastic, an example of which is HIPS. The lids 330 and the tab closures 332 are formed in a thermoforming station 12 having lid forms and tab closure forms identical to the lid forms 62 and the tab closure forms 64 of the first embodiment, except that the forms 62 , 64 are organized into rows and columns in order to form the plastic web 320 shown in FIG. 21 .
FIGS. 22 and 23 illustrate the details of the second embodiment assembly station wherein the tab closures 332 are removed from the plastic web 320 and mounted to the lids 330 . Referring to FIG. 22 , the assembly station comprises a trim assembly in the form of a punch tool assembly 300 comprising an upper row formed from alternating tab punch assemblies 102 for separating the tab closures 332 from the plastic web 320 , and lid support assemblies 104 for supporting a lid 330 when the tab closure 332 is mounted to the lid 330 . The punch tool assembly 300 further comprises a lower row formed from lid punch assemblies 302 for separating a lid 330 with an assembled tab 332 from the plastic web 320 . A lid punch assembly 302 is located beneath each of the support assemblies 104 .
The punch assemblies 102 and lid support assemblies 104 were described in detail for the first embodiment. The only distinction between the punch assemblies 102 and the lid support assemblies 104 between the first and second embodiments is their rotational orientation and arrangement on the punch tool 300 as preferred to implement the horizontal assembly.
The lid punch assembly 302 is used to trim the lid 330 from the plastic web 320 . In the first embodiment, the lid punch assembly 302 would have been located on the first embodiment trimming station 18 . The lid punch assembly 302 comprises a generally columnar base 304 on which is mounted a circular lid punch 306 . The lid punch 306 comprises an annular mounting ring 308 , a neck 310 that supports an annular trim ring 312 , and a pilot 314 extending from the trim ring 312 .
The lid punch assemblies 302 are vertically aligned with the lid support assemblies 104 . The mounting ring 308 abuts the base 304 . The pilot 314 is shaped for insertion into the lid 330 and aligns and supports the lid 330 during the trimming process. The trim ring 312 is used to physically trim the lid 330 from the plastic web 320 .
FIGS. 24 and 25 illustrate a die assembly 350 that cooperates with the punch tool assembly 300 to trim the tab closures 332 from the web 320 , mounts the tab closures 332 to the lids 330 , and trims the assembled lids 330 from the plastic web 320 . The die assembly 350 comprises a die shoe 352 in which are formed a top row of access openings 154 and a bottom row of access openings 154 . The number of access openings 154 in the top row at least corresponds to the number of lids 330 and tab closures 332 in each row of the web 320 . The number of access openings 154 in the bottom row at least corresponds to the number of assembled lids 330 in each row of the plastic web 320 .
A tab die 156 is mounted to the die shoe 352 at alternating access openings 154 of the top row. Thus, the top row comprises a row of alternating access openings 154 without dies 156 and with dies 156 . A lid die 340 is mounted to the die shoe 352 at each of the openings 154 of the lower row, which alternates with the tab dies 156 on the top row. Each lid die 340 comprises a main body 346 from which extends a support element 344 , which supports the portion of the web 320 surrounding the area from which the assembled lid 330 is to be punched. The lid die 340 includes a die opening 342 that transitions from a first diameter to a larger second diameter at the junction of the support element 344 and body 346 . The first diameter is sized to receive the trim ring 312 of punch assembly 302 . The larger second diameter aids in removing the trimmed lid 330 from the lid die 340 since the trimmed lid 330 is less likely to get caught in the opening.
The punch tool assembly 300 is mounted for relative movement to the die assembly 350 . When the plastic web 320 is disposed between the punch tool assembly 300 and the die assembly 350 , the tab punch assemblies 102 and the lid support assembly 104 are aligned to be received within the die openings 158 and the access openings 154 , respectively, in the top row of the die assembly 350 , and the lid punches 306 are aligned to be received within the die openings 342 in the bottom row of the die assembly 350 . Upon movement of the punch tool assembly 300 toward the die assembly 350 , the tab punch 108 is received within the die opening 158 to trim the tab closures 332 from the plastic web 320 , the lid support assembly 104 supports the back of the lid 330 for assembly of a tab closure 332 onto the lid 330 , and the lid punch 306 is received within the die opening 342 to trim the assembled lid 330 from the plastic web 320 .
FIG. 26 illustrates the tab assembly mechanism 354 for the second embodiment used to pick up the separated tab closures 332 and assemble them to the horizontally adjacent lid 330 . The tab assembly mechanism 354 comprises two tab assembly devices 356 , with each tab assembly device 356 corresponding to two pairs of tab closure 332 and lid 330 columns comprising the plastic web 320 . That is, each tab assembly device 356 is designed to pick up two tabs 332 and place each of the tabs 332 on a separate lid 330 in one stroke.
Referring now to FIGS. 26-28 , each tab assembly device 356 comprises a base frame 376 that is slidably mounted to rails 200 fixedly mounted in the assembly station 16 to permit the tab assembly devices 356 to reciprocate relative to the die assembly 350 . The base frame 376 is shown as a generally plate-like structure to which is fixedly mounted a servomotor 372 .
A pair of upper plate drive wheels in the form of timing pulleys 364 , 365 are attached to axles 370 , which are journaled to and extend through the base frame 376 , preferably along the longitudinal axis of the base frame 376 in line with the servomotor 372 . Lower plate drive wheels in the form of a wheel 377 and a driven gear 378 are fixedly mounted to the axles 370 on the opposite side of the base 376 and secured on the axle 370 with a suitable fastener, shown in FIG. 27 as axle locking collars 382 . The wheel 377 is mounted to the axle 370 on which the timing pulley 365 is mounted. The driven gear 378 is mounted to the axle 370 to which the timing pulley 364 is mounted. As so assembled, the upper and lower plate drive wheels 364 , 365 , 377 , 378 rotate in unison with their corresponding axle 370 .
A toothed drive gear 380 is fixedly attached to the output shaft 373 of the servomotor 372 by a suitable connector, such as a drive gear locking collar 381 , for rotation of the drive gear 380 with rotation of the servomotor 372 . The drive gear 380 engages the lower plate driven gear 378 for rotation of the lower plate driven gear 378 in response to the actuation of the servomotor output shaft 373 . The rotation of the lower plate driven gear 378 also rotates the upper plate timing pulley 364 . A toothed belt 366 connects the upper plate timing pulleys 364 , 365 so that rotation of the timing pulley 364 also rotates the timing pulley 365 . Since the timing pulley 365 is coupled to the wheel 377 , the wheel 377 rotates along with the timing pulley 365 . Thus, the rotation of the output shaft 373 rotates all of the upper and lower plate drive wheels 364 , 365 , 377 , 378 .
The tab assembly device 356 is also provided with a belt tensioner wheel 374 which is adjustable for maintaining proper tension of the belt 366 around the upper plate timing pulleys 364 , 365 .
A receiver arm frame 362 is mounted to each pair of the upper and lower plate drive wheels for horizontally reciprocating in a U-shaped path in response to the rotation of the drive wheels 364 , 365 , 377 , 378 . The receiver arm frame 362 is a generally plate-like structure having a pair of bearings 368 , which receive one end of a pin 369 . Each of the upper plate timing pulleys 364 , 365 is provided with an upper drive wheel pivot pin hole 384 that fixedly receives the other end of the pin 369 . Similarly, a receiver arm frame 362 is also mounted to the lower plate wheel 377 and driven gear 378 with bearings 368 and pins 369 . The receiver arm frames 362 are mounted to the upper plate timing pulleys 364 , 365 and the lower plate wheel 377 and driven gear 378 at diametrically-opposed juxtaposition so that the upper and lower receiver arm frames 362 have an opposed reciprocal movement.
Attached to the receiver arm frames 362 are a pair of receiver arms 360 having attached tab receivers 220 , force relievers 260 , and air lines 254 (air lines are not shown in FIG. 27 for clarity) having the same structure and configuration as for the first embodiment. The receiver arms 360 are spaced on the receiver arm frame 362 such that each arm 360 is aligned with an opening 154 in the upper row of the die shoe 352 .
It should be noted that while each receiver arm frame 362 is sized to mount two receiver arms 360 to effect the simultaneous pick-up and assembly of two tabs 332 , it is within the scope of the invention for each receiver arm frame 362 to mount only one receiver arm 360 or more than two receiver arms 360 . It is also within the scope of the invention for multiple receiver arm frames 362 to be mounted to a single base plate 376 . Also, the invention can have one, two, or more tab assembly devices 356 . The number of receiver arms 360 and tab assembly devices 356 can be adjusted as needed for a given assembly configuration depending on the type and size of product being assembled.
The second embodiment of the tab assembly mechanism 354 operates in a similar manner to the first embodiment, except that as the plastic web 320 moves vertically through the assembly station 16 , and the tab closures 332 are picked up from the tab punch assembly 102 and moved horizontally to the lid support assembly 104 . Additionally, an assembled lid 330 occupying a lower row in the plastic web 320 is trimmed from the plastic web 320 at the same time that a tab closure 332 in the row above is assembled to a lid 330 and a second tab closure 332 is picked up from the plastic web 320 .
FIGS. 29-31 illustrate the same significant steps in the operation of the second embodiment as disclosed in the first embodiment. FIGS. 29-31 are arranged in pairs 29 - 29 A, 30 - 30 A, and 31 - 31 A. The first drawing of each pair illustrates the operation from the section line 25 - 25 or side view and shows the operation of the tab punch 108 and lid punch assembly 302 with their corresponding dies. The second drawing of each pair, the “A” drawing, illustrates the operation from a top view and shows the operation of the tab punch 108 and the lid support assembly 104 .
In FIGS. 29 and 29A , as with the first embodiment shown in FIG. 17 , the operation is assumed to begin when the punch tool assembly 300 is near its backstroke. The tab punch assembly 102 and lid punch assembly 302 are in operable juxtaposition to the tab die 156 for punching out the tab closures 332 in the upper row and the assembled lid 330 in the lower row. The receiver arms 360 on the upper receiver frame 362 are aligned with the tab dies 156 to pick up the punched tab closures 332 . The receiver arms 360 on the lower receiver arm frame 362 are already carrying a previously punched tab closure 332 and are aligned with the openings 154 for the subsequent assembly of the tab closures 332 to the corresponding lids 330 . In general, the separation of the tab closures 332 from the plastic web 320 , the retention of the tab closures 332 on the tab receivers 220 by an applied vacuum, and the mounting of the tab closures 332 to the lids 330 are identical to these operations performed with the first embodiment.
The plastic web 320 is advanced to an indexed position in which a row of tab closures 332 and lids 330 is aligned with the tab dies 156 and the access openings 154 , respectively, comprising the top row of the die assembly 350 . At the same time, a row of lids 330 with assembled tab closures 332 is aligned with the lid die 340 comprising the bottom row of the die assembly 350 .
Referring to FIGS. 30 and 30A , the tab assembly mechanism 354 is then advanced toward the die assembly 350 to extend the tab receivers 220 into and through the die openings 158 to clear the die openings 158 of any tab closures 332 that might remain from a previous operation. The tab assembly mechanism 354 is then withdrawn to move the tab receivers 220 into the standby position, and the punch tool assembly 300 is advanced toward the die assembly 350 .
Referring to FIGS. 31-31A , as the punch tool assembly 300 moves toward the forward stroke limit, the lid support assembly 104 is received within the lids 330 , the tab punch assembly 102 initiates contact with the plastic web 320 for removal of a tab closure 332 , and the lid punch assembly 302 initiates contact with the plastic web 320 for removal of the assembled lid 330 . The tab closures 332 are removed from the plastic web 320 and are picked up by the tab receivers 220 mounted to the receiver arms 360 attached to the upper receiver arm frame 362 . In the same operation, the tab closures 332 attached to the receiver arms 360 on the lower receiver arm frame 362 are assembled to the lids 330 . In the same operation, the assembled lids 330 are separated from the plastic web 320 and pushed through the lid die opening.
After the tab closures 332 are picked up by the upper receiver arms 360 and the tab closures 332 carried by the lower receiver arms 360 are mounted to the lids 330 , the tab assembly devices 356 are moved on the rails away from the die shoe 352 a sufficient distance such that the receiver arms 360 can be reciprocated without contacting the die shoe 352 , the punch assembly 300 is moved toward its backstroke position, and the plastic web 320 is indexed one row. The tab closures 332 held by the upper receiver arms 360 are moved horizontally into position by the reciprocating movement of the receiver arm frames 362 for assembly to the lids 330 in response to the servomotors 372 . At the same time, the lower receiver arms 360 , having assembled their tab closures 332 to the lids 330 , are moved horizontally into position for receiving a new set of tab closures 332 as they are separated from the plastic web 320 . This process is repeated continuously so long as the plastic web 320 is supplied to the assembly station 16 .
FIG. 32 illustrates an alternative lid support assembly 404 , which can be used in place of any of the previously described lid support assemblies 104 . The lid support assembly 404 has the same general structure as the previously described lid support assemblies 104 in that it has a base 426 and a support element 428 having an exterior surface 430 . The main difference in the lid support assembly 404 is that the exterior surface 430 is does not conform to the shape of the lid. For example, the exterior surface 430 comprises a peripheral wall, which has a diameter less than the inner diameter of the lid. While the exterior surface 430 does include a top surface support 436 , a reservoir support 438 , and a drink opening support 440 , it does not have the upper support surface 134 as found in the previously described lid support assemblies 104 . The structure of the lid support assembly 404 is such that it generally supports only those areas of the lid against which the tab closure will contact during assembly. This structure reduces the surface area of the lid support assembly 404 that will contact the lid and thereby reduces the likelihood that the lid will become stuck on the lid support assembly 404 and ease the removal of the lid from the lid support assembly 404 .
While the invention has been specifically described in connection with certain specific embodiments thereof, it is to be understood that this is by way of illustration and not of limitation, and the scope of the appended claims should be construed as broadly as the prior art will permit.
|
A method and apparatus for assembling a first thermoformed workpiece, such as a tab closure, to a second thermoformed workpiece, such as a lid.
| 1
|
FIELD OF THE INVENTION
[0001] This invention relates generally to construction, and, more specifically, to systems and methods for diverting fluids.
BACKGROUND OF THE INVENTION
[0002] Water and other liquids can collect on the edges of decks, porches, patios, roofs and other surfaces around buildings. When left in place, the liquids can cause molds, mildews, and rot, as well as creating a safety hazard for pedestrians. Due to surface tension, water tends to pool at points where an edge meets a wall, such as where the front edge of a balcony meets an adjoining wall. This is particularly so when the flat surface is treated with non-slip material, such as a textured polyurethane, which gives the water more surface area to which it clings. These are just some of the problems the invention disclosed herein aims to overcome.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] Certain embodiments of the present invention are described in detail below with reference to the following drawings:
[0004] FIG. 1 is an isometric view of the system for diverting fluids;
[0005] FIG. 2 is a side view thereof;
[0006] FIG. 3 is an isometric view of a different embodiment of the system for diverting fluids; and
[0007] FIG. 4 is an environmental view of the system for diverting fluids as installed.
DETAILED DESCRIPTION
[0008] This invention relates generally to construction, and, more specifically, to systems and methods for diverting fluids.
[0009] Specific details of certain embodiments of the invention are set forth in the following description and in FIGS. 1-4 to provide a thorough understanding of such embodiments. The present invention may have additional embodiments, may be practiced without one or more of the details described for any particular described embodiment, or may have any detail described for one particular embodiment practiced with any other detail described for another embodiment.
[0010] Importantly, a grouping of inventive aspects in any particular “embodiment” within this detailed description, and/or a grouping of limitations in the claims presented herein, is not intended to be a limiting disclosure of those particular aspects and/or limitations to that particular embodiment and/or claim. The inventive entity presenting this disclosure fully intends that any disclosed aspect of any embodiment in the detailed description and/or any claim limitation ever presented relative to the instant disclosure and/or any continuing application claiming priority from the instant application (e.g. continuation, continuation-in-part, and/or divisional applications) may be practiced with any other disclosed aspect of any embodiment in the detailed description and/or any claim limitation. Claimed combinations which draw from different embodiments and/or originally-presented claims are fully within the possession of the inventive entity at the time the instant disclosure is being filed. Any future claim comprising any combination of limitations, each such limitation being herein disclosed and therefore having support in the original claims or in the specification as originally filed (or that of any continuing application claiming priority from the instant application), is possessed by the inventive entity at present irrespective of whether such combination is described in the instant specification because all such combinations are viewed by the inventive entity as currently operable without undue experimentation given the disclosure herein and therefore that any such future claim would not represent new matter.
[0011] The system is comprised essentially of a wedge 100 as shown in FIG. 1 . Wedge 100 is, in preferred embodiments, defined by a sloped face 101 , lower edge 102 , sides 103 and 104 , and a substantially flat bottom 105 . In some embodiments, wedge 100 may include corner 106 . In other embodiments, corner 106 may not be necessary or desirable (see FIG. 3 ). When installed, wedge 100 creates a raised area by virtue of sloping sides 103 and 104 and the sloped face 101 . See FIG. 2 . This induces water and other materials to slide down wedge 100 and off by virtue of lower edge 102 , which is substantially flush with the surface upon which wedge 100 is installed. In preferred embodiments, wedge may be comprised of a substantially waterproof or water-resistant material. In some embodiments, wedge 100 may be comprised of a urethane material, a polyurethane material, other plastics, rubbers, resins, etc. In preferred embodiments, wedge 100 may be comprised of a substantially rigid material, but one that still has some elasticity, such as urethane. In other embodiments, wedge 100 may be comprised of a material similar or identical to the surface upon which it is installed. For one non-limiting example, wedge 100 may be formed out of teak if it is to be installed on a teak deck. Wedge 100 may be installed by adhesive, weld, fasteners, or other means appropriate for joining the material of the wedge with the material upon which it is being installed. In some embodiments, wedge 100 may be placed upon the surface and then adhered thereto by use of a sealing material (see discussion of FIG. 4 ).
[0012] In some embodiments, wedge 100 may be substantially triangular in area. In other embodiments, wedge 100 may be a half-circle, a trapezoidal shape, or rectangular. In some embodiments, wedge 100 may be placed into a corner or a joint between a floor and a wall or post of a structure. Wedge 100 may be aligned along one side with the joint between the floor and the wall, and along another side with an edge or ledge of a deck, patio, balcony, roof, or other overhang. In some embodiments, wedge 100 may be aligned along a post or beam. In a further embodiment, the system may include a plurality of wedges configured to direct fluids away from multiple sides of a beam or a post. FIG. 3 shows wedge 100 in an elongated form, which would allow contractors to cut the wedge in the field for a precise fit.
[0013] FIG. 4 shows the wedge 100 installed on a deck 200 . This is one application of the system and should not be construed as limiting. Here, wedge 100 is installed where the deck 200 meets the wall 201 , with side 104 abutting the wall and side 103 facing outward. This configuration allows fluids to run off wedge 100 and back onto the deck 200 , where they are less likely to pool and cause rot or other problems. In some embodiments, wedge 100 may be used in combination with a sealing material 202 . Sealing material 202 may be an adhesive, a texture coating, a waterproof coating, a weather-resistant material, a polymer concrete, cement, concrete, vinyl flooring material, stain, sealant, paint, or other material generally used in the construction of walking surfaces. One function of sealing material 202 may be to fix wedge 100 in place. Another function may be to provide a seamless surface, such that water and other materials cannot encroach between wedge 100 and the surface upon which it is installed. In some embodiments, the sealing material may be placed under wedge 100 and used as an adhesive to join wedge 100 with the floor or wall which it will be protecting. In some embodiments, the sealing material may be placed over wedge 100 , such as with a polyurethane or urethane coating on a deck, a boat deck, or a truck bed. In some embodiments, the sealing material may be placed both over and under wedge 100 , protecting the construction from fluid incursion in multiple layers.
[0014] While particular aspects of the present subject matter described herein have been shown and described, it will be apparent to those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from the subject matter described herein and its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of this subject matter described herein. Furthermore, it is to be understood that the invention is defined by the appended claims. It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to inventions containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.).
[0015] While preferred and alternative embodiments of the invention have been illustrated and described, as noted above, many changes can be made without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is not limited by the disclosure of these preferred and alternate embodiments. Instead, the invention should be determined entirely by reference to the claims that follow.
|
A system for diverting fluids consisting essentially of a wedge installed on a surface. The wedge is preferably triangular in area, but may be in the form of other shapes as required by the application. When viewed from the side, the wedge will often have a triangular shape because the front edge of the wedge is substantially lower than the rear edge, corner, or other shape to induce fluids and other materials to run off the sloped surface of the wedge. The system may include an adhesive to join the wedge and the surface. It may also include a sealing material disposed over the wedge and the surface to prevent incursion of fluids and other materials between the wedge and the surface.
| 4
|
CLAIM OF PRIORITY
[0001] The present application claims priority to the provisional application 60/939,443 filed to the United States Patent and Trademark Office on May 22, 2007, the content of which is hereby incorporated by reference into the present application.
FIELD OF THE INVENTION
[0002] The present invention relates in general to medical imaging systems, and more specifically, to a method for generating an automatic segmentation of the prostate boundary from 2D and 3D images.
BACKGROUND OF THE INVENTION
[0003] The prostate gland is an essential part of the male reproductive system. Located in the pelvis behind the pubic bone and right in front of the rectum and below the neck of the bladder, the prostate completely surrounds the urethra, which is the passageway that carries urine from the bladder through the penis and out of the body. In a healthy adult male, the prostate is approximately the size and shape of a walnut, weighing about 20 grams and measuring about 3 cm in width and 2.8 cm in length. Partly fibromuscular and partly glandular, the prostate gland is divided into the following four regions: Anterior fibromuscular zone, peripheral zone, central zone, and transition zone (McNeal 1988). One of the functions of the prostate is to produce a thin and milky seminal fluid that mixes with the fluid produced by the seminal vesicles, a pair of glands attached to it, to make the semen. The sperm, carried from the testicles to the prostate through the vas deferens tube, mixes with the semen. The resulting fluid is then ejaculated during orgasm first by the ejaculatory ducts to the urethra and then through the urethra out of the body.
[0004] Prostate cancer occurs when cells of the prostate begin to grow and to multiply out of control. These cells may spread out of the prostate to the nearby lymph nodes, bones or other parts of the body. This spread is called metastasis. Prostate cancer is the most commonly diagnosed malignancy in men, and is found at autopsy in 30% of men at the age of 50, 40% at age 60, and almost 90% at age 90 (Garfinkel et al. 1994). Worldwide, it is the second leading cause of death due to cancer in men. At its early stages, the disease might not have any symptoms. Some men, however, might experience symptoms that could indicate the presence of prostate cancer. Some of these symptoms include frequent and burning urination, difficulty starting a urinary stream, difficulty in having an erection, and painful ejaculation. Since these symptoms could also indicate other diseases, these men would undergo screening for prostate cancer.
[0005] When diagnosed at an early stage, prostate cancer is curable. The purpose of screening is to detect prostate cancer at its early stages before the development of any symptoms. It can be performed using two tests: the prostate-specific antigen (PSA) blood test, and the digital rectal exam (DRE).
[0006] If the DRE finds an abnormality in the prostate, or the blood test reveals a high level of PSA, then a biopsy of the prostate is recommended. A biopsy is a surgical procedure that involves removing samples of prostate tissues for microscopic examination to determine if they contain cancer cells. In the transrectal biopsy, which is the most commonly used method, a hand-held biopsy gun with a spring-loaded slender needle is guided through the wall of the rectum into the prostate gland then quickly removed. This is done under transrectal ultrasound (TRUS) guidance—a procedure that uses ultrasound generated from a probe that is inserted into the rectum to create an image of the prostate gland. The biopsy needle will contain a cylinder of a prostate tissue sample used for histological examination. This is repeated several times; each biopsy resulting in a sample from a different area of the prostate. Despite the fact that many samples (around 12) are obtained, cancer can still be missed if none of the biopsy needles pass through the cancerous growth. Although this procedure is low-risk, complication may occur. Some possible treatable complications could include prolonged bleeding into the urethra, and infection of the prostate gland or urinary tract.
[0007] An appropriate treatment choice of the prostate cancer is based primarily on its stage, PSA level, and other factors like the man's age and his general health. Treatment options change considerably if the cancer has already spread beyond the prostate. The results of this project will be used in procedures to treat localized prostate cancer, which has four treatment options, (Bangma et al. 2001), of which include brachytherapy.
[0008] Brachytherapy is radiation therapy that is minimally invasive and that involves inserting seeds containing radioactive material directly into the prostate. LDR, or low-dose-rate brachytherapy, consists of inserting low-dose or low-energy seeds permanently into the prostate. HDR, or high-dose-rate brachytherapy, on the other hand, involves placing high-dose or high-energy seeds temporarily into the prostate, and then removing them once the desired radiation dose has been delivered. HDR provides better dose control, whereas LDR is simpler and with lower risk of infection since it doesn't involve a removal procedure (Nag S. 1997). Appropriate candidates for brachytherapy are men with cancer confined to the prostate gland.
[0009] Implantation techniques for prostate brachytherapy had started as early as 1913 by inserting radium through a silver tube that was introduced into the urethra. Brachytherapy evolved in the 1970's with Whitmore who invented an open implant technique that involved interstitial implantation using an open retropubic surgery. In 1980, Charyulu described a transperineal interstitial implant technique. Then, in 1983, Holm, an urologist from Denmark, invented the TRUS-guided technique for implanting permanent radioactive seeds transperineally into the prostate (Nag et al. 1997). This technique became very popular for many reasons including the fact that it is a minimally invasive, outpatient and one-time procedure (Nag et al. 1997).
[0010] Transperineal prostate brachytherapy employs TRUS as the primary imaging modality. Under TRUS guidance, a needle carrying the radioactive seeds is inserted through the perinium and into the prostate via a template.
[0011] A successful brachytherapy procedure requires several steps, including preoperative volume study using TRUS, computerized dosimetry, pubic arch interference determination since the pubic arch is a potential barrier to the passage of the needles, and postoperative dosimetric evaluation (Pathak et al. 2000). Image processing and specifically outlining the prostate boundary accurately plays a key role in all four steps (Grimm et al. 1994). In the volume study, the TRUS probe is inserted into the rectum to acquire a series of cross-sectional 2D images at a fixed interval from the base to the apex (Nag et al. 1997). Then, the prostate boundary is outlined on these cross-sectional 2D image slices using a segmentation algorithm.
[0012] Traditional segmentation algorithms involved a skilled technician to manually outline the prostate boundary. Although this provides an acceptable result (Tong et al. 1996), it is time consuming and is prone to user variability. Therefore, several semi-automatic and fully automatic algorithms, which can be classified into edge-based, texture-based and model-based, have been proposed for segmenting the prostate boundary from 2D TRUS images.
[0000] Edge-Based Prostate Boundary Detection Methods from 2D TRUS Images:
[0013] These algorithms first find image edges by locating the local peaks in the intensity gradient of the image, and then they outline the prostate boundary by performing edge selection followed by edge linking (Shao et al. 2003). Aamink et al. presented an edge-based algorithm for determining the prostate boundary using the gradient of the image in combination with a Laplace filter. They located possible edges at the zero crossings of the second derivative of the image and determined the edge strength by the value of the gradient of the image at that location. Then they used knowledge-based features and ultrasonic appearance of the prostate to choose the correct edges. Finally, they used adaptive interpolation techniques to link the edges that actually present a boundary (Aamink et al. 1994). This method gave good results but it could generate erroneous edges due to artifacts in the image (Shao et al. 2003).
[0014] Pathak et al. also used an edge-based method for outlining the prostate boundary from transrectal ultrasound images. First, they enhanced the contrast and reduced image speckle using the sticks algorithm (Pathak et al. 2000). Then, they further smoothed the resulting image using an anisotropic diffusion filter, and used prior knowledge of the prostate and its shape and echo pattern in ultrasonic images to detect the most probable edges. Finally, they overlaid the detected edges on the top of the image and presented them as a visual guide to the observers to manually delineate the prostate boundary (Pathak et al. 2000).
[0015] Liu et al. also used an edge-based technique called the radial “bas-relief” (RBR) method for prostate segmentation where they obtained a “bas-relief” image, which they superimpose on the original TRUS image to obtain the edge map (Liu et al. 1997). Its insensitivity to edges parallel to the radial direction from the centre of the prostate was the weakness of this method (Chiu et al. 2004). In addition, this method failed if the image centre and the prostate boundary centroid were far from each other.
[0000] Texture-Based Prostate Boundary Detection Methods from 2D TRUS Images
[0016] These techniques characterize regions of an image based on the texture measures. They can determine regions of the image with different textures, and create borders between them to produce an edge map. In their work, Richard and Keen presented an automatic texture-based segmentation method, which was based on a pixel classifier using four texture energy measures associated with each pixel in the image to determine the cluster it belongs to (Richard & Keen 1996). One of the drawbacks of this method was that the resulting prostate may be represented by a set of disconnected regions (Chiu et al. 2004).
[0000] Model-Based Prostate Boundary Detection Methods from 2D TRUS Images
[0017] These techniques use prior knowledge of 2D TRUS images of the prostate to delineate the prostate boundary efficiently. Some model-based methods are based on deformable contour models, in which a closed curve deforms under the influence of internal and external forces until a curve energy metric is minimized (Ladak et al. 2000). Other methods are based on statistical models, in which the variation of the parameters describing the detected object are estimated from the available segmented images and are used for segmentation of new images. The statistical models are obtained from a training set in an observed population (Shao et al. 2003).
[0018] Prater et al. presented a statistical model-based method for segmenting TRUS images of the prostate using feed-forward neural networks. They presented three neural network architectures, which they trained using a small portion of a training image segmented by an expert sonographer (Prater et al. 1992). Their method had the disadvantage of needing extensive training data.
[0019] Pathak et al. presented a method based on snakes to detect the prostate boundary from TRUS images. They first used the sticks algorithm to selectively enhance the contrast along the edges, and then integrated it with a snakes model (Pathak et al. 1998). This algorithm required the user to input an initial curve for each ultrasound image to initiate the boundary detection process. This algorithm is very sensitive to the initial curve and only works well when this initial curve is reasonably close to the prostate boundary (Shao et al. 2003).
[0020] Ladak et al. presented a model-based algorithm for 2D semi-automatic segmentation of the prostate using a discrete dynamic contour (DDC) approach. It involved using cubic spline interpolation and shape information to generate an initial model using only four user-defined points to initialize the prostate boundary. This initial model was then deformed with the DDC model (Ladak et al 2000).
[0021] Ladak's segmentation algorithm gave good results, demonstrating an accuracy of 90.1% and a sensitivity of 94.5%. In this approach, manual initialization required about 1 min, but the prostate segmentation procedure required about 2 seconds. (Ladak et al. 2000). However, this method requires careful manual initialization of the contour and further user interaction to edit the detected boundary, which introduces complexity and user variability.
[0022] Reducing or removing user interaction, and as a result the variability among observers, would produce a faster, more accurate and reproducible segmentation algorithm. In addition, it may remove the need for the user to initialize the segmentation procedure, a critical criteria for an intraoperative prostate brachytherapy procedure.
[0023] The present invention provides an automatic prostate boundary segmentation method that minimizes and/or eliminates user initialization for segmenting the prostate in 2D or 3D images; thereby reducing both the time required for the procedure and the inter/intra-operator variability ultimately improving the effectiveness and utility of medical in the diagnosis and treatment of prostate cancer.
SUMMARY OF THE INVENTION
[0024] The present invention relates generally to a method and approach for generating automatic prostate boundary segmentation for 2D and 3D images. A fully-automated algorithm to select the prostate boundary is provided.
[0025] The method is composed of:
prostate initialization by making an assumption about the center of the prostate, edge detection using a filter to remove detail and noise, length thresholding to remove false edges and keep true edges on the prostate boundary, use of prior knowledge to aid in determining the prostate boundary by removing any prostate boundary candidates that are false edge pixels, scanning along radial lines to keep first boundary candidates. polynomial fitting to remove remaining false edge pixels and to identify unconnected edge pixels that are on the prostate boundary, and the use of pixels as initial points to a DDC model to obtain a closed contour of the prostate boundary.
[0033] Shown in this present invention is that the fully-automatic version of the algorithm performs well. Thus this method for automatic prostate boundary segmentation eliminates user initialization for segmenting the prostate from 2D TRUS images, minimizes the time required for complete prostate segmentation, reduces inter and intra-operator variability and improves the effectiveness and utility of TRUS in diagnosis and treatment of prostate cancer. Although shown here is the use of this method in prostate boundary segmentation, this method is also applicable to segmentation of any object including, tumors, kidneys, and other organs. Also shown in this present invention is the use of 2D TRUS images for initialization, however, it is also applicable to other 2D or 3D US, CT and MRI images.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] The present invention will be further understood and supported using the following drawings and their associated descriptions. These descriptions and drawings are not meant to limit the invention by any circumstance and are to be interpreted as possible embodiments of the invention disclosed herein. The methods utilized in the generation of the data represented by these drawings are commonly known within the art and may be reproduced identically by employing the methods described herein.
[0035] FIG. 1 shows a flow chart of our proposed prostate segmentation algorithm. The following sections describe the steps used to generate the initial prostate boundary that is used as an input into Ladak's DDC segmentation algorithm.
[0036] FIG. 2 shows prostate initialization. Approximate prostate center is chosen manually or automatically.
[0037] FIG. 3 shows a mask used to implement the digital Gaussian filter with σ=1.
[0038] FIG. 4 shows masks used to implement the digital 3×3 Laplacian filter.
[0039] FIG. 5 shows 5×5 digital approximation to the LoG filter.
[0040] FIG. 6 shows the LOG filter result of the prostate image in FIG. 2.2 for T=0 and σ=7.
[0041] FIG. 7 shows results after removing short-length connected components. (a) After removing connected components less than 120 pixels from the image in FIG. 6 . (b) After removing connected components shorter than 425 pixels with a minimum distance to the centre less than 50 pixels. One connected component inside the prostate gland was removed.
[0042] FIG. 8 shows an image in which matrices I in and I out represents two 5×5 regions at the pixel P on the inside and the outside of the prostate respectively. X out is the mean of I out , X in the mean of I in , σ out the standard deviation of I out and σ in the standard deviation of I in .
[0043] FIG. 9 shows t-values with their corresponding P-values.
[0044] FIG. 10 shows contrast-test membership function.
[0045] FIG. 11 shows distance test membership function.
[0046] FIG. 12 shows pixels' membership values. (a) is an image showing the membership value at each pixel based on the contrast test, (b) is an image showing the membership value at each pixel based on the distance test, (c) is an image showing the membership value at each pixel based on the product of the contrast test and the distance test, and (d) is an image showing the pixels left after keeping the pixels detected first along radial lines and removing the ones detected later.
[0047] FIG. 13 shows different F-values with their corresponding P-values.
[0048] FIG. 14 shows F-test membership function.
[0049] FIG. 15 shows remaining pixels based on the M membership function.
[0050] FIG. 16 shows remaining pixels based on the M final membership function.
[0051] FIG. 17 shows polynomial fit. Gray: Candidate prostate boundary pixels; Black: fit.
[0052] FIG. 18 shows final polynomial fit showing that the maximum distance from the fit is less than 4 mm. Gray: Candidate prostate boundary pixels; Black: fit
[0053] FIG. 19 shows the final pixels on the prostate boundary.
[0054] FIG. 20 shows the final results. (a) and (c) show the final pixels generated by our initialization algorithm before applying the DDC segmentation for two different prostate images, and (b) and (d) show the final result after deformation using DDC segmentation.
[0055] FIG. 21 shows the LoG filter output for one prostate image. (a) σ=5, (b) σ=7, (c) σ=9, and (d) σ=11.
[0056] Table 1 shows t statistic's significance level optimization. Mean number of clusters on prostate boundary, mean of their maximum gap, and mean number of clusters off the boundary for the four prostate images used for different significant level values.
[0057] Table 2 shows F statistic's significance level optimization. Mean number of clusters on prostate boundary for the four prostate images used, mean of their maximum gap, and mean number of clusters off the boundary for each significant level value α F .
[0058] Table 3 shows evaluation metrics MD, MAXD, PC, AO, and AD for the semi-automatic version of our segmentation algorithm for the entire set of 51 prostate images. The first six entries are for the images shown in FIG. 4 .
[0059] Table 4 shows evaluation metrics MD, MAXD, PC, AO, and AD for the fully-automatic version of our prostate segmentation algorithm for the entire set of 51 prostate images, and the mean and the standard deviation for the entire set.
DETAILED DESCRIPTION OF THE INVENTION
[0060] In accordance with one aspect of the present invention, as an input, the algorithm requires the approximate prostate centre. For prostate brachytherapy, the prostate gland is typically centred at the approximate centre of the image. In this case, the user does not need to select the prostate centre; as a result, the algorithm of the present invention would be fully-automatic. In cases when the prostate is not centred at the centre of the image, the user must select the approximate centre; as a result, our algorithm would be semi-automatic. FIG. 2 shows a 2D prostate TRUS image with the location of the user-selected centre shown by a dot and the centre of the image shown as a cross.
[0061] The Gaussian filter is used to blur the image and remove some detail and noise by convolving it with the 2D Gaussian distribution h(x, y):
[0000]
h
(
x
,
y
)
=
1
2
π
σ
2
-
x
2
+
y
2
2
σ
2
(
1
)
[0000] where σ is the standard deviation that determines the degree of smoothing. A digital approximation to the Gaussian function with σ=1 can be implemented using a 5×5 mask shown in FIG. 3 . A larger σ would require a larger mask.
[0062] Used for edge detection, the Laplacian of a function (image), f(x, y) , is a 2D second-order derivative defined as (Gonzalez and Woods 2002):
[0000]
∇
2
f
=
∂
2
f
∂
x
2
+
∂
2
f
∂
y
2
(
2
)
[0063] The Laplacian highlights regions of rapid intensity change. FIG. 4 shows two most commonly used digital approximations to the Laplacian filter for a 3×3 region.
[0064] The Laplacian filter is very sensitive to noise since it is a second-order derivative, is unable to detect an edge direction and its magnitude produces double edges (Gonzalez and Woods 2002).
[0065] Since the Laplacian filter is very sensitive to noise, the image can first be smoothed by convolving it with a Gaussian filter; the result is then convolved with a Laplacian filter. Since the convolution operator is associative, the same result can be obtained by convolving the Gaussian filter with the Laplacian filter first to obtain the Laplacian of Gaussian (LoG) filter, which is then convolved with the image as shown in equation 3.
[0000]
Output
Image
=
(
Input
Image
*
Gaussian
filter
)
*
Laplacian
filter
=
(
Input
Image
)
*
(
Gaussian
filter
*
Laplacian
filter
)
=
(
Input
Image
)
*
(
Laplacian
of
Gaussian
filter
)
(
3
)
[0000] The 2-D LoG operator with Gaussian standard deviation σ is given by:
[0000]
LoG
(
x
,
y
)
=
-
1
π
σ
4
[
x
2
+
y
2
2
σ
2
-
1
]
-
x
2
+
y
2
2
σ
2
(
4
)
[0066] The LoG filter consists of convolving the image with LoG(x, y) operator, which yields an image with double edges. Then, finding edge location consists of finding zero crossings between the double edges.
[0067] The LOG filter inputs two parameters: the standard deviation, σ, and a sensitivity threshold in the range [0,1] used to ignore edge points with 2D first-order derivative (gradient magnitude at that location) not greater than T. Setting T to 0 produces edges that are closed contours. We used the built-in Matlab command, edge, specifying the two parameters σ and T of the LoG filter. The size of the filter is n×n, where n=ceil (σ×3)×2+1, and ceil rounds (σ×3) to the nearest integer greater than or equal to (σ×3). The output of the edge command is a logical array with 1's where edge points were detected, and 0's elsewhere as shown in FIG. 6 (Gonzalez et al. 2004).
[0068] Visual comparison of FIGS. 2 and 6 shows that some of the edges in FIG. 6 are “true” edges on the prostate boundary, and others are “false” edges that represent noise, calcifications and other structures. The aim of the next steps is to remove most of the false edges and keep as many correct edges as possible.
[0069] Groups of edge pixels in FIG. 6 are linked together to form the image's connected components, some are short lengths consisting of few pixels and others are long lengths consisting of many pixels. For most prostate images, connected components less than 120 pixels, or 24 mm, are not part of the prostate boundary; therefore such connected components are removed. FIG. 7 ( a ) shows the results of applying this step to the image in FIG. 6 . In addition, connected components are removed with lengths less than 425 pixels, or 85 mm, and with a distance to the prostate centre that is less than 50 pixels, or 10 mm, as they would lie inside the gland since an average prostate gland measures more than 25 mm in width and height. The result of applying this step to the image in FIG. 6 is shown in FIG. 7 ( b ).
[0070] To identify the boundary of an object in an image, experts use a prior knowledge of the particular image class (Nanayakkara et al. 2006, Karmakar et al. 2002). To remove more of the “false” edges from the image shown in FIG. 7 ( b ), a prior knowledge of a typical prostate image was also used to help with determining the boundary. Some observations about 2D TRUS images of the prostate include:
The inside of the prostate gland is typically darker than the outside. The inside of the prostate gland is typically smoother than the outside. An average prostate in patients undergoing a brachytherapy procedure is approximately 3 cm in width and 2.8 cm in height.
Using these criteria, three tests were performed on each edge pixel, where each is assigned a probability of being part of the prostate boundary.
[0074] In this test, the following observation was used: inside of the prostate is typically darker than the outside. Matrices I out and I in represent two 5×5 regions at a border candidate pixel, P, with mean grey levels X out and X in respectively as shown in FIG. 8 . To prevent any overlap between these 2 matrices, their centres were chosen to be 10 pixels, or 2 mm, away from P. In order for the pixel P to be on the prostate boundary, I out has to be brighter than I in , and as a result X out should be greater than X in (Nannayakkara et al. 2006).
[0075] Since estimates of X out and X in are subject to variation due to image noise, it was tested whether X out is greater than X in , and assigned a probability of boundary membership based on the t-test where t-statistic is defined as (Rosner 2000):
[0000]
t
=
(
X
out
-
X
i
n
)
(
σ
out
2
n
)
+
(
σ
i
n
2
n
)
(
5
)
[0000] where σ out 2 is the variance of region I out , σ in 2 is the variance of I in , and n is the size of I out and I in .
[0076] If a pixel is indeed on the prostate boundary, its t-value has to be positive and significantly different than zero. The significance of the difference is measured by a P-value. FIG. 9 shows the t-values of the image pixels with their corresponding P-values.
[0077] Although conventional biomedical statistical analysis typically uses a P-value of 0.05 as a threshold for significance, a threshold value P th was chosen to optimize the segmentation performance, and t th is its corresponding t-value. Using P th , a contrast membership function, M c , was constructed as defined in equation (6), which assigns for each pixel being tested a probability of being on the prostate boundary based on its t-value. A plot of the contrast-test membership function M c is shown in FIG. 10 .
[0000]
M
c
(
pixel
)
=
{
(
P
th
-
P
pixel
)
P
th
t
pixel
>
t
th
t
value
0
else
(
6
)
[0078] The image showing each pixel's probability measure is shown in FIG. 12 a . The darker font represents pixels with a higher membership value, the lighter font represents pixels with a lower membership value, and the pixels with zero membership value are of course eliminated.
[0079] In this test, the following fact is used: typical prostates in patients scheduled for brachytherapy are on average 3 cm in width and 2.8 cm in height. Therefore, assuming a circular shape of the prostate in the 2D ultrasound image, the boundary should be found between two distances, which encompass the mean size of the prostate. The following two distances were used from the centre, d 1 =7 mm and d 2 =14 mm, and constructed a membership function, M D , as shown in FIG. 11 , which assigns for each pixel being examined a probability value based on its distance from the prostate centre. This membership function is the built-in Matalb function pimf given by equation (7).
[0000]
M
D
(
pixel
,
[
a
,
b
,
c
,
d
]
)
=
pimf
(
pixel
,
[
a
,
b
,
c
,
d
]
)
=
smf
(
pixel
,
[
a
,
b
]
)
×
zmf
(
pixel
,
[
c
,
d
]
)
;
(
7
)
[0000] where the parameters [a, b, c, d]=[minimum(dist), d1, d2, maximum(dist)]; dist is the vector of distance values from the edge pixels to the prostate centre; and the two functions smf and xmf are defined as shown in equations (8) and (10), respectively (MATLAB—The Language of Technical Computing).
[0000]
smf
(
pixel
,
[
a
,
b
]
)
=
{
1
if
(
a
≥
b
)
and
(
d
pixel
≥
a
+
b
2
)
0
if
(
a
≥
b
)
and
(
d
pixel
<
a
+
b
2
)
0
if
d
pixel
≤
a
2
×
[
(
d
pixel
-
a
b
-
a
)
2
]
if
a
<
d
pixel
and
(
d
pixel
≤
a
+
b
2
)
1
-
2
×
[
(
b
-
d
pixel
b
-
a
)
2
]
if
(
a
+
b
2
<
d
pixel
)
and
(
d
pixel
≤
b
)
1
if
b
≤
d
pixel
(
8
)
zmf
(
pixel
,
[
c
,
d
]
)
=
{
1
if
(
d
≥
c
)
and
(
d
pixel
≤
c
+
d
2
)
0
if
(
d
≥
c
)
and
(
d
pixel
>
c
+
d
2
)
1
if
d
pixel
≤
d
1
-
2
×
[
(
d
pixel
-
d
d
-
c
)
2
]
if
d
<
d
pixel
and
(
d
pixel
≤
d
+
c
2
)
2
×
[
(
c
-
d
pixel
d
-
c
)
2
]
if
(
d
+
c
2
<
d
pixel
)
and
(
d
pixel
≤
c
)
0
if
c
≤
d
pixel
(
9
)
[0000] where d pixel is the distance from the pixel under consideration to the prostate centre.
[0080] The image showing each pixel's probability for being part of the prostate boundary based on the distance test is shown in FIG. 12( b ). As with the contrast-test membership function, the darker font represents pixels with a higher membership value, the lighter font represents pixels with a lower membership value, and the pixels with zero membership value are of course eliminated.
[0081] Since a pixel on the prostate boundary has to satisfy both the contrast-test and the distance-test, we multiply the contrast-test membership function and the distance-test membership function to obtain M CD membership function as follows:
[0000] M CD (pixel)= M c (pixel)× M D (pixel) (10)
[0000] The image showing each pixel's probability value based on M CD is shown in FIG. 12( c ) using the same colour codes described previously. Although some of the false edge pixels are inside the gland, most of them are on the outside. Therefore, M CD was modified by removing more false edge pixels by assuming that true pixels are the first to be detected when scanning the image shown in FIG. 12( c ) along radial lines from the centre. Therefore, a modified membership function M′ CD was constructed as shown in equation 11 where the membership value of the first detected pixels along each radial line will be equal to M CD , and those that lie along same radial lines but are further away from the centre will have a zero membership value. The image showing each pixel's probability value based on M′ CD is shown in FIG. 12( d ) using the same colour codes described previously. As shown in this figure, more false edges have been removed.
[0000]
M
C
D
(
pixel
)
=
{
M
C
D
(
pixel
)
if
pixel
is
first
to
be
detected
along
a
given
radial
line
0
else
(
11
)
[0000] Since many false edge pixels still remain inside and outside the prostate gland, as shown in FIG. 12( d ), the observation that the inside of the prostate is typically smoother than the outside was used to perform a texture test. If σ out 2 and σ in 2 are the intensity variances of the regions I out and I in respectively, then in order for an edge pixel to be on the prostate boundary, I in should be smoother than I out , and as a result σ out 2 >σ in 2 . Since estimates of σ out 2 and σ in 2 are subject to variation due to image noise, it was tested whether σ out 2 is greater than σ in 2 , and assign a probability of boundary membership based on the F-test where F-statistic is defined as (Rosner 2000):
[0000]
F
th
F
=
σ
out
2
σ
i
n
2
(
12
)
[0000] If a pixel is indeed on the prostate boundary, its F-value has to be significantly greater than 1. FIG. 13 shows the F-values of the image pixels with their corresponding P-values.
[0082] Although conventional biomedical statistical analysis typically uses a P-value of 0.05 as a threshold for significance, a threshold value P th was chosen to optimize the segmentation performance, and F th is its corresponding F-value. Using P th , we constructed a membership function, M T , described in equation (13), which assigns for each pixel being tested a probability of being on the prostate boundary based on its F-value. A plot of the texture-test membership function M T is shown in FIG. 14 .
[0000]
M
T
(
pixel
)
=
{
(
P
threshold
-
P
pixel
)
P
threshold
if
F
pixel
>
F
threshold
0
else
(
13
)
[0083] A pixel on the prostate boundary has to satisfy all three tests; therefore, the final membership function M should be the product of M CD and M T , as described in equation 14. The image showing each pixel's probability value based on the final membership function M using the colour codes as before is shown in FIG. 15 . Most of the edge pixels with a probability greater than 0.7 are on the prostate boundary. Therefore, the final membership function, M Final , was constructed as described in equation (15), which assigns a membership of zero to the pixels with probability less than 0.7. FIG. 16 shows all edge pixels remaining after removing those with a probability less than 0.7.
[0000] M (pixel)= M CD (pixel)× M T (pixel) (14)
[0000]
M
Final
(
pixel
)
=
{
1
if
M
(
pixel
)
≥
0.7
0
else
(
15
)
[0084] As shown in FIG. 16 , some false edge pixels remain. If the prostate gland is perfectly circular, then mapping the image into (R,Θ) coordinates (where R is the distance from a pixel to the prostate centre and Θ is the clockwise angle that the pixel forms with the horizontal diameter) should result in the true edge pixels forming a straight line. However, if the prostate gland is elliptical, then this kind of mapping should result in the true edge pixels forming a curve that could be described by a 9 th order polynomial; false edge pixels would be far from the curve. Since a typical prostate gland in a transverse plane is elliptical, the removal of the false edge pixels remaining in the image shown in FIG. 16 can be carried out by mapping that image into (R,Θ) coordinates and fitting a polynomial to the pixels, as shown in FIG. 17 . We then remove a candidate pixel with the maximum distance from the resulting fit and repeat the fit and the removal of the furthest pixel until the maximum distance of pixels away from the curve is less than 4 mm. The final polynomial fit is shown in FIG. 18 , and the final image showing the remaining pixels on the prostate boundary is shown in FIG. 19 .
[0085] After the polynomial fitting, we are left with unconnected edge pixels that are highly probable to be on the prostate boundary. Some of these pixels might not be exactly on the boundary. To obtain a closed contour of the prostate boundary, we use these pixels as initial points to Ladak's et al. DDC model (Ladak et al. 2000), a polyline that deforms under the influence of internal and external forces to fit features in an image (Lobregt and Viergever 1995, Ladak et al. 2000). FIG. 20 shows two prostate images with their respective initialization points resulting from our algorithm, and final contours. FIG. 20 ( a ) shows a prostate image with the result from the initialization algorithm, and FIG. 20 ( b ) shows its closed contour after deformation with the DDC model. FIG. 20 ( c ) shows another prostate image with the result from our initialization algorithm, and FIG. 20 ( d ) shows its closed contour that results from the DDC segmentation.
[0086] To evaluate the algorithm in this present invention, we segmented 51 2D TRUS prostate images obtained from three different patients scheduled for brachytherapy using both versions of the algorithm: the semi-automatic version and the fully-automatic version. The 51 images were acquired using a transrectal ultrasound coupled to a 3D TRUS system developed in our lab (Tong et al. 1998). The images were 468×356 pixels each with pixel size approximately 0.2 mm×0.2 mm. The ‘gold standard’ in evaluating the proposed algorithm was manually outlined prostate boundaries of the same images performed by an expert radiologist.
[0087] Four different images were used to optimize the parameters employed in the algorithm. To optimize the standard deviation, σ, which determines the degree of smoothing of the LOG filter, we varied its value from σ=1 to σ=11 in increments of 2, and visually determined the value that resulted in more true edge pixels, less false edge pixels, and a contour that is closer to the prostate boundary for four different prostate images. FIG. 21 shows examples of the result of the LOG filter for one of the prostate images used with different values of σ. The optimum a value was found to be 7 ( FIG. 21 b ).
[0088] The null hypothesis for the contrast-test was that the regions I in and I out on both sides of the boundary (see FIG. 8 ) have the same mean brightness level; in which case, it would be less probable that the pixel is a part of the prostate boundary. The alternative hypothesis was that these two regions have different mean brightness levels with the outside being brighter than the inside; in which case, it is more probable that the pixel is a part of the prostate boundary. For each pixel in question, we performed a T-test with a significance level α T , and obtained a p-value. If this p-value is less than α T , then we reject the null hypothesis and assume that the alternative hypothesis is true. The higher the value of α T , the more pixels we accept as being part of the prostate boundary. To determine the optimal significance level, we performed the T-test using 7 different values of α T for each of the four images, from α T =0.001 to α T =0.05 and then computed the followings: the number of clusters on the prostate boundary, the gap between these clusters, and the number of clusters off the true prostate boundary. The objective was to find a combination that generated more clusters on the prostate boundary, smaller gaps between them, and fewer clusters off the prostate boundary. Table 1 shows for each α T the mean of the values obtained for the four prostate images. α T =0.03 was found to be the optimum.
[0089] The F-test was used to compare the standard deviation on each side of a candidate boundary pixel. The null hypothesis was that the region inside, R in , and the region outside, R out , (see FIG. 8 ) have the same variance; in which case, it would be less probable that the pixel is a part of the prostate boundary. The alternative hypothesis was that these two regions have different variances; in which case, it is more probable that the pixel is a part of the prostate boundary. After multiplying the contrast-test membership function and the distance membership function using the optimum values for the parameters σ and σ T , we performed an F-test with a significance level α F for each pixel left in question, and obtained a p-value. Like the t-test, if this p-value is less than α F , then we reject the null hypothesis and assume that the alternative hypothesis is true. The higher the value of α F , the more pixels we accept as being a part of the prostate boundary. To determine the optimal α F value, we performed the F-test using 7 different values for a for each of the four images, from α F =0.001 to α F =0.05 and then computed the followings: the number of clusters on the prostate boundary, the gap between these clusters, and the number of clusters off the prostate boundary. The objective was to find the value of α F , which generated more clusters on the prostate boundary, smaller gaps between them, and fewer clusters off the prostate boundary. Table 2 shows for each α F the mean of the values obtained for the four prostate images. α F =0.03 was found to be the optimum for the F-test.
[0090] To test the overall performance of the algorithm, the following was determined: (1) the accuracy when the user inputs the prostate centre; (2) the sensitivity to the user input position and (3) the accuracy when the prostate centre is assumed to be the centre of the image and found automatically:
[0091] Automated initialization: Assuming that the prostate is centred at the centre of the image, and there is no need for the input of the user, the fully-automatic version of our proposed segmentation algorithm was used with the optimum parameter values found above to segment the prostate boundary using the set of 51 prostate images. The results of the fully-automatic version of the segmentation algorithm were compared with the manually segmented boundaries using the evaluation metrics described below.
[0000] Distance-based and area-based metrics were used to compare the boundaries outlined using either version of our algorithm (the semi-automatic version or the fully-automatic version) to the manually outlined boundaries (Nannayakkara et al. 2006, Chiu et al. 2004, Ladak et al. 2000).
[0092] Distance-based metrics were used to measure the distance between the contour generated using either version of our segmentation algorithm and the manually outlined contour. Let C={c i , i=1, 2, . . . K} be the set of vertices that define the algorithm-generated contour, and M={m j =1:2, . . . N} be the set of vertices that define the manually generated contour. To obtain a measure of the distance between both contours, these contours were linearly interpolated to have vertices 1 pixel apart, and then the distance between a vertex, c i , from C and M, d(c 1 ,M), was computed as shown in equation (16):
[0000]
d
(
c
i
,
M
)
=
min
j
c
i
-
m
j
.
(
16
)
[0000] For each image, we computed the following three parameters:
[0093] 1) MAD, the mean absolute distance that measures the mean error in the segmentation:
[0000]
MAD
=
1
k
∑
i
=
1
k
d
(
c
i
,
M
)
.
(
17
)
[0094] 2) MAXD, the maximum distance that measures the maximum error in segmentation:
[0000]
MAXD
=
max
i
∈
[
1
,
k
]
{
d
(
c
i
,
M
)
}
.
(
18
)
[0095] 3) PC, which is the percentage of vertices in C that have a distance to M less than 4 mm, evaluates the percentage of vertices in C considered to be very close to M. 4 mm, or 20 pixels, was used because previous studies showed that using an uncertainty of contouring less than 4 mm results in an impact on the dose that covers 90% of the target volume of less than 2%, and an impact on tumour control probability of less than 10%, which was not a significant impact on the implant dosimetry (Tong et al. 1998, Lindsay et al. 2003).
[0000]
PC
=
number
of
elements
in
{
c
i
∈
C
:
d
(
c
i
:
d
(
c
i
,
M
)
≤
20
pixels
}
k
×
100
%
(
19
)
[0096] In order to evaluate the performance of the semi-automatic version and the fully-automatic version of the proposed algorithm on all images, the average of MID, MAXD, PC, was calculated along with their standard deviation for the complete set of 51 images. For each image; two area-based metrics were used to compare the area enclosed by the algorithm-generated contour and the area enclosed by the manually generated contour (Ladak et al. 2003, Chiu et al. 2004, Nanayakkara et al. 2006). Let A C and A M be the area enclosed by the algorithm-generated contour and the manually-generated contour respectively, then we define the following:
[0097] 1) AO is the percent area overlap, which measures the proportional area correctly identified by the algorithm:
[0000]
AO
=
A
C
⋂
A
M
A
M
×
100
%
(
20
)
[0098] 2) AD is the area difference, which measures the proportional area falsely identified by the algorithm:
[0000]
AD
=
A
C
-
A
M
A
M
×
100
%
(
21
)
[0099] In order to further evaluate the performance of the semi-automatic version and the fully-automatic version of the proposed algorithm on all images, the average of AO, AD was calculated along with their standard deviation for the complete set of 51 prostate images.
[0100] The initialization point for the same entire set of the 51 images analysed was fixed in table 3 to be the centre of the image. Table 4 shows the results of all the metrics described in section 3.3. The prostate images are tabulated in the same order as in table 3. Table 4 shows that the fully-automatic version of our proposed algorithm produced prostate boundaries with an average error of 0.82±0.4 mm, and an average maximum distance of 2.66±1.92 mm; over 99% of points within 4 mm from the manually generated contour. The resulting boundaries show an area overlap, AO, of 91.2% and an error, AD, of 7.09%.
[0101] The AO resulting from the semi-automatic version of our algorithm is 0.8% higher than AO produced by the fully-automatic version of our algorithm, and the AD resulting from the semi-automatic version of our algorithm is 1.4% higher than AD produced by the fully-automatic version of our algorithm. This demonstrates that the fully-automatic version of our proposed algorithm gave good results, very close to those obtained from the semi-automatic version.
[0102] The average run time for the present algorithm was approximately 10 seconds on a personal computer with a Pentium 4, 2.6 GHz, when implemented in Matlab. The time would be significantly reduced if the algorithm were implemented in C++.
[0000] The summary of the method described here is as follows:
A) A fully automated algorithm to select an object boundary.
B) A method for automatic object boundary segmentation using an image, comprising the steps of: acquiring a point at the approximate center in said image which is assumed to be the center of said object; filtering said image to identify said object edge candidates; length thresholding to remove false edges on said object boundary and keep as many true edges on said object boundary as possible; domain knowledge to remove any said object boundary candidates that are false edges and aid in identifying said object boundary; scanning of said image along radial lines keeping only first-detected said object boundary candidates; removal of remaining false edge pixels by fitting a polynomial to the said image points; generating an initial closed contour of said object's boundary using the Discrete Dynamic Contour (DDC) model.
C) The method of B), wherein said images are 2D TRUS, US, MRI and CT images of said object.
D) The method of B) and C), wherein no user selection of the said object center is needed since said object is typically centered at the approximate center of said ultrasound image.
E) The method of B) and C), wherein said filtering could be performed by and filtering system including but not limited to a Laplacian of Gaussian (LOG) filter and/or zero-crossing filtering.
F) The method of B) and C), wherein polynomial fitting removes the point with the maximum distance from the fit, and repeats the process until this maximum distance is less than 4 mm.
G) The method of A), wherein the use of pixels as initial points are used to generate an initial boundary which is deformed in a DDC model to obtain a closed contour of said object's boundary.
H) The method of A) and B), wherein said object is the prostate.
I) The method of H), wherein said domain knowledge includes; the inside of the prostate gland being typically darker than the outside, the inside of the prostate gland being typically smoother than the outside and an average prostate in patients undergoing a brachytherapy procedure being approximately 3 cm in width and 2.8 cm in height.
J) The method of claim H) and I), wherein since the average width and height of the prostate are known a circular or elliptical shape of the prostate in the 2D ultrasound image can be assumed, in which the boundary should be found between two distances that encompasses the mean size of the prostate.
K) A method for initializing a DDC model to obtain a closed contour of said object's boundary, comprising the steps of: acquiring a point at the center in said image which is assumed to be the approximate center of said object; filtering said image to identify said object edge candidates; length thresholding to remove false edges on said object boundary and keep as many true edges on said object boundary as possible; domain knowledge to remove any said object boundary candidates that are false edges and aid in identifying said object boundary; scanning of said image along radial lines keeping only first-detected said object boundary candidates; removal of remaining false edge pixels by fitting a polynomial to the said image points; generating an initial closed contour of said object's boundary using the Discrete Dynamic Contour (DDC) model.
|
Segmenting the prostate boundary is essential in determining the dose plan needed for a successful bracytherapy procedure—an effective and commonly used treatment for prostate cancer. However, manual segmentation is time consuming and can introduce inter and intra-operator variability. This present invention describes an algorithm for segmenting the prostate from two dimensional ultrasound (2D US) images, which can be full-automatic, with some assumptions of image acquisition. Segmentation begins with the user assuming the center of the prostate to be at the center of the image for the fully-automatic version. The image is then filtered to identify prostate edge candidates. The next step removes most of the false edges and keeps as many true edges as possible. Then, domain knowledge is used to remove any prostate boundary candidates that are probably false edge pixels. The image is then scanned along radial lines and only the first-detected boundary candidates are kept the final step includes the removal of some remaining false edge pixels by fitting a polynomial to the image points and removing the point with the maximum distance from the fit. The resulting candidate edges form an initial model that is then deformed using the Discrete Dynamic Contour (DDC) model to obtain a closed contour of the prostate boundary.
| 6
|
CROSS REFERENCE TO RELATED APPLICATION
The subject matter of this application is related to the subject matter of an application entitled "Reconfigurable Remote Control" filed by Kenneth B. Welles II, Ser. No. 610,377 filed concurrently herewith and assigned to a common assignee with this application. The subject matter of that application is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention generally relates to remote control transmitters of the type used with various consumer products such as television receivers and the like and, more particularly, to a reconfigurable remote control transmitter which may be programmed to emulate any one of a plurality of individual transmitters.
BACKGROUND OF THE INVENTION
Many new consumer electronic products, particularly video products, are available with hand held infrared remote control transmitters. A consumer may have separate remote control transmitters for a television, a cable converter, video cassette recorder, and a video disc player, for example. In such a case, it is confusing to know which transmitter to pick up to control which product. Moreover, carrying around four different remote control transmitters spoils the convenience of the remote control feature. It is therefore desirable to provide a single remote control transmitter for controlling each of the several products.
A number of solutions have been proposed for this problem in the prior art. One example is disclosed in the patent to Litz et al, U.S. Pat. No. 4,274,082. In the Litz et al system, an amplifier, a tuner, a tape recorder, and a turntable are interconnected by a two-conductor cable. Each of these devices is controlled by a corresponding microprocessor, and a hand held transmitter is used to transmit coded signals that control the operation of the individual devices. The coded signals are received by a common receiver and first conversion circuit to provide voltage pulses on the two-wire cable. Additional conversion circuits are required for each microprocessor in order to convert the voltage pulses on the two-wire cable to pulses which can be used by the microprocessors.
Another example is disclosed in U.S. Pat. No. 4,200,862 to Campbell et al. The Campbell et al system includes a single receiver/transmitter unit which may be placed on a table, for example, and a hand held transmitter, but in this case, the receiver/transmitter unit injects digital pulses onto the house mains at times of zero crossing of the mains voltage. Various appliances are plugged into the house mains via slave units which are each responsive to an assigned digital address and a digital operation code to control its appliance.
Common to both the Litz et al and Campbell et al systems is the use of a central receiver, an interconnecting transmission line and the requirement of a separate controller device for each product or appliance. Clearly, this approach solves the basic problem of multiple transmitters for multiple products or appliances, but the solution is both complex and expensive from the point of view of the consumer. A simpler, less expensive solution to the problem is needed.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a single remote control transmitter which can operate any product or appliance with a remote control feature without modification or interconnection of the individual products or appliances.
It is another object of the invention to provide a simple and inexpensive control for a plurality of remotely controlled consumer products even though those products may be produced by different manufactures and respond to different transmission protocols.
The objects of the invention are accomplished by providing a reconfigurable remote control transmitter that has the ability to learn, store and repeat the remote control codes from any other infrared transmitter. The reconfigurable remote control transmitter includes an infrared receiver, a microprocessor, nonvolatile and scratch pad random access memories, and an infrared transmitter. The microprocessor application is divided into four main categories: learning, storing, retransmitting, and user interface. In the learning process, the reconfigurable remote control transmitter receives and decodes the transmissions from another remote control transmitter for, say, a television receiver. The process is repeated at least twice for each key to make sure that it has been properly received and decoded. Once the data has been received and decoded, it must be stored for later use; however, in order to do this, the received and decoded data must be compressed so that it can fit into the nonvolatile memory. This process is repeated for each of the several remote control transmitters that are to be replaced by the reconfigurable remote control transmitter. When the learning and storing operations have been completed, the reconfigurable remote control transmitter is ready to use.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, advantages and aspects of the invention will be better understood from the following detailed description of the invention with reference to the drawings, in which:
FIGS. 1a to 1i are graphical representations of several modulation schemes which are used in infrared remote control transmitters;
FIGS. 2a to 2d are graphical representations of several keyboard encoding schemes that may be used with the modulation schemes illustrated in FIGS. 1a to 1i;
FIG. 3 is a plan view of the reconfigurable remote control transmitter according to a preferred embodiment of the present invention;
FIGS. 4a-4d, when aligned from left to right, constitute a block diagram of the reconfigurable remote control transmitter according to a preferred embodiment of the invention;
FIGS. 5a and 5b are graphical and tabular representations of the data collection and initial data compression technique performed by the preferred embodiment shown in FIG. 4;
FIG. 6 is a tabular representation of the correlation process performed during the learning procedure;
FIG. 7 is a tabular representation of the process of removing repeats from the learned code in order to further compress the data for storing in the nonvolatile memory; and
FIG. 8 is a tabular representation of the compressed learned code.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In order to understand the learning process, the available infrared codes to be learned must first be understood. This turns out to be a very wide range of different codes. FIG. 1 illustrates several modulation schemes. FIGS. 1a through 1g are different types of gated carrier frequency. Typical carrier frequencies for infrared remote transmitters are 20 KHz to 45 KHz, with the majority at 38 KHz and 40 KHz. The gating schemes illustrated include both fixed and variable bit periods, non-return to zero (NRZ), variable burst width, single/double burst modulation schemes, and a final catch-all category called random because there is no readily distinguishable pattern of ones and zeros. In addition to these schemes, there is also a transmitter which puts out a different continuous frequency (CW) for each key at approximately 300 Hz spacings as represented in FIG. 1h. Finally, several new types of transmitters do not use a carrier frequency at all but, instead, send a stream of pulses where the data is encoded in the spacing between infrared pulses as shown in FIG. 1i.
FIG. 1 shows the data modulation schemes, but most transmitters also have a higher level of data organization, which may be called a keyboard encoding scheme. This causes data to be sent in different formats depending on the transmitter and the key pressed. FIG. 2 shows several of these keyboard encoding schemes. FIG. 2b shows data that is sent once for each key press. FIG. 2c shows data that is repeated three times and then stopped for each key press. These schemes are used to conserve power and extend battery life. FIG. 2c also shows data that continues to repeat as long as the key is pressed. This is often used for continuous functions such as volume control or channel scanning. FIG. 2d shows a modification of the continuous repeat scheme shown in FIG. 2c where the initial key data is sent, followed by a series of "keep-alive" pulses as long as the key is pressed. This scheme is also used to conserve power and extend battery life. In addition to schemes 2b through 2d, some remote control transmitters precede all transmitted key data with some form of preamble data stream to get the receiver's attention. This is shown in FIG. 2a, but it will be understood that such preamble data stream can be used with each of the keyboard encoding schemes shown in FIG. 2.
Reference is now made to FIG. 3 which shows in plan view the reconfigurable remote control transmitter according to a preferred embodiment of the invention. The first thing to be observed is that this unit is not much more complicated than a single transmitter for a single product. This is accomplished by the use of a combination of hard keys and soft keys and an liquid crystal display (LCD) about which more will be said later. Suffice it to say for now that hard keys are those which have a predefined function and soft keys are those which have a programmable function. The reconfigurable remote control transmitter shown in FIG. 3 is capable of emulating up to four different transmitters which are indicated in the liquid crystal display 10 adjacent the legend "SOURCE" as TV, VCR, CABLE, and AUX, the latter being for "auxiliary" which may be any fourth device such as, for example, a video disc player. The user selects the desired source by pressing the source key 12 each time a change in the source is desired, which causes the individual legends TV, VCR, CABLE, and AUX to be successively displayed in accordance with the succession of source key depressions. When the legend for the desired source is displayed, the user simply stops depressing the source key and proceeds to operate the selected source. There is also provided a learning switch (not shown) which may be provided in a protected location on the side or bottom of the transmitter case since this switch is used only once (typically) for each transmitter which is to be emulated. This switch might be located, for example, behind a slidable or pivotal cover 67 in order to prevent younger members of the family from operating it. In the learning mode, the switch is moved to the learning position and the transmitter which is to be emulated is placed so that its transmitter infrared light emitting diode (LED) is adjacent the photoelectric receiver in the reconfigurable remote control unit. The photoelectric receiver 14 might, for example, be located at the end opposite to the infrared LED transmitter 16 in the reconfigurable remote control transmitter as shown in FIG. 3. The source is selected by pressing the source key 12 as described above, and when the legend for the desired source is displayed, the user presses the enter key 78. The user is then prompted in the liquid crystal display 10 to press a key on the reconfigurable remote control transmitter and a corresponding key on the transmitter to be emulated so that the transmitted code can be received and encoded. As will be explained in further detail, this prompt is repeated at least twice for each key in order to insure that the transmitted signal has been properly received and encoded.
Turning now to FIG. 4, the receiver 14 for the reconfigurable remote control transmitter includes a photodiode 18 connected by a differentiating capacitor 20 to the variable input of threshold amplifier 22. The output of this amplifier 22 is a series of pulses having a frequency equal to the frequency of the transmitted signal. The output of amplifier 22 is connected to an input of the microprocessor 24 and also to a detector diode 26. The output of the detector diode 26 is integrated by capacitor 28 and supplied to the variable input of a second threshold amplifier 30. The output of this amplifier is the detected envelope of the transmitted signal and is supplied to another input of the microprocessor 24. Also supplied as inputs to the microprocessor 24 are the outputs of the push button keyboard 32 and the learn switch 34. The microprocessor 24 has its own internal clock which is controlled by a crystal 36. The microprocessor 24 provides addresses for the nonvolatile random access memory 38 and the scratch pad memory 40 to the address register 42 which comprises an 8-bit latch. The two memories are essentially the same except that the nonvolatile random access memory 38 is provided with a low voltage power supply 45, typically a lithium battery, in addition to being supplied from the main power supply in order to maintain the data stored in the memory even when the main battery supply is off or dead. The microprocessor 24 also provides the control signals to the LCD driver 46 which in turn controls the liquid crystal display 10. In addition, the microprocessor provides the drive signals for the infrared transmitter 16. In order to minimize battery drain, the several integrated circuits shown in FIG. 4 are made with CMOS (complementary metal oxide semiconductor) technology. For example, the microprocessor may be an Intel 87 C51 or a Mitsubishi 50741 microprocessor, and the memories may be Intel 2816 or Hitachi HM6116 random access memories.
The reconfigurable remote control, in the learning process, must be able to receive, learn and repeat all of the schemes described with reference to FIGS. 1 and 2. In addition, in the learning process the reconfigurable remote control must read each code at least twice to make sure that it has been properly received and decoded. Small variations in the incoming code must be tolerated while large variations (errors) must be recognized and rejected. The process is illustrated with reference to FIGS. 5 and 6. Referring to FIG. 5a first, the modulation scheme represented by FIG. 1b is taken as exemplary. This modulation scheme uses a fixed bit time but the burst width is modulated. In other words, the time for a binary "1" is the same as the time for a binary "0" but, in the case illustrated, the number of pulses transmitted for a "1" is more than for a "0". The time period for a binary bit is nominally 1.85 milliseconds, the number of pulses for a binary "1" is nominally 37, and the number of pulses for a binary "0" is nominally 16. When the learn switch 34 is switched to the "learn" position, the liquid crystal display 10 flashes the letter "L" to constantly remind the user that the reconfigurable remote control transmitter is in the learn mode. The user is then prompted to press a key on the reconfigurable remote control transmitter and a corresponding key on the transmitter to be emulated in order to transmit a signal to be received and encoded. The first step in the receiving and encoding process is to count the number of pulses in each burst and the time period of each pause between pulses. This pulse count and pause duration data completely defines the incoming signal. From this data the frequency of the transmitted signal is computed by dividing the largest number of pulses in a single burst by its corresponding time duration. For example, in FIG. 5a the largest number of pulses is 38 and its time period is 0.95 milliseconds. The reason for using the largest number of pulses and its time period is to obtain the most accurate determination of the frequency of the transmitted signal. This initial raw data consists of 100 states, each state being defined as two 16-bit numbers (between 1 and 65535). The first 16-bit number represents the number of infrared pulses in the pulse train. The second 16-bit number represents the time interval that the infrared pulse train was off. An additional 16-bit number represents the frequency of the infrared pulse train (typically from 30 KHz to 100 KHz). This data requires about 3200 bits of data per key pressed.
The first compression of this data is made by categorizing the pulse bursts and pauses into "bins", each bin being two bytes with the most significant bit indicating whether the bin is a burst or a pause. As shown in FIG. 5a, four bins are established for the illustrated example. These are labled A, B, C, and D with A and C being designated as bins for bursts and B and D being designated as bins for pauses. It will of course be understood that more or fewer bins may be required depending on the modulation scheme which is being learned. In order to categorize the pulse bursts and pauses into the several bins, a tolerance is established so that all the bursts and pauses within a nominal range are appropriately categorized into one or another of the bins. This is indicated in FIG. 5b which shows lower, middle and upper values of the number of pulses in a burst and the duration of a pause. Those bursts or pauses not falling into one of these bins would be assigned to another bin established for that burst or pause. By creating these bins, the initial raw data or about 3200 bits is stored to 1600 bits per key and 16 bits per bin in the scratch pad memory 40 of FIG. 4. The user is then prompted in the liquid crystal display 10 to press the encoded key a second time and the process is repeated. Then correlation is performed on the encoded data for that key as illustrated by FIG. 6. Suppose that for key one, the two encoded data are the same as shown at the top of the figure. In this case, the key code sequence has been properly learned and can be further compressed for storage in the nonvolatile memory 38. On the other hand, assume that in the process of pressing key two for the second time, the user inadvertently moves the transmitter to be emulated and the reconfigurable remote control transmitter with respect to one other so that the encoding for the second key press is an error. In this case, the user will be prompted on the liquid crystal display 10 to press the key a third time. If the third encoding matches the first as illustrated in the figure, then the key code sequence is considered to be properly learned and can be further compressed for storage in the nonvolatile memory. A third possibility is illustrated in FIG. 6 and this is the case where the initial encoding is in error. Under these circumstances, no successive encoding would ever match the first. What the correlation algorithm does in this case is if the third encoding does not match the first, then the fourth is compared with the third and so on until a match of alternate encodings is obtained.
When each key has been properly learned, the initially encoded data or each key must be further compressed to such an extent that the data for all four remote transmitters will fit into a 2K byte memory. This data compression must maintain all of the vital information so that the infrared signal can be accurately reconstructed during transmission. The first step is illustrated in FIG. 7 and involves the removal of repeats from the key encoding. It will be recalled that some of the keyboard encoding schemes shown in FIGS. 2c and 2d involved repeated transmission patterns. As illustrated in FIG. 7, the first two bytes (each representing a different bin) are compared with the second two bytes, and if there is no match, then the first four bytes are compared with the next four bytes. Again, if there is no match, the first six bytes are compared with the next six bytes and so on increasing in two byte intervals until a total of half of the stored bytes are being compared with the other half of the stored bytes. If no match is obtained, then the process is repeated from the start but omitting the first two bytes and then the first four bytes. In the case illustrated in the figure, a repeating pattern of ten bytes is found after an initial four byte preamble. The number and pattern of the repeats are then encoded in a reduced format, as shown in FIG. 8. This reduces data to between 6 and 60 states per key, 96 to 960 bits of data per key. Once this has been accomplished, the encoding for all keys is examined in order to determine if there is a common preamble. If there is, this preamble is separately encoded and stripped from the encoding of all keys. This reduces data to (typically) 96 to 480 bits per key. Then the number of bins is represented by a smaller number of bits than the eight bits comprising each byte. For the case illustrated in FIG. 5, for example, the number of bits required to represent the four bins is only two. Typically, the 8-bit pin pointer or number is reduced to a 5-bit or less bin pointer depending on the number of bins required to encode the original data. This typically reduces data to 48 to 240 bits per key. In this way, data is reduced to a manageable storage size, and all of the compression data is also retained to allow re-expansion of the data to its uncompressed format for retransmission during emulation. More specifically, the compressed data comprises the bin code, the position of the start of any repeating patterns, the length of the repeating pattern, the number of repeats, and the frequency of the transmission. If there is a preamble, this is stored separately to be generated for each key pressed. This compressed data is then stored in the nonvolatile memory 38 of FIG. 4.
This completes the learning and storing processes which are common to all the keys on the transmitter to be emulated. Certain keys are common to most remote transmitters, and these keys are included on the reconfigurable remote control transmitter as shown in FIG. 3. For example, the upper part of the transmitter includes a power key 46, a mute key 48, a channel up key 50, a channel down key 52, a volume up key 54, and a volume down key 56. In addition, specific keys may be provided for a video cassette recorder such as a record key 58, a play key 60, a fast forward key 62, a rewind key 64, a stop key 66, and a pause or stop motion key 68. At the lower part of the transmitter there is the usual numerical keypad and enter key. Other keys shown may be assigned other predetermined functions. However, because the remote transmitters from different manufacturers vary widely, providing all the keys from even four different remote control transmitters on one unit would unduly complicate the reconfigurable remote control transmitter of the present invention and make operation confusing to the user. To avoid this, programmable or "soft" keys are provided which are controlled by means of the function key 70. These keys include an on/off key 72, an up key 74 and a down key 76. The function performed by these keys depends on the function selected by the function key 70. More particularly, when the function key is pressed, a sequence of functions is displayed by the liquid crystal display depending upon the source that has been selected. The desired function is selected by sequencing the function key until that function is displayed. Examples of specific functions which may be performed by the several sources are listed in the following tables.
______________________________________LCD - TV FUNCTIONS LCD - VCR FUNCTIONSClear Scr. SlowSound Cont. SlowVIR SearchChan Block SearchOff Timer Reverse PlaySound + Fast PlayCable Frame Advan.Audio Mode AVideo Mode BPict. Cont. CPict. Cont. LCD - CABLE FUNCTIONSBrightness TuningBrightness TuningColor ATint BTint CTreble LCD - AUX FUNCTIONSTreble TBDBass ABass BBalance CBalanceSharpnessSharpnessHomenetBC______________________________________
In FIG. 3, the function "Sharpness" has been selected for the source TV and the up and down arrows indicate that the up and down keys are to be used to control this function. It will be observed that each of the function tables include the functions "A", "B" and "C". These are for user defined functions for those situations that a transmitter to be emulated includes a function that is not previously stored in the reconfigurable remote control transmitter. In such a case, the user selects one of these functions and provides it with a label. This label is generated by either the + key or the - key to cycle through the alphabet. Once the correct letter is displayed, the user presses the enter key 72 to enter it and the display indexes over one character position where the process is repeated and so on until the complete label is generated. Thus, the liquid crystal display 10 and the keys of the reconfigurable remote control transmitter of the invention have been designed to provide a user freindly interface which is simple and easy to use no matter what combination of remote transmitters it is configured to emulate.
After the transmitter has been configured as desired by the user, it is ready to use. This requires that the transmitter recall, expand and transmit the required code. This is accomplished by first determining which source has been chosen so that the correct block of data in the nonvolatile memory 38 is addressed. Then when a key is pressed, the entire block of data for that source is transferred to the scratch pad memory 40. If a preamble code exists, it is copied into a 200 byte array in memory 40. Next, the key code is copied into the 200 byte array after the preamble code. At the same time, the bit compressed codes for the preamble and the key code are expanded into byte codes. Then the start, length and repeat number values are added to the code for this key. All that remains is to generate the required carrier frequency. This is accomplished by software rather than provide individual carrier generators. In other words, the microprocessor uses its own clock and a divider process in order to generate the required frequency. Transmission of the expanded code is done by setting a pointer at the start of the 200 byte array and taking the 16-bit pulse count from the category indicated by the byte at the pointer. These pulses are transmitted at the carrier frequency for the pressed key. The 16-bit pause count from the category indicated by the byte at pointer +1 is then taken to determine the required length of time for the pause, and then the next pointer is taken and so on until the entire expanded code is transmitted.
Thus, there has been provided a reconfigurable remote control transmitter capable of emulating several remote control transmitters which is simple to use and requires no interconnection or modification of the products controlled. While a specific preferred embodiment has been described, those skilled in the art will recognize that the invention can be modified within the scope of the appended claims to provide for the control of more or less than four products or appliances which may or may not include video products. In addition, the specific data encoding and compression techniques may be modified to accomodate the data to the storage space available in the nonvolatile memory.
The program specification for the programming sequence of the reconfigurable remote control transmitter is set forth below. Following that is a listing for a finite statement machine which specifies the program of the microprocessor. ##SPC1##
|
A reconfigurable remote control transmitter is disclosed that has the ability to learn, store and repeat the remote control codes from any other infrared transmitter. The reconfigurable remote control transmitter includes an infrared receiver, a microprocessor, nonvolatile and scratch pad random access memories, and an infrared transmitter. The microprocessor application is divided into four main categories: learning, storing, retransmitting, and user interface. In the learning process, the reconfigurable remote control transmitter receives and decodes the transmissions from another remote control transmitter. The process is repeated at least twice for each key to make sure that it has been properly received and decoded. Once the data has been received and decoded, it is stored for later use. In order to do this, the received and decoded data is compressed so that it can fit into the nonvolatile memory. This process is repeated for each of the several remote control transmitters that are to be replaced by the reconfigurable remote control transmitter. When the learning and storing operations have been completed, the reconfigurable remote control transmitter is ready to use.
| 6
|
CROSS-REFERENCE TO RELATED APPLICATIONS
Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable
BACKGROUND OF THE INVENTION
1. Field of Invention
This invention pertains to an electrical device that provides power to an electrical appliance. More particularly, this invention pertains to an electrical receptacle that interrupts the power circuit to the electrical appliance based on the ambient temperature proximate the electrical receptacle.
2. Description of the Related Art
Every year there are thousands of electrical fires in homes. Hundreds die every year in these fires, with many more injured. Some of these fires are caused by electrical system failures and defective appliances. But, many more of these fires are caused by the misuse and poor maintenance of electrical appliances, incorrectly installed wiring, and overloaded circuits and extension cords.
Electrical circuits are protected from overcurrent conditions by circuit breakers. These circuit breakers are centrally located. Fixed wiring runs from the circuit breakers to power receptacles located throughout the home. The typical receptacle is configured to receive two plugs from electrical devices. It is not uncommon for people to use adapters in order to plug more than two electrical devices into such a receptacle. Such misuse, although not commonly resulting in an overcurrent condition that will trip a circuit breaker, often exceeds the capabilities of the adapter, which may result in overheating of the adapter and/or the receptacle. Also, the adapter or one of the multitude of electrical plugs may have a high resistance connection, which results in resistance heating of the connection. Another type of misuse is the continued use of frayed or damage electrical cords. Without the protection of the circuit breaker tripping the circuit, such misuse can result in an electrical fire.
Ground fault circuit interrupters (GFCIs) are becoming more common. Ground fault circuit interrupters monitor the circuit for ground faults, and trip the circuit when one is detected. A ground fault is a condition where the current flowing through the hot lead to the device is not equal to the current flowing through the neutral lead to the device. When the two current values are not equal, then some amount of current must be flowing through a ground connection, which indicates a potential electrical safety hazard. Although GFCIs provide electrical safety to people, GFCIs do not protect against hazards that typically result in electrical fires.
Arc fault circuit interrupters (AFCIs) are also becoming common. Arc fault circuit interrupters monitor the circuit for electrical arcs, such as caused by loose connections or frayed wiring that causes a short circuit. The AFCI typically reacts to an arcing condition before a traditional circuit breaker, which operates based on current flow or thermal heating of a trip element. Arc fault circuit interrupters are an important line of defense against electrical fires, but AFCIs do not detect all conditions that result in electrical fires.
Attempts have been made to provide a device useful for reducing the number of electrical fires. For example, U.S. Pat. No. 7,400,225 discloses a receptacle that includes a fusible link that interrupts the circuit upon detecting an overheating condition, such as a glowing contact or series arcing. The fusible link opens the circuit permanently, thereby requiring replacement of the receptacle in order to return the connected devices back to service.
BRIEF SUMMARY OF THE INVENTION
A temperature switch is incorporated in a ground fault interrupter (GFI) or other circuit interrupter in such a way that the test feature of the interrupter is actuated upon detection of an elevated ambient temperature, thereby causing the interrupter to break the circuit for the load. The broken circuit is latched until a reset switch is actuated. The temperature switch has a tripping setpoint between the maximum operating rating of the cable and/or wiring and the insulation melting point. In this way, potentially hazardous conditions that do not involve current flow sufficient to trip upstream circuit breakers are prevented from developing into a hazardous condition. The temperature switch is responsive to the ambient temperature proximate the receptacle.
In one embodiment, the temperature switch is a normally open switch with the switch contacts in parallel with the normally open contacts of the test switch of the interrupter. The temperature switch is positioned proximate the receptacle housing in such a manner that the temperature switch is responsive to heat generated from the various electrical connections within and/or plugged into the receptacle housing. In various embodiments the receptacle is configured for permanent mounting with connections to the service wiring or as a portable unit that plugs into another receptacle.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The above-mentioned features of the invention will become more clearly understood from the following detailed description of the invention read together with the drawings in which:
FIG. 1 is a schematic diagram of one embodiment of a heat actuated interrupter receptacle;
FIG. 2 is a perspective view of one embodiment of a heat actuated interrupter receptacle; and
FIG. 3 is a perspective view of another embodiment of a heat actuated interrupter receptacle.
DETAILED DESCRIPTION OF THE INVENTION
Apparatus for interrupting an electrical circuit upon detecting a high temperature is disclosed. The high temperature is greater than the wire/cable temperature rating and less than the melting temperature of the insulation. The high temperature is often caused by misuse of the receptacle 102 , such as by using an adapter to plug multiple devices into the receptacle 102 and/or using frayed or damaged cords.
FIG. 1 illustrates a schematic diagram of one embodiment of a heat actuated interrupter receptacle device 100 . A receptacle 102 houses an interrupting module 104 that includes a set of input connections 112 , such as those that connect to a power source, and a set of output connections 110 , such as those of a receptacle socket. The receptacle 102 also includes a test switch 106 that is connected to the module 104 . Connected in parallel with the test switch 106 is a temperature switch 108 .
The module 104 , in one embodiment, is a ground fault interrupting (GFI) module that breaks, or interrupts the circuit between the input connections 112 and the output connections 110 . Corresponding ones of the input connections 112 are connected to the output connections 110 to form a circuit between the input 112 and the output 110 during normal, or non-tripped, operation. The module 104 interrupts the circuit upon detection of a ground fault condition. A ground fault condition is a current imbalance between the hot H and neutral N connections of the input connections 112 , such as when the current flow through the hot H connection 110 -H is greater than the current flow through the neutral N connection 110 -N. In a three-conductor system, such a condition can occur when a portion of the current flowing through the hot H lead 110 -H also flows through the ground G lead 110 -G or through another ground connection, such as an electrical earth. The test switch 106 in such an embodiment simulates an imbalance, or a ground fault, and causes the GFI module 104 to trip, thereby interrupting the circuit connected to the output connections 110 .
The module 104 , in another embodiment, is a circuit interrupting module that breaks, or interrupts the circuit between the input connections 112 and the output connections 110 . The circuit interrupting module 104 includes a relay or circuit breaker that breaks the circuit between the input connections 112 and the output connections 110 . In such an embodiment, the test switch 106 actuates the relay or circuit breaker and causes the circuit interrupting module 104 to trip, thereby interrupting the circuit connected to the output connections 110 .
A temperature switch 108 is connected in parallel with the test switch 106 . In the illustrated embodiment, the test switch 106 is a normally open switch and the temperature switch 108 is also a normally open switch before it is actuated by a sensed high temperature. In this way, either the temperature switch 108 or the test switch 106 will actuate the module 104 and interrupt the circuit between the input connections 112 and the output connections 110 . In another embodiment, the test switch 106 is a normally closed switch that opens to test. In such an embodiment, the temperature switch 108 is a normally closed switch in series with the test switch 106 .
The temperature switch 108 includes a temperature sensor 118 that is responsive to the ambient temperature around the receptacle 102 . In one embodiment, the temperature switch 118 is a mercury switch in which the mercury level in a capillary rises with increasing temperature. When the temperature setpoint is reached, the mercury bridges a gap between two conductors, thereby causing the temperature switch 108 to close and actuate the module 104 . In other embodiments, the temperature switch 108 includes other temperature sensors that cause the temperature switch 108 to actuate upon detection of a high temperature.
The temperature switch 108 is responsive to a high local temperature. Typically, the temperature rating of cables and wiring used for a receptacle 102 is 75 degrees Centigrade. The insulation of such cables and wiring often has a melting point of 95 degrees Centigrade. In one embodiment, the temperature switch 108 has a high temperature setpoint between the cable/wiring temperature rating value and the insulation's melting temperature. In an embodiment with a cable rating of 75 degrees and an insulation melting temperature of 95 degrees, the temperature switch 108 has a setpoint at approximately 85 degrees Centigrade.
The temperature of a receptacle device 100 will increase above the room's ambient temperature for various reasons, including high current levels that are not sufficiently high to trip an upstream circuit breaker. The elevated temperature is transferred from the metal conductors to the receptacle 102 . The potentially thermally hot conductors include the prongs on the plug that connects to the output connectors 110 and the service wiring that connects to the input connectors 112 . The temperature sensor 118 is responsive to the temperature of the thermally hot conductors. In one embodiment, the temperature sensor 118 is in thermal contact with the receptacle 102 , which has a temperature corresponding to that of the thermally hot conductors. In another embodiment, the temperature sensor 118 is positioned proximate the conductors, for example, within a cavity containing the input connections 112 .
The illustrated embodiment also shows a jumper 114 . The jumper 114 plugs into or otherwise connects to the receptacle 102 to connect the neutral N of the power connections 112 to the ground G of the test switch 106 . The ground G of the test switch 108 is also connected to the ground G of the input 112 and output 110 . In other embodiments, the function of the jumper is performed by a switch or other device that selectively connects the neutral N of the power connections 112 to the ground G of the module 104 . With the jumper 114 connected, the embodiment with the GFI module 104 will function when a two-conductor plug is connected to the output connections 110 . With the jumper 114 disconnected, the module 104 is suitable for three-conductor plugs.
FIG. 1 illustrates a simplified schematic of one embodiment of a heat actuated interrupter receptacle 100 . The simplified schematic does not illustrate various connections, for example, the reset switch connections; however, those skilled in the art will recognize the need for such wiring and understand how to wire such a circuit, based on the components ultimately selected for use.
FIG. 2 illustrates a perspective view of one embodiment of a heat actuated interrupter receptacle device 100 -A. The illustrated heat actuated interrupter receptacle device 100 -A includes an in-wall mountable receptacle 102 -A that has a pair of sockets for the output connections 110 . The illustrated configuration is configured to be received by a wall mounted electrical box that has fixed wiring installed. Such wall mounted electrical boxes are used to receive electrical receptacles. The illustrated heat actuated interrupter receptacle device 100 -A is dimensioned to replace a conventional receptacle in the box.
Accessible between the two sockets 110 are pushbuttons for the test switch 106 and a reset switch 202 . On the rear of the receptacle 102 -A are the input connections 112 -A. The input connections 112 -A are configured for connecting to fixed, or service, wiring that is terminated at a central circuit breaker panel. The illustrated input connections 112 -A are screw terminals positioned on the rear of the receptacle 102 -A in a recessed area.
Attached to the side of the receptacle 102 -A is a temperature sensor 108 -A. In various embodiments, the temperature sensor 108 -A is embedded within the receptacle 102 -A or attached to the surface of the receptacle 102 -A. For the embodiment in which the temperature switch 108 includes a mercury switch, the mercury switch is attached to the receptacle 102 -A such that the mercury switch is positioned with the proper orientation when the receptacle 102 -A is installed.
Operating the test switch 106 interrupts the electrical circuit between the input connections 112 -A and the output connections 110 . When the temperature switch 108 actuates upon sensing a rising temperature greater than or equal to the setpoint, the electrical circuit between the input connections 112 -A and the output connections 110 is broken or interrupted. Operating the reset switch 202 resets the heat actuated interrupter receptacle device 100 -A and completes the interrupted circuit between the input connections 112 -A and the output connections 110 .
FIG. 3 illustrates a perspective view of another embodiment of a heat actuated interrupter receptacle device 100 -B. The illustrated embodiment includes an adapter receptacle 102 -B that is portable, that is, the adapter receptacle 102 -B is configured to be plugged into a mating receptacle and the adapter receptacle 102 -B is not permanently installed to the wiring connected to the central circuit breaker panel.
The adapter receptacle 102 -B has an enclosure with input connections 112 -B configured as a conventional plug that mates with a receptacle socket. In various embodiments, the adapter receptacle 102 -B has one or a pair of input connections 112 -B. In the illustrated embodiment, the temperature switch 108 -B is positioned proximate the surface of the housing of the adapter receptacle 102 -B. The position of the temperature switch 108 -B is such that the temperature switch 108 -B is responsive to heat generated by the input connections 112 -B, the output connections 110 , and/or internal to the interrupter receptacle device 100 -B.
The heat actuated interrupter receptacle device 100 includes various functions. The function of sensing misuse that results in an elevated operating temperature of the receptacle 102 is implemented, in one embodiment, by the temperature switch 108 that is positioned at a location that has a thermally conductive path between the temperature switch 108 and the heat generating component.
The function of repeatedly detecting an over-temperature condition is implemented, in one embodiment, by a temperature switch 108 that is capable of being repeatedly actuated. In one such embodiment, the temperature switch 108 is one that does not self-destruct upon actuation, such as one that relies upon a material to melt in order to operate. An example of a temperature switch 108 that is capable of being operated repeatedly is a switch in which a sensor or material 118 moves as the temperature increases until the material causes a circuit to be completed between two conductors, thereby operating the switch. In various embodiments, the material is a liquid, such as mercury, or a metal, such as a bimetallic member. In other embodiments, the temperature switch 108 is an electronic device that senses the temperature and causes a switch to operate. In one such embodiment, the temperature switch includes a temperature sensor such as a resistance temperature device (RTD) connected to a switching circuit.
The function of interrupting a circuit is implemented, in one embodiment, by the module 104 that contains a circuit interrupting component. In one such embodiment, the module 104 is a ground fault circuit interrupter that breaks the circuit upon detection of a ground fault and also when the test switch 106 is actuated. In another such embodiment, the module 104 is a circuit interrupter, such as a relay or circuit breaker similar to that in a GFCI, that includes a test switch 106 .
The function of resetting the interrupted circuit is implemented, in one embodiment, by the reset switch 202 that causes the module 104 to restore the interrupted circuit, providing that the over-temperature condition that caused the module 104 to interrupt the circuit has been cleared. In other words, the module 104 latches the interrupted condition when the module 104 is actuated. The module 104 is reset only when the condition causing the circuit interruption is cleared.
From the foregoing description, it will be recognized by those skilled in the art that a reusable heat actuated interrupter receptacle device 100 has been provided. The interrupter receptacle device 100 includes an interrupting module 104 that is actuated by a temperature switch 108 that is responsive to the temperature of the receptacle 102 . The temperature switch 108 is a non-destructive switch that is operable repeatedly. The interrupting module 104 is resettable after the circuit interrupting condition is corrected and the device 100 is ready for use without requiring replacement of any components.
While the present invention has been illustrated by description of several embodiments and while the illustrative embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept.
|
Apparatus for detecting an overheating condition at an electrical power device and automatically breaking the circuit when the temperature exceeds a setpoint value. In various configurations the device is a receptacle adapted to be used in a wall mounted box or a receptacle unit that is plugged into an existing receptacle and supported in place by the existing receptacle. A temperature switch is wired parallel to a normally open test switch on a ground fault circuit interrupter or other circuit interrupting device. The temperature switch is responsive to the temperature local to the receptacle, such as is caused by poor connections to or in the receptacle. The temperature setpoint is less than the melting temperature of the insulation of the electrical wiring. Upon actuation of the temperature switch, the circuit interrupting device is latched in a tripped position until the device is reset for reuse.
| 7
|
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 60/947,595, filed Jul. 2, 2007, which is incorporated herein by reference.
BACKGROUND
[0002] A rope is a large stout cord of strands of fibers or wire twisted or braided together for strength. The making of rope dates to ancient times. Originally, strands of fibers were twisted by hand, until the Egyptians developed tools to make ropes from papyrus fibers and leather strips. Hemp, used in Asia and adopted in Europe, became the chosen material for ropes until recently, when it was replaced by Manila hemp, an unrelated plant from the Philippines. Synthetic fibers supplanted Manila hemp as the prime rope material in the 1950s.
[0003] Working with ropes is a vital part of many industries and particularly essential to seafaring. Nineteenth century sailors knew and used hundreds of knots, some simple and others exceedingly complicated, each for a specific purpose. Accidents are common on ships, such as when a seaman falls into the water—for which an English word “overboard” was coined to succinctly capture the situation in the twelfth century. In cold waters, as the victim is experiencing hypothermia, his hands and fingers lose dexterity and he cannot hold on to a thin rescue rope that is thrown towards him. Larger diameter ropes, however, are too heavy to throw to a long distance where the victim may be located in the waters.
SUMMARY
[0004] 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.
[0005] In accordance with various aspects of the invention, an article of manufacture form of the invention includes an inflatable rope, which comprises a bladder formed from plastic to receive, transport, and contain an inflatable medium. The inflatable rope also comprises a sheath formed from a weave of man-made fibers that expands or compresses. The inflatable rope further comprises a fitted, perforated plastic layer into which the bladder and the sheath are rolled or folded so as to allow the inflatable rope to be wound into a spool housed in a drum.
[0006] In accordance with another aspect of the invention, a system form of the invention includes a system for hurling an inflatable rope, which comprises the inflatable rope having three layers including a bladder, a phosphorescent sheath, and a fitted, perforated plastic layer and being wound into a spool. The system also comprises a drum for storing the spool and for containing a source of radiation to irradiate the phosphorescent sheath through the fitted, perforated plastic layer. The system further comprises a device that propels a distal end and a portion of the inflatable rope toward a person in water.
[0007] In accordance with another aspect form of the invention, a method form of the invention includes a method for containing a chemical spill, which comprises unwinding a spool of a first inflatable rope made from an ultra high molecular weight polyethylene to encompass an area of the chemical spill in water. The method also comprises pumping a nostril of the first inflatable rope with an inflatable medium while a curtain attached to the bottom of the first inflatable rope unfurls toward the water. The method further comprises turning on light emitting diodes on the top of the first inflatable rope to aid in visibility of the location of the first inflatable rope and the chemical spill.
DESCRIPTION OF THE DRAWINGS
[0008] The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
[0009] FIG. 1 is a pictorial diagram illustrating an exemplary application of an inflatable rope, according to one embodiment of the present invention;
[0010] FIG. 2 is a pictorial diagram illustrating an exemplary application of an inflatable rope, according to one embodiment of the present invention;
[0011] FIG. 3 is a perspective diagram illustrating exemplary layers of an inflatable rope, according to one embodiment of the present invention;
[0012] FIG. 4 is a perspective diagram illustrating exemplary layers of an inflatable rope, according to one embodiment of the present invention;
[0013] FIG. 5 is a perspective diagram illustrating an exemplary inflated inflatable rope, according to one embodiment of the present invention;
[0014] FIG. 6 is a perspective diagram illustrating exemplary layers of an inflatable rope including an exemplary threaded nostril;
[0015] FIG. 7 is a plan view of an exemplary inflatable rope with an exemplary pattern, according to one embodiment of the present invention;
[0016] FIG. 8 is a plan view of an exemplary inflatable rope with an exemplary pattern, according to one embodiment of the present invention;
[0017] FIG. 9 is a plan view of an exemplary inflatable rope with an exemplary pattern, according to one embodiment of the present invention;
[0018] FIG. 10 is a pictorial diagram of an exemplary inflatable rope with an exemplary lanyard, according to one embodiment of the present invention;
[0019] FIG. 11 is a pictorial diagram of an exemplary containment boom, according to one embodiment of the present invention; and
[0020] FIG. 12 is a pictorial diagram of exemplary containment booms, according to one embodiment of the present invention.
DETAILED DESCRIPTION
[0021] Unpredictability is one among many risks facing those at seas and even on minor waterways. Ocean marine insurance, one of the oldest forms of insurance, recognizes the need for mitigating against loss from the dangers experienced by boats, cargo, and passengers. One of those dangers is illustrated by FIG. 1 in which a person 102 is overboard. A boat 100 includes a vehicle from which the person 102 fell off, or a ship from a rescuing organization, such as the Coast Guard. When the person 102 is overboard and he wears a radio-frequency tag, a radio-frequency receiver on the boat 100 will annunciate an alert signal to others on board the boat 100 .
[0022] On the boat 100 are several deckhands. Generally, it will take too long to steer the boat 100 to orient the boat to rescue the person 102 . A quicker rescuing operation is needed. In the case illustrated in FIG. 1 , some of the deckhands recognize that the person 102 is in the water and one of the deckhands has picked up a device 104 that hurls a projectile, which can propel an inflatable rope 108 towards the person 102 . In one embodiment, the inflatable rope 108 can be hurled up to about 200 feet from the boat 100 . Any suitable device that hurls a projectile, such as the inflatable rope 108 , can be used. One suitable device includes a grapnel launcher manufactured by H. Henriksen Mekaniske Verksted A/S, but any suitable devices can be used.
[0023] The device 104 is fitted with a drum 106 in which the inflatable rope 108 is stored in a spool like fashion. The inflatable rope 108 has a distal end and a proximal end. The spool is wound into a cylinder-like shape so that the distal end protrudes from the center of the spool at one end of the spool and the proximal end protrudes from the center of the spool at the other end of the cylinder. The spool is placed inside a drum 106 , which is coupled to the device 104 , so as to allow the device 104 to propel, at first, the distal end of the inflatable rope, and after which, a portion of the inflatable rope connected to the distal end toward the person 102 .
[0024] The inflatable rope 108 as hurled from the device 104 is manufactured so that it is initially small in diameter so as to easily cut through the air to quickly reach the person 102 . Its small shape is maintained by a small diameter, elongated plastic bag that has a perforation to allow the inflatable rope 108 to tear the small diameter, elongated plastic bag, and emerge when it is inflated. When a desired portion of the inflatable rope 108 has been propelled toward the person 102 , the inflatable rope 108 is inflated using its proximal end 108 a. FIG. 1 shows a deckhand holding and coupling the proximal end 108 a of the inflatable rope 108 to a source of air (not shown) or other medium (gas, solid, or liquid) to inflate the inflatable rope 108 .
[0025] In one embodiment, the proximal end 108 a can be coupled to a wench-like mechanism to pull the person 102 toward the boat 100 . In another embodiment, the device 104 can include a wench that retrieves the hurled portions of the inflatable rope 108 and thereby pulls the person 102 to safety. FIG. 2 illustrates the inflated inflatable rope allowing the person 102 to grab hold for the deckhands to pull the person 102 to safety. In one embodiment, the inflatable rope 108 can be inflated so that it expands to about 150% of its original, uninflated size.
[0026] The inflatable rope 108 , in its natural, uncompressed, and uninflated form, includes at least two layers 108 b, 108 c as illustrated in FIG. 3 . The layer 108 b is a bladder formed from a suitable material into which a gas, such as air, can be pumped to cause the layer 108 b to expand into a suitable diameter, such as 3 inches. Any suitable material may be used to form the bladder of the layer 108 b, such as plastic, as long as it allows the bladder to receive, transport, and contain an inflatable medium. The layer 108 c is a sheath, which is woven from man-made fibers, such as polyethylene terephthalate, a thermoplastic polymer resin in the polyester family. The weave of the sheath of the layer 108 c provides the tensile strength of the inflatable rope 108 while the bladder of the layer 108 b allows the inflatable rope 108 to be inflatable or compressible. Any suitable weave pattern can be used as long as it allows the sheath of the layer 108 c to expand with the expansion of the bladder of the layer 108 b.
[0027] Both the sheath of the layer 108 c and the bladder of the layer 108 b can lay flat allowing both layers 108 b, 108 c to be rolled or undulated to form multiple compressed folds. The shape of the layers 108 b, 108 c formed after being rolled or folded can be maintained by slipping a fitted, perforated plastic layer 108 d over the rolled or folded layers 108 b, 108 c. The inflatable rope 108 with the three layers 108 b, 108 c, and 108 d can be wound into a spool, a center of which at one end protrudes the distal end of the inflatable rope 108 and at the other end protrudes the proximal end. As previously discussed, the distal end of the inflatable rope 108 along with a portion of the inflatable rope 108 will be hurled to the person 102 while the proximal end of the inflatable rope 108 remains behind to be tethered to the boat 100 and is coupled to a source of air or other medium to inflate the inflatable rope 108 .
[0028] As the inflatable rope 108 is pumped with air or another suitable medium, the layer 108 d is torn off along the perforated path allowing the sheath of the layer 108 c and the bladder of the layer 108 b to emerge. See FIG. 5 . The inflated inflatable rope 108 floats and allows a portion of the person 102 to be lifted from the water. A threaded nostril 110 , as shown in FIG. 6 , allows the proximal end of the inflatable rope 108 to be coupled to a source of air. In one embodiment, the sheath of the layer 108 c is painted with a phosphorescent paint, which allows the sheath to absorb radiation at one wavelength followed by a reradiation at another wavelength in a visible color, such as yellow or orange, that continues for a noticeable amount of time after the incident radiation stops. In this embodiment, the spool containing the phosphorescent inflatable rope also contains a source of incident radiation in the drum 106 to charge, periodically and continuously, the phosphorescent paint on the sheath of the layer 108 c.
[0029] The sheath of the layer 108 c, in one embodiment, is solid and in a color, such as yellow or orange. In another embodiment, as illustrated in FIG. 7 , a v-shape pattern is periodically repeated on the sheath of the layer 108 c. The v-shape pattern may be comprised of a solid color different from the color comprising the remaining portions of the sheath of the layer 108 c. In a further embodiment, the remaining portions of the sheath of the layer 108 c include the word “exit,” which is repeated along the two spines of the v-shape pattern. The v-shape pattern, alone or in combination, with the word “exit” allow the inflatable rope 108 to be used by firemen to deliver water to quench a fire in a direction opposite to the apexes of the v-shape pattern and at the same time guide people, who follow the direction pointed by the apexes of the v-shape pattern away from the fire to safety.
[0030] A candy stripe pattern is available, in an additional embodiment, to mark the sheath of the layer 108 c. See FIG. 8 . For some population of people, the candy stripe pattern may be more visually arresting to the eyes. In an added embodiment, the portions of the sheath of the layer 108 c that lack the candy stripe pattern may include the word “caution” periodically repeated. FIG. 9 illustrates another stripe pattern, in as yet another embodiment, that periodically repeats. Many other patterns are possible as long as they functionally alert people to a situation that requires caution.
[0031] The inflated inflatable rope 108 is shown in FIG. 10 . The nostril 110 is shown at the proximal end of the inflated inflatable rope 108 . As previously discussed, the nostril 110 allows air or another medium to be delivered into the bladder of the inflatable rope 108 so as to inflate it. A distal end of a lanyard 1002 is attached to the distal end of the inflatable rope 108 . In one embodiment, the lanyard 1002 is manufactured from the same material used to manufacturer the sheath of the layer 108 c. Preferably, the lanyard 1002 has a similar or longer length than the inflatable rope 108 . When the inflatable rope 108 is hurled to the person 102 , in a further embodiment, the distal ends of the inflatable rope 108 and the lanyard 1002 are propelled together toward the person 102 . A proximal end of the lanyard 1002 is tethered to the boat 100 so as to allow the inflatable rope 108 to be manipulated directionally by the lanyard 1002 . More than one lanyard can be coupled to the inflatable rope 108 to provide different controlling options.
[0032] An inflatable rope 1100 can be used as a containment boom, which is a temporary floating barrier used to contain an oil or chemical spill. The inflatable rope 1100 includes elements similar to those of the inflatable rope 108 , such as a bladder, a sheath, and a nostril 1110 . Preferably the sheath of the inflatable rope 1100 is made from an ultra high molecular weight polyethylene, which is highly resistant to corrosive chemicals. The inflatable rope 1100 includes a curtain 1104 , which is unfurled when the inflatable rope 1100 is inflated with air or another medium through the nostril 1110 . The curtain 1104 preferably is created from the ultra high molecular weight polyethylene used for the sheath of the inflatable rope 1100 . In one embodiment, the inflatable rope 1100 is wound into a spool and is stored in a 55 gallon drum or similar canister. The curtain 1104 has a length similar to the length of the inflatable rope 1100 . The top of the curtain 1104 is attached to the bottom of the inflatable rope 1100 using a suitable fastening means, such as Velcro. The bottom 1104 a of the curtain 1104 is preferably weighted so as to ease the process of unfurling and to maintain the drape of the curtain 1104 in the vertical direction to contain the spill. A number of light emitting diodes 1102 are periodically placed along the inflatable rope 1100 to allow visibility at night. In an embodiment, the light emitting diodes 1102 are placed between the bladder and the sheath.
[0033] A system 1200 of inflatable ropes 1100 a, 1100 b expand an area within which a spill can be contained. Both the inflatable ropes 1100 a, 1100 b include nostrils 1100 a, 1100 b, adapted to receive air or another medium to inflate the inflatable ropes 1100 a, 1110 b. Check valves (not shown) are provided at ends 1202 , 1204 , to regulate air or another medium that inflates the inflatable ropes 1100 a, 1100 b, and are adapted to close when the pressure in both inflatable ropes 1100 a, 1100 b is approximately equal. Light emitting diodes 1102 are provided on the top of the inflatable ropes 1100 a, 1100 b to provide visibility at night. The system 1200 allows each inflatable rope to be a component that can be interfaced together to expand to contain an enlargement of a spill.
[0034] 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.
|
An inflatable rope comprises three layers, a bladder, a sheath, and a fitted, perforated plastic bag to keep the inflatable rope in a compressed form. The compressed form can be hurled through the air at great distance to a person overboard. The inflatable rope can be inflated to a size that eases the ability of the person, who has lost dexterity in frigid water, to hold on to it for rescuing.
| 3
|
[0001] This application claims the benefit of U.S. Provisional Application No. 61/513,576, filed Jul. 30, 2011, the content of which is herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to systems and methods for accelerating or improving the success rate of a behavior change in an organization, group or community.
BACKGROUND OF THE INVENTION
[0003] Innovation has been shown to be key driver of corporate success; this is especially true for younger companies whose growth comes from finding new markets with innovative new products. The acceptance of new innovations or new technologies such as information systems is also becoming more critical in the competitive global environment.
SUMMARY OF THE INVENTION
[0004] Embodiments of the invention include systems and methods for accelerating or improving the success rate of a behavior change in an organization, group or community. In an embodiment, the invention includes a method for accelerating or improving the success rate of a behavior change, the method including gathering primary and secondary relationship data of an informal network of individuals and behavior change constructs for a plurality of individuals within the informal network of individuals; performing social network analysis of the informal network with a computing system using the gathered primary and secondary relationship data and behavior change constructs; and performing the statistical perception analysis of the individuals within the informal network using gathered primary and secondary relationship data and behavior change constructs; wherein the behavior change constructs include at least one of change perception, behavior intention, and behavior measures.
[0005] In an embodiment, the invention includes a system for accelerating or improving the success rate of a behavior change initiative in an organization, group or community, the system including a processor; and memory in operative communication with the processor; the system configured to process as input primary and secondary relationship data of an informal network of individuals and behavior change constructs for a plurality of individuals within the informal network of individuals; the system configured to perform social network analysis of the informal network using the gathered primary and secondary relationship data and behavior change constructs; and the system further configured to perform perception analysis of the individuals within the informal network using the gathered primary and secondary relationship data and behavior change constructs; wherein the behavior change constructs include at least one of change perception, behavior intention, and behavior measures.
[0006] This summary is an overview of some of the teachings of the present application and is not intended to be an exclusive or exhaustive treatment of the present subject matter. Further details are found in the detailed description and appended claims. Other aspects will be apparent to persons skilled in the art upon reading and understanding the following detailed description and viewing the drawings that form a part thereof, each of which is not to be taken in a limiting sense. The scope of the present invention is defined by the appended claims and their legal equivalents.
BRIEF DESCRIPTION OF THE FIGURES
[0007] The invention may be more completely understood in connection with the following drawings, in which:
[0008] FIG. 1 is a schematic logical component view of the system which includes a database, potential interfaces to other systems, and the components that make up the functionality in some embodiments.
[0009] FIG. 2 is a schematic generalized network view of the application and system used on a computer and across a network in accordance with some embodiments.
[0010] FIG. 3 is a schematic view of the computer that the application resides on in accordance with some embodiments.
[0011] FIG. 4 is a flow chart showing exemplary detailed operations in the assessment functionality in accordance with various embodiments.
[0012] FIG. 5 is a flow chart showing exemplary detailed operations in the feedback and recommendation functionality in accordance with various embodiments.
[0013] FIG. 6 is a flow chart showing exemplary detailed operations in the implementation functionality in accordance with various embodiments.
[0014] FIG. 7 is a flow chart showing exemplary detailed operations in the evaluation functionality in accordance with various embodiments.
[0015] FIG. 8 is a flow chart showing exemplary operations of a method and/or the configuration of a system in accordance with various embodiments herein.
[0016] While the invention is susceptible to various modifications and alternative forms, specifics thereof have been shown by way of example and drawings, and will be described in detail. It should be understood, however, that the invention is not limited to the particular embodiments described. On the contrary, the intention is to cover modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The embodiments of the present invention described herein are not intended to be exhaustive or to limit the invention to the precise forms disclosed in the following detailed description. Rather, the embodiments are chosen and described so that others skilled in the art can appreciate and understand the principles and practices of the present invention.
[0018] All publications and patents mentioned herein are hereby incorporated by reference. The publications and patents disclosed herein are provided solely for their disclosure. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate any publication and/or patent, including any publication and/or patent cited herein.
[0019] Change management or behavior change initiatives create issues for organizations who need to be able to successfully implement them to gain the potential benefits or return on investment. For example, within organizations, older technologies and processes are continually being replaced by new innovations. Examples of innovations include, but are not limited to changes such as new technologies, wellness programs, engagement programs, innovation programs, recognition programs and systems, sales incentive systems, or significant business process changes. Innovations can be pursued to drive improved productivity or deliver new services, but they are only successful when the employees or participants accept and effectively use the new technology. Thus many innovations also fail due to the lack of acceptance and usage by employees or participants.
[0020] Management of behavior change initiatives for groups has been evolving and shown to be heavily influenced by psychological factors such as social influence, perceived usefulness or ease of use, enjoyment and habits. Regardless of this new knowledge on how people perceive change, common approaches and systems to manage change or innovations are traditionally focused on up-front roll-out plans, communication plans, training plans, and other facilitating conditions such as a help-desk, and deploying subject matter experts with little concern of the individual or group psychological factors. This traditional approach only provides the planners with a limited understanding of the potential participant's needs, the influences of their informal social network connections, or physiological perceptions of the new innovation or change initiatives.
[0021] Organizational Change, Technology Acceptance, and Social Network Analysis research is advancing and rich network data is becoming easier to gather, but its complexity is prohibitive to implementation by practitioners managing change. By not accounting for this rich network data, current approaches are resulting in sub-optimal deployment of resources and money to manage change, higher levels of failure, and sub-optimal return on investment in new innovations.
[0022] Referring now to FIG. 1 , a schematic logical component view of a system in accordance with various embodiments herein is shown which includes a database, potential interfaces to other systems, and the components that make up the functionality. In specific, there is shown a system 1 with a database 2 , a component to manage program/campaigns 8 , a component to manage participants/groups/attributes 9 , a component to gather primary data 10 , a component to run social network analysis 11 . In FIG. 1 there is also shown a component to run perception analysis 12 , a component to auto-recommend change roles 13 , a component to manually select and assign change/innovation roles 14 , a component to auto-recommend training, communications & facilitating conditions 15 , a component to manually select and configure training, communications, and facilitating conditions 16 , a component to simulate change/innovation acceptance longitudinally over time 17 , a component to monitor change 18 , and a component to manage a cost and benefit calculator 19 . These components or modules can represent a configuration of a system as implemented across one or more computing devices. In FIG. 1 there is also shown components or interfaces to external systems or data feeds which include an external data interface 3 , an external statistics interface 4 , an external survey tool interface 5 , and external social network analysis interface 6 , and an external change/innovation system usage interface 7 .
[0023] In more detail, still referring to an embodiment of FIG. 1 , the database 2 contains, but is not limited to, the necessary data to execute the functionality of the components 8 to 19 which can include, but is not limited to participants, groups, participant attributes, change/innovation perceptions, social network connections which are also referred to as dyads, participant network attributes such as centrality or group membership. The database 2 could also contain a repository of training, communications, facilitating conditions and their impacts.
[0024] In further detail, still referring to an embodiment in FIG. 1 , the component to manage programs/campaigns 8 can have the functionality to, but is not limited to, manage templates of different types of changes or new innovation initiatives which could act as starting points for planning, simulation, managing, and monitoring. This component to manage programs or campaigns 8 also allows the selection of permissions and access for users of the system for a particular program or campaigns.
[0025] In further detail, still referring to an embodiment in FIG. 1 , the component to manage participants, groups, and attributes 9 can be used to allow creating, viewing, updating, and deleting of the participants who are targeted for the new change or innovation. This also includes removing duplicates or managing additional previously unknown participants who were forwarded a survey or identified during the process of gathering primary connection data from the targeted participants of the behavioral change initiative.
[0026] In further detail, still referring to an embodiment in FIG. 1 , the component to gather primary data 10 can be used to gather perceptions, network connections, and actual usage information. The perceptions could include the ability to configure online surveys to gather perceptions using previously validated or new scales based on areas such as usefulness, ease of use, social influence, or habits, behavioral intention, and actual usage. The network connections could include survey questions asking for whom the individuals they go to for different modes such as help, information, resources and others. Actual usage of a system or innovation could be gathered in this section via a survey question, manually entering it, a file import or integration to a separate system such as usage logs.
[0027] In further detail, still referring to an embodiment in FIG. 1 , the component to gather primary data 10 can also be able to track responses, view respondents, offer incentives to complete the survey, and manage messaging. Since all the connections or targeted participants for a change or innovation initiative might not be known at the beginning of the initiative, this component also includes functionality to configure “snowball survey” options, which essentially allows the system to discover connections to unknown participants (i.e. outside of the organization or target group) via the surveys, then follow up with an additional survey to the new participant.
[0028] In further detail, still referring to an embodiment in FIG. 1 , the component to run social network analysis 11 can be used to create the social network models and their attributes based on the primary and other data available to the system. Social Network Analysis uses a combination of theories and algorithms building upon Graph Theory such as Centrality in Social Networks by Freeman in 1979, or Structural Hole Theory by Burt in 1992, or Graph Theory & Group Structure by Harary in 1965. This could include natural groups of the organizations which need to be identified to bring close groups through change together (i.e. determine training groups). An example of using social network analysis can be found in Sykes et al., 2009, Model of Acceptance with Peer Support: A Social Network Perspective to Understand Employees System Use, MIS Quarterly, (33:2) pp. 371-393. Social network analysis can be used to determine the boundaries of an informal network, factions, cliques, natural groups, structural hole positions, opinion leaders, isolates, and network attributes such as centrality.
[0029] In further detail, still referring to an embodiment in FIG. 1 , the component to run perception analysis 12 can be used to run a statistical analysis of the perceptions of the group as well as merge the results with the social network analysis results. This allows the change or innovation planners to view the actual perceptions overlaid onto the social networks of the organization. This allows the planners to view the perceptions and actual usage of the innovation at aggregate group or individual level. These perceptions are also used to determine the appropriate training and communication treatments (i.e. target hands-on technical training to those with low perceived ease of use perceptions). The system also calculates the perception metrics of a person's neighborhood in the informal networks which is used to help predict participants own perceptions and future usage
[0030] In further detail, still referring to an embodiment in FIG. 1 , the component to recommend change roles 13 can be used to identify subject matter experts or super-users based on their centrality of different network modes. For example, if there are certain people that everyone goes to for help, they would be an ideal candidate to be a subject matter expert. This component can also recommend training groups based on the natural groups which allows tight-knit groups to go through acceptance or adoption of the change or innovation together. Isolates or individuals who are not connected to the informal networks can also be identified as part of the social network analysis. The analysis results enable better targeting of training and communications based on the informal network structure and positions. The system can also identify how to improve the network structure to increase the speed of change, for example, aligning subject matter experts with isolates or building connections between natural groups. This component can also recommend participants who should be targeted for communication or events like team-events to increase the number of connections they have for getting help, information, and knowledge around the change or innovation. One objective of this social network analysis can be to recommend specific actions that can maximize the effectiveness of the coping and influencing networks.
[0031] In further detail, still referring to an embodiment in FIG. 1 , the component to select and assign change and innovation roles 14 can be used to view the recommendations generated from component 13 , then make any adjustments to the assignments of subject matter experts, training & communication groups, and super-participants/isolate pairings. The system user can view opinion leaders and groups based on the social network analysis. This allows them to view who has the most influential power regarding multiple modes of the change (i.e., where do they go for help, who has access to resources, information, domain knowledge, or other modes). Those with high centrality should be incorporated as SMEs into the change or innovation initiative. This component allows the system user to view groups, factions, and auto-generated suggested training groups
[0032] In further detail, still referring to an embodiment in FIG. 1 , the component to recommend training, communications, and facilitating conditions 15 can be used allow the system to auto-generate training and communication plans. The system can choose the best communication and training options based on previously validated research results and similar initiatives. These are auto-generated appropriate communication and training for each individual and groups to maximize intention and usage where each participant could be different based on their perceptions, group membership, centrality, and moderating effects such as experience, and voluntariness of the change or innovation.
[0033] In further detail, still referring to an embodiment in FIG. 1 , the component to select and configure training, communications and facilitating conditions 16 can be used to view the recommendations from the system and select from a list of training and communication treatments which can impact participant's perceptions, intentions, and usage. The potential impact of the communication and training options are based on prior published research, previous calibration via testing, or expert estimate. Impacts are categorized similar to the main constructs for change and innovation acceptance based on published research, previous testing, or expert estimate (usability, ease of use, facilitating conditions, social influence, habits). The system user can select from a list of facilitating conditions offered (help desk, online help, and others). New training options, communications, training and facilitating conditions can also be added by the system user. This is needed in some embodiments because most large behavioral change initiatives will have suggested roll-out activities. This could also include configuring incentives, such as giving an incentive to the first segment of participants that go through training To facilitate simulation of the acceptance of this change or innovation later, the timing of the training, communications, or facilitating conditions can be entered prior to using the simulation component 17 .
[0034] In further detail, still referring to an embodiment in FIG. 1 , the component to simulate change and innovations longitudinally over time 17 can be used to quickly simulate multiple change and communication plans over-time across the networks and view the effectiveness of the different plans. In configuring the scenario for simulations, the system user can configure the target perceptions, intention, and usage which would be considered success. This allows the system user to adjust communication, training, or facilitating conditions as needed until they are satisfied with the results. The simulations can take into account the particular subject matter experts, change in perceptions over a series of times steps, network neighbor perceptions, network neighbor intentions, network neighbor usage, training, communications, centrality, moderating affects, facilitating conditions, and others. The simulations can be re-run using multiple scenarios based on a range of a particular variable or configuration
[0035] In further detail, still referring to an embodiment in FIG. 1 , the component to monitor the change or innovation initiative 18 can be used to view reports or dashboards of relevant change metrics such as usage, perceptions, effectiveness of communications and training treatments based on the most current data. Periodic surveys are one way that a current status is maintained of the perceptions and usage. Actual system usage logs of a new technology or innovation are another source of information for these dashboards that could imported through an external data interface 3 .
[0036] In further detail, still referring to an embodiment in FIG. 1 , the component to monitor the change or innovation initiative 19 can be used to calculate a cost-benefit comparison of the overall change or innovation initiative. This calculation uses the estimated or actual costs of the communication, training, and facilitating condition treatments and additional participant entered data such as benefits, participant hourly costs, and others.
[0037] In further detail, still referring to an embodiment in FIG. 1 , the component that is an external data interface 3 can be used to integrate to an external system via real-time or batch file to access other participant attributes, connections, or affiliations. These could include email systems, social media applications such as Facebook or LinkedIn, HR systems or others.
[0038] In further detail, still referring to an embodiment in FIG. 1 , the component that is an external statistics interface 4 can be used to run statistical processing such as perception descriptive statistics or regressions using a standard statistics package such as IBM's SPSS.
[0039] In further detail, still referring to an embodiment in FIG. 1 , the component that is an external survey tool interface 5 can be used to gather perceptions, network connections, and other attributes.
[0040] In further detail, still referring to an embodiment in FIG. 1 , the component that is an external social network analysis 6 can be used to perform social network analysis calculations, transformations, and render social network graphs.
[0041] In further detail, still referring to an embodiment in FIG. 1 , the component that is an external change or innovation usage interface 7 can be used to integrate to a separate system or file via real-time or batch processing to gather actual usage of a new innovation or change.
[0042] Referring now to an embodiment in more detail in FIG. 2 there is shown a computer network view. In FIG. 2 there is shown an administrator role 21 , a user role 22 , interacting via a private or public network 23 used for connecting the different participants and components, a computer with the data and application 24 as described in FIG. 3 , an external data interface 29 , an external statistics interface 28 , an external survey tool interface 27 , and external social network analysis interface 26 , and an external change/innovation usage interface 25 .
[0043] In further detail, still referring to an embodiment in FIG. 2 , the component that is an external data interface 29 can be used to integrate to an external system via real-time or batch file to access other participant attributes, connections, or affiliations. These can include email systems, social media applications such as Facebook or LinkedIn, HR systems or others.
[0044] In further detail, still referring to an embodiment in FIG. 2 , the component that is an external statistics interface 28 can be used to run statistical processing such as perception descriptive statistics or regressions using a standard statistics package such as IBM's SPSS.
[0045] In further detail, still referring to an embodiment in FIG. 2 , the component that is an external survey tool interface 27 can be used to gather perceptions, network connections, and other attributes directly from participants 22 .
[0046] In further detail, still referring to an embodiment in FIG. 2 , the component that is an external social network analysis 26 can be used to perform social network analysis calculations, transformations, and render social network graphs.
[0047] In further detail, still referring to an embodiment in FIG. 2 , the component that is an external change or innovation usage interface 25 can be used to integration to a separate system or file via real-time or batch processing to gather actual usage of a new innovation or change.
[0048] FIG. 3 illustrates one possible hardware configuration of systems and to implement methods described herein. It is to be appreciated that although a standalone computing architecture is illustrated, that any suitable computing environment can be employed in accordance with some embodiments. For example, computing architectures including, but not limited to, stand alone, multiprocessor, distributed, client/server, minicomputer, mainframe, supercomputer, digital and analog can be employed in accordance with some embodiments.
[0049] With reference to FIG. 3 , an exemplary environment for implementing various aspects of the intention includes a computer 301 , including a processing unit 302 , a system memory 318 , and a system bus 303 that couples various system components including the system memory to the processing unit 302 . The processing unit 302 can be any of the various commercially available processors. Dual microprocessors and other multi-processor architectures also can be used as the processing unit 302 .
[0050] The system bus 303 can be any of the several types of bus structure including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of commercially available bus architectures. The computer memory 318 includes read only memory (ROM) 316 and random access memory (RAM) 317 . A basic input/output system (BIOS), containing the basic routines that help to transfer information between elements within the computer 301 , such as during startup, can be stored in ROM 316 .
[0051] The computer 301 can further include a hard disk drive 315 , e.g., to read from or write to a removable disk 314 , and an optical disk drive 311 , e.g., for reading a CD-ROM disk 312 or to read from or write to other optical media. The hard disk drive 315 , magnetic disk drive 314 , and optical disk drive 311 are connected to the system bus 303 by a hard disk drive interface 304 , a magnetic disk drive interface 305 , and an optical drive interface 306 , respectively. The computer 301 can include at least some form of computer readable media. Computer readable media can be any available media that can be accessed by the computer 301 . By way of example, but not limited to this example, computer, readable media, and communication media. Computer storage media includes volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer readable instructions, data structures, program modules or other data. Computer storage media includes, but is not limited to RAM, ROM, EEPROM, flash memory or the memory technology, CD-ROM, digital versatile disks (DVD) or the magnetic storage devices, or any other medium which can be used to store the desired information and which can be accessed by the computer 301 . Communications media can include computer readable instructions, data structures, program modules or other data in a modulated data single such as carrier wave or other transport mechanism and includes an information delivery media. The term “modulated data signal” means a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal. By way of example, and not limitation, communication media includes wired media such as wired network or direct-wired connection, and wireless media such as acoustic, RF, infrared and other wireless media. Combinations of any of the above can also be included within the scope of computer readable media.
[0052] A number or program modules can be stored in the drives and RAM 317 , including an operating system 319 , one or more application programs 320 , other program modules 321 , and program non-interrupt data 322 . The operating system 319 in the computer 301 can be of any of a number of commercially available operating systems.
[0053] A user can enter commands and information in the computer 301 through a keyboard 324 and a pointing device such as a mouse 325 . Other input devices (not shown) including a microphone, an IR remove control, a joystick, a game pad, a satellite dish, a scanner, or the like. These and other input devices are often connected to the processing unit 302 through a serial port interface 308 that is coupled to the system bus 303 , but can be connected by other interfaces, such as a parallel port, a game port, a universal serial bus, a IR interface, etc. A monitor 323 , or other type of display device, can be also connected to the system bus 303 via an interface, such as a video adapter 307 . In addition to the monitor, a computer can include other peripheral output devices (not shown), such as speakers, printers etc.
[0054] The computer 301 can operate in a networked environment using logical and/or physical connections to one or more remote computers, such as remote computer(s) 326 . The remote computer(s) 326 can be a workstation, a server's computer, a router, a personal computers, microprocessor based entertainment appliance, a peer device or other common network node, and can include many or all of the elements described relative to the computer 301 , although, for purposes of brevity, only a memory storage device 327 is illustrated. The logical connections depicted include many or all of the elements described relative to the computer 301 , although, for purposes of brevity, only a memory storage device 327 is illustrated. The logical connections depicted include a local area network (LAN) 328 and a wide area network (WAN) 329 . Such networking environments are commonplace in offices, enterprise-wide computer networks, intranets, and the Intranet.
[0055] When used in a LAN networking environment, the computer 301 can be connected to the local network 328 through a network interface or adapter 309 . When used in a WAN networking environment, the computer 301 can include a modem 310 (or functionally similar device), or can be connected to a communications server on the LAN, or has other means for establishing communications over the WAN 329 , such as the Internet. The modem 310 , which can be internal or external, can be connected to the system bus 303 via the serial port interfaces 308 . In a networked environment, program modules depicted relative to the computer 301 , or portions therefor, can be stored in the remote memory storage device 327 . It will be appreciated that the network connections shown are exemplary and other means of establishing a communications link between the computers can be used.
[0056] Referring now to an embodiment in more detail in FIG. 4 there is shown a flowchart of an exemplary order, but not the only order, of using an embodiment for the assessment of the change, innovation, or new technology initiative. FIG. 4 shows the start of an initiative to manage a behavior change initiative 41 , an operation to setup and manage program/campaigns 42 , an operation to setup and manage participants/groups/attributes 43 , an operation to gather primary data 44 , a decision operation to survey new network actors 45 , an operation to run social network analysis 46 . In more detail, still referring to an embodiment in FIG. 4 , the database 2 contains, but is not limited to, the necessary data to execute the functionality of the operations 8 to 19 which could include, but is not limited to, participants, groups, participant attributes, change/innovation perceptions, social network connections which are also referred to as dyads, participant network attributes such as centrality or group membership. The database 2 could also contain a repository of training, communications, facilitating conditions and their impacts.
[0057] In further detail, still referring to an embodiment in FIG. 4 , the operation to manage programs/campaigns 42 has the functionality, but is not limited to, manage template of different types of changes or new innovation initiatives which could act as starting points for planning, simulation, managing, and monitoring. This operation to manage programs or campaigns 42 also allows the section of permissions and access for participants of the system for a particular program or campaigns.
[0058] In further detail, still referring to an embodiment in FIG. 4 , the operation to manage participants, groups, and attributes 43 can be used to allow creating, viewing, updating, and deleting of the participants who are targeted for the new change or innovation. This also includes removing duplicates or managing additional previously unknown participants who were forwarded a survey or identified during the process of gather primary connection data from the targeted participants of the innovation or change.
[0059] In further detail, still referring to an embodiment in FIG. 4 , the operation to gather primary data 44 can be used to gather perceptions, network connections, and actual usage information. The perceptions could include the ability to configure online surveys to gather perceptions using previously validated or new scales based on for areas such as usefulness, ease of use, social influence, or habits, behavioral intention and actual usage. The network connections could include survey questions asking for whom the individuals they go to for different modes such as help, information, resources and others. Actual usage of a system could gather in this section via a survey question, manually entering it or a file import or integration to a separate system such as usage logs.
[0060] In further detail, still referring to an embodiment in FIG. 4 , the operation to gather primary data 44 can be also able to track responses, view respondents, or offer incentives to complete the survey, and manage messaging. Because all the connections or targeted participants for a change or innovation initiative might not be known at the beginning of the initiative, there can be a decision operation 45 also includes functionality to configure “snowball survey” options, which essentially allows the system to allow participants to identify connections to originally non-targeted participants (i.e. outside of organization or target group) via the surveys, then follow up with an additional survey to the new connection or generate a list allowing an administrator to configure the new participant and send a new survey to them.
[0061] In further detail, still referring to an embodiment in FIG. 4 , the operation to run social network analysis 46 can be used to create the social network models and their attributes based on the primary and other data available to the system. This could include factions of the organizations which were identified to bring close groups through change together (i.e. determine training groups). This analysis can also be used to determine networks, factions, opinion leaders, isolates, and network attributes such as centrality.
[0062] In further detail, still referring to an embodiment in FIG. 4 , the operation to run perception analysis 47 can be used to run a statistical analysis of the perceptions of the group as well as merge the results with the social network analysis results. This allows the change or innovation planners to view the actual perceptions overlaid onto the social networks of the organization. This allows the participants to view the perceptions and actual usage of the innovation at an aggregate group or individual level. These perceptions are also used to determine the appropriate training and communication treatments. The system also calculates the perception metrics of a person's neighborhood to better predict their future usage
[0063] Referring now to an embodiment in more detail in FIG. 5 there is shown a flowchart of the recommendation and feedback operations within an embodiment, which would often happen as a continuation of the flowchart from FIG. 4 which shows an exemplary, but not the only order of using the invention. FIG. 5 shows an operation to generate recommend change roles 52 , an operation to select and assign change/innovation roles 53 , an operation to generate recommended training, communications & facilitating conditions 54 , an operation to select and configure training, communications, and facilitating conditions 55 .
[0064] In further detail, still referring to an embodiment in FIG. 5 , the operation to generate change roles 52 can be used to identify subject matter experts or super-users based on their centrality of different network modes. For example, if there are certain people that everyone goes to for help, they would be an ideal candidate to be a subject matter expert. This operation can also recommend training groups based on the networks which allows tight-knit groups to go through acceptance or adoption of the change or innovation together. Isolates can be identified here, because their training and communications could be chosen based on their position. The system can also identify how to improve the network structure to increase the speed of change. For example align subject matter experts with isolates, build connections between groups such as team events. This operation can also recommend participants who should be targeted for communication or events like team-events to increase the number of connections they have for getting help, information, and knowledge around the change or innovation.
[0065] In further detail, still referring to an embodiment in FIG. 5 , the operation to select and assign change and innovation roles 14 can be used to view the recommendations generated from operation 53 , then make any adjustments to the assignments of subject matter experts, training & communication groups, and super-participants/isolate pairings. The system user can view opinion leaders and groups based on the social network analysis. This allows them to view who has the most influential power regarding multiple modes of the change (i.e. where do they go for help, who has access to resources, information, domain knowledge, or other modes). Those with high centrality should be incorporated as subject matter experts into the change or innovation initiative. This operation allows the system user to view groups, factions, and auto-generated suggested training groups.
[0066] In further detail, still referring to an embodiment in FIG. 5 , the operation to generate training, communications, and facilitating conditions 54 can be used allow the system to auto-generate training and communication plans. The system chooses the best communication and training options based on the program template which includes prior research and similar initiatives. The objective is to generate appropriate communication and training for each individual and groups to maximize intention and usage where each participant could be different based on their individual current perceptions, group membership, centrality in the network, and moderating effects such as experience, and voluntariness of the change or innovation.
[0067] In further detail, still referring to an embodiment in FIG. 5 , the operation to select and configure training, communications, and facilitating conditions 55 can be used to view the recommendations from the system and select from list of training and communication treatments which have be shown to impact participant's perceptions, intentions, and usage. The potential impact of the communication and training options are based on prior published research, previous calibration via testing, or expert estimate. Impacts are categorized similar to the main constructs for change and innovation acceptance based on published research, previous testing, or expert estimate (usability, ease of use, facilitating conditions, social influence, habits). The system user can select from a list of facilitating conditions offered (help desk, online help, and others). New training options, communications, training and facilitating conditions can also be added by the system user. This is applicable in some embodiments because most large technology companies will have suggested roll-out activities. This could also include configuring incentives, such as giving an incentive to the first segment of participants that go through training To facilitate simulation of the acceptance of this change or innovation later, the timing of the training, communications, or facilitating conditions are entered.
[0068] Referring now to an embodiment in more detail in FIG. 6 there is shown a flow chart of exemplary implementation operations which could be seen in an exemplary usage further to FIG. 5 , but not the only order of using the invention. FIG. 6 shows an operation to an operation to monitor change using social networks, perceptions and usage data 63 which can be done in parallel with the execution of the change, innovation or new technology initiative. FIG. 6 also shows a decision operation 65 , where the larger process can be repeated if the initiative is not done or the results are not meeting the objectives.
[0069] In further detail, still referring to an embodiment in FIG. 6 , the operation to monitor the change or innovation initiative 61 can be used to view integrated social network views integrated in a way such as color-coded with relevant change metrics which could include usage, perceptions, effectiveness of communications and training treatments based on the most current data. Periodic surveys are one way that a current status is maintained of the perceptions and usage. Actual system usage logs of a new technology or innovation are another source of information for these dashboards that could imported through an external data interface 3 from FIG. 1 .
[0070] Referring now to an embodiment in more detail in FIG. 7 there is shown a flow chart of an implementation of operations which could be seen in an exemplary usage further to FIG. 6 , but not the only order of using the invention. FIG. 7 shows an operation to simulate change/innovation acceptance longitudinally over time 71 and an operation to manage a cost and benefit calculator 72 .
[0071] In further detail, still referring to an embodiment in FIG. 7 , the operation to simulate change and innovations longitudinally over time 71 can be used to quickly simulate multiple change and communication plans over-time across the networks and view the effectiveness of the different plans. In configuring the scenario for simulations, the system user can configure the target perceptions, intention, and usage which would be considered acceptable for success of the effort. This allows the system user to adjust communication, training, or facilitating conditions as needed until they are satisfied with the results. The simulations could take into account the particular subject matter experts, change in perceptions over a series of times steps, network neighbor perceptions, network neighbor intentions, network neighbor usage, training, communications, centrality, moderating affects, facilitating conditions, and factors that have been show through multiple regression or other statistical regression analysis to impact the usage, perceptions, and behavioral intentions of participants. The simulations can be re-run to test multiple scenarios based on a range of a particular variable or configuration (i.e. how much hand-on training to conduct)
[0072] In further detail, still referring to an embodiment in FIG. 7 , the operation to calculate the changing cost and benefit of the change or innovation initiative 72 can be used to calculate the return on a cost-benefit comparison of the overall change or innovation initiative. This calculation uses the communication, training, and facilitating condition treatments costs and additional participant entered data such as benefits, participant hourly costs, and others.
[0073] Referring now to an embodiment in more detail in FIG. 8 there is shown a high level flow chart of the overall intention that describes an exemplary order of the groups of operations shown in FIGS. 4-7 . This is an exemplary order, but not the only order contemplated of these larger groups of operations. What is shown is a step showing the start a change or innovation initiative 801 , an operation to complete the assessment 802 , which is detailed in FIG. 4 , an operation to complete the feedback and recommendation, which is detailed in FIG. 5 , an operation to complete the implementation, which is detailed in FIG. 6 , a decision operation to determine if an evaluation is necessary which 805 , an operation to iterate through the larger process if there are additional phases or iterations 806 , and an operation to complete the evaluation operations as detailed in FIG. 7 .
[0074] In more detail, still referring to an embodiment in FIG. 8 , which is a simplified example of business process flow in using the system to assess 802 , provide feedback and recommendation 803 , support the implementation 804 , and evaluate the larger change 808 , he interfaces 3 , 4 , 5 , 6 , and 7 detailed in FIG. 1 could also be used in conjunction with its appropriate needs of various operations such as the cost and benefit calculator 72 which could be used iteratively throughout the process. These components can be used in a serial fashion in some embodiments, but one familiar with change management or acceptance of new innovations, will appreciate the iterative dynamics of planning and executing these initiatives and usage of the functionality.
[0075] Some embodiments can achieve better planning, management, predictive simulation, and monitoring of adoption on acceptance of one or more significant change or new innovation initiatives. Some embodiments can maximize the cost and benefit, increase the responsiveness of the participants to adopt innovations and change, and minimize the likelihood of failure of change or innovation programs. Some will allow change management and innovation planners to optimize their plan via predictive simulations. Some embodiments can allow for active monitoring of the effectiveness of the behavioral change initiative so corrective actions can be taken quickly if necessary. Some embodiments can operationalize the complex social network and psychological dynamics of innovation and change acceptance into a system that is usable by the practitioners or planners managing change and innovations. It can make recommendations for many of the key decisions around change and innovation initiatives for the system user such as choosing subject matter experts and suggesting the appropriate communication and training treatments for a particular type of change.
[0076] It should be noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
[0077] It should also be noted that, as used in this specification and the appended claims, the phrase “configured” describes a system, apparatus, or other structure that is constructed or configured to perform a particular task or adopt a particular state of configuration. The phrase “configured” can be used interchangeably with other similar phrases such as arranged and configured, constructed and arranged, constructed, manufactured and arranged, and the like.
[0078] All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated by reference.
[0079] The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.
|
Embodiments of the invention include systems and methods for accelerating or improving the success rate of a behavior change in an organization, group or community. In an embodiment, the invention includes a method for accelerating or improving the success rate of a behavior change, the method including gathering primary and secondary relationship data of an informal network of individuals and behavior change constructs for a plurality of individuals within the informal network of individuals; performing social network analysis of the informal network; and performing statistical perception analysis of the individuals within the informal network. In an embodiment, the invention includes a system for accelerating or improving the success rate of a behavior change initiative in an organization, group or community. Other embodiments are also included herein.
| 6
|
FIELD OF THE INVENTION
This invention relates to a composition as well as to a method for providing slow release compositions containing an organic surfactant which inhibits acid producing bacteria from catalyzing metal sulfides such as iron sulfide.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,314,966 to Kleinmann relates to a rubber matrix containing a surfactant therein to inhibit the bacteria Thiobacillus ferrooxidans.
"Developments in Controlled Release Technology and Its Application in Acid Mine Drainage", by L. A. Fox and Vijay Rastogi, 1983 Symposium on Surface Mining, Hydrology, Sedimentology and Reclamation, Nov. 27 - Dec. 2, 1983, relates to controlling acid mine drainage wherein rubber matrix as well as a thermoplastic matrix, for example polyethylene, were utilized in association with anionic detergents such as sodium lauryl sulfate.
"Laboratory Methods for Determining the Effects of Bactericides on Acid Mine Drainage", by Mark A. Shellhorn and Vijay Rastogi, 1984 Symposium on Surface Mining, Hydrology, Sedimentology, and Reclamation, Dec. 2-7, 1984, relates to laboratory tests wherein surfactants were utilized to control acid-producing bacteria.
"Use of Controlled Release Bactericides for Reclamation and Abatement of Acid Mine Drainage", by Andrew A. Sobek, Mark A. Shellhorn, and Vijay Rastogi, preprint of Presentation to the International Mine Water Congress, Granada, Spain, Sept. 17-21, 1985, relates to tests controlling acid mine drainage through the use of surfactants as well as control release compositions.
"The Effects of Particle Size Distribution on the Rate of Mine Acid Formation and its Mitigation by Bacterial Inhibitors", by Mark A. Shellhorn, Andrew A. Sobek, and Vijay Rastogi, American Society of Surface Mining & Reclamation, Denver, Colo., Oct. 8-10, 1985, relates to the effect of particle size of metal sulfide refuse on acid water production.
"Effect of Bactericide Treatments on Metalliferrous Ore Tailings", by Andrew A. Sobek, Vijay Rastogi, and Mark A. Shellhorn, Society for Surface Mining & Reclamation, Mar. 17-20, 1986, Jackson, Miss., relates to bactericide treatments of uranium, copper, nickel, etc. tailings.
"ProMac Systems for Reclamation and Control of Acid Production in Toxic Mine Waste" by Vijay Rastogi, Richard Krecic, and Andrew Sobek, Surface Mine Drainage Task Force Symposium, March 31 - Apr. 1, 1986, relates to a system utilizing surfactants to treat a reclaimed area.
SUMMARY OF THE INVENTION
Accordingly, it is an aspect of the present invention to provide a method of making and a controlled release surfactant bactericide composition to control acid production in active and/or reclaimed mines.
It is yet another aspect of the present invention to provide a controlled release surfactant bactericide, as above, wherein said surfactant is generally a biodegradable organic anionic surfactant.
It is a further aspect of the present invention to provide a controlled release surfactant bactericide, as above, wherein said controlled release surfactant bactericide is contained in a thermoplastic matrix having a low softening point.
It is a still further aspect of the present invention to provide a controlled release surfactant bactericide, as above, wherein the slow release bactericide is a heterogeneous blend of the thermoplastic compound and the surfactant bactericide.
It is yet another aspect of the present invention to provide a controlled release surfactant bactericide, as above, wherein said thermoplastic matrix has a suitable porosity so that release of said surfactant bactericide is over an extended period of time.
It is yet another aspect of the present invention to provide a controlled release surfactant bactericide, as above, wherein the slow release thermoplastic matrix is formed by dry blending the thermoplastic and at least one compounding agent, and subsequently mixing and shearing a molten mass thereof containing the surfactant bactericide therein.
It is yet another aspect of the present invention to provide said slow release thermoplastic matrix in the form of pellets by extruding said molten mass and pelletizing the same.
These and other aspects of the present invention will become apparent from the following detailed description.
In general, a slow release composition for reducing acid water formation from a metallic sulfide material exposed to water and an acid catalyzing bacteria, comprises a heterogeneous matrix containing a theromplastic domain and a surfactant domain, said thermoplastic domain made from a thermoplastic material, said surfactant domain made from an effective concentration of an organic surfactant inhibiting acid forming bacteria so that said heterogenous matrix has a porosity capable of extended slow release upon contact with water.
DETAILED DESCRIPTION OF THE INVENTION
The controlled release composition of the present invention comprises a blend of thermoplastic compound with an immiscible surfactant bactericide so that the resultant thermoplastic matrix has a porosity capable of extended long term release of the surfactant. By "controlled release" it is meant that the release rate and/or duration of release of the surfactant can be varied. The thermoplastic compound utilized to form the matrix can generally be any thermoplastic polymer which is not degraded at processing temperatures and is compatible, that is accepts the surfactant. Inasmuch as many surfactant bactericides degrade at temperatures at about 211° C. or even less, the Vicat softening point of the thermoplastic compound is generally 210° C. or less, desirably 150° C. or less, and preferably 110° C. or less. Various suitable thermoplastic compounds include polyproplyene, polystyrene, styrene-butadiene-styrene triblock copolymers such as the various Kraton block copolymers manufactured by Shell, polyester, polyurethane, nylon, polyvinyl chloride, ethylene-vinylacetate copolymers and polyethylene. While the ethylene-vinylacetate copolymers are a desired thermoplastic, the various low melting point polyethylenes are preferred such as those that have a Vicat softening point at a temperature of from about 60° C. to about 90° C. The various other components of the present invention are generally based upon 100 parts by weight of the thermoplastic material.
In the reclamation or treating of various metal sulfides, and especially iron sulfide, acid forming bacteria such as Thiobacillus ferrooxidans catalyze the oxidation of metal sulfides and produce acids as well as soluble metals. Over a period of time, a considerable acid content can build up. Such buildup is usually in association with various earth disturbance activities including earth mines as well as surface mines since large amounts of the various sulfides are available. Such acid buildup is undesirable in that it is damaging to the ecology in that it prevents vegetation from sprouting and growing as well as killing existing vegetation, causing erosion and sedimentation problems down stream, and the acid itself causing destruction of aqueous life. The production of the acid must generally be prevented for at least three years or more to break the acid production cycle and to permit three main natural biological processes to occur; that is (1) a healthy root system which competes for both oxygen and moisture with the acid producing bacteria, (2) populations of beneficial heterotrophic soil bacteria and fungi are reestablished, resulting in the formation of organic acids which are inhibitory to Thiobacillus ferrooxidans, and (3) the action of plant-root respiration and the heterotrophic bacteria which increase CO 2 levels in the soil resulting in an unfavorable microenvironment for growth of Thiobacillus ferrooxidans.
In order to permit ground cover to continue to grow or reestablish itself, a surfactant bactericide, that is a biodegradable organic surfactant inhibitory to acid producing bacteria such as Thiobacillus ferrooxidans, is utilized in the thermoplastic matrix. Generally, cationic and especially anionic surfactants are very effective biocides with regard to acid producing bacteria. Considering the cationic surfactants, examples of such suitable surfactants include cocodimethylbenzylammonium chloride and N(acylocolaminoformylmethyl)pyridinium chloride. The anionic surfactants and salts thereof, especially sodium, are preferred. A group of preferred anionic surfactants are the various linear alkylbenzene sulfonates (LAS) as for example dodecylbenzene sulfonate, and the like. Especially preferred compounds of the present invention are the sodium salts of alkylbenzene sulfonic acid containing a combination of different alkyl chain lengths having a typical average of approximately 11.8 or 12, such salts having an alkyl average length of approximately 13 and such sodium salts having approximately an average alkyl chain length of 14. Generally the alkyl chain can have from about 9 to about 18 carbon atoms.
Another group of suitable anionic surfactants which function as effective bactericides are the various alkyl sulfates and sodium salts thereof wherein the alkyl group has from about 12 to 18 carbon atoms. Another suitable anionic surfactant is the various alpha olefin sulfonates wherein the total number of carbon atoms is from about 16 to about 20, and the sodium salts thereof. Yet another suitable surfactant bactericide is the various secondary alkane sulfonates having a total number of about 14 to about 18 carbon atoms. The various alcohol ethoxy sulfates constitute another suitable anionic surfactant bactericide wherein the total number of carbon atoms is from about 12 to about 22 carbon atoms. Another suitable bactericide is the various alkylphenol ethoxylates having a total number of from about 18 to about 72 carbon atoms. The various alcohol ethoxylates can also be utilized as suitable surfactant bactericides containing a total number of from about 14 to about 58 carbon atoms.
It is to be understood that various salts of the above surfactants and especially sodium salts can be utilized. The various alkyl surfates constitute a desired group such as sodium lauryl sulfate with the linear alkylbenzene sulfonates constituting a preferred group.
Still other anionic surfactants include a 1 to 18 carbon atom alkyl-phenoxy benzene disulfonic acid; an alkyl- or alkenyl phenoxy benzene disulfonic acid where the alkyl-and alkenyl-groups are C 8 -C 16 ; naphthalene sulfonic acid, alkyl-naphthalene sulfonic acid, or alkenyl-naphthalene sulfonic acid, especially where the alkyl- or alkenyl- groups have relatively short chain lengths, of C 8 or below and preferably C 1 -C 4 .
A list of various other cationic as well as anionic surfactants can be found in the 1978 annual edition or the 1983 annual edition of McCutcheon's Detergents and Emulsifiers, North American Edition, which is hereby fully incorporated by reference.
The surfactants are blended with the thermoplastic compounds at specific concentrations to produce a slow release composition or matrix at temperatures below the degradation point of the surfactant and yet at temperatures above the softening point of the thermoplastic compound. That is, a matrix is formed having distinct phases therein, a continuous thermoplastic phase or domain and a surfactant phase. The surfactants are generally immiscible with the thermoplastic compound and hence release of the surfactant occurs through elution, that is through solubility and hydrostatic pressure. A heterogeneous matrix is thus formed having a pore structure therein formed by the surfactant bactericide. The resulting porosity, that is the amount of pore structure formed within the theromplastic matrix by the surfactant bactericide is important and critical to effective slow release rates in order to achieve release over an extended period of time. In other words, long term leaching of the surfactant is achieved upon contact with water with a surfactant filled porous network within the thermoplastic matrix. Naturally, the thermoplastic matrix is formed by mixing the thermoplastic compound and the surfactant compound in a manner as described hereinbelow and forming an article therefrom such as a pellet.
According to the concepts of the present invention, it has been found that a suitable porosity for long term release, that is generally at least 1 or 2 years, desirably at least 3 to 5 years, and preferably at least 5 years, can be achieved by the utilization of desired amounts of the surfactant. Thus, a maximum amount of surfactant is approximately about 150 parts by weight or less for every 100 parts by weight of a thermoplastic compound. The concentration of the surfactant can vary to approximately 5 parts by weight based upon 100 parts by weight of the thermoplastic compound. A desired range is from about 25 parts to about 120 parts by weight, and preferably from about 35 parts to about 50 parts by weight per 100 parts by weight of the thermoplastic compound. Generally, the slow release will vary with the type of thermoplastic compound utilized and especially with the concentration of the surfactant. Smaller amounts or concentrations of the surfactants form a smaller porous network or porosity and result in longer release periods. Generally, approximately 50 parts by weight of surfactant will result in a release period of about 2 to 5 years whereas smaller amounts such as about 25 to about 35 parts by weight will result in release periods of approximately 5 to 10 years.
The slow release composition of the present invention is added to a particular environment to effectively control, that is to retard the formation of acid water. Naturally, the amount of acid water varies with the amount of metal sulfide present such as iron sulfide, and the like, the amount of water drainage, oxygen, bacteria, and the like. An effective amount of slow release material added to a specific site area is site specific and based upon hydrology, topography, climatic factors, and physical and chemical parameters of the site material. Such effective amounts can be from about 10 lbs. to about 425 lbs. by weight of surfactant per acre foot and more desirably from about 90 lbs. to about 200 lbs. per acre foot.
The application of the slow release thermoplastic composition of the present invention will retard or substantially eliminate acid water for extended periods of time such that ground cover or vegetation can commence growth and take a sufficient foothold whereby the natural biological processes of the vegetation will break the acid production cycle, as noted hereinabove.
In order to aid in initially abating or eliminating the production of the acid producing bacteria such as Thiobacillus ferrooxidans, an initial application of only a surfactant, is applied to the specific site, area, etc. The amount of such surfactant bactericide which is generally the same type of surfactant set forth hereinabove and thus is hereby fully incorporated by reference, is an amount of matrix containing from about 7 lbs. of surfactant to about 300 lbs. of surfactant per acre foot, and desirably from about 45 lbs. to about 150 lbs. of surfactant per acre foot. In other words, an amount of matrix material is utilized such that the weight of surfactant therein is generally within the above ranges.
The method of application of the raw surfactant can be in any conventional manner as by spraying a solution and/or spreading in a wet or dry form.
The slow release composition of the present invention is made by mixing the various ingredients in a manner as set forth hereinbelow. The composition is then generally extruded and pelletized. Accordingly, various compounding ingredients can be used to aid in the mixing and extruding of the slow release composition. Such compounding aids are generally known to the compoundng and extruding art and can be used in conventional amounts. Thus, various antioxidants can be utilized such as hindered phenols to aid in preventing degradation of the polymer matrix and the surfactant. Various conventional types of pigments such as titanium dioxide, carbon black, and the like can be utilized in small amounts in order to achieve a desired color of hue so as to color code various concentrations or porosities.
Processing aids such as lubricants, silicas, and fluxing agents are utilized to optimize mixing and processing operations. Suitable lubricants which also control dust problems include high grade mineral oils, polymer processing oil, and the like. The amount thereof is usually quite small, as 1 or 2 parts by weight per 100 parts by weight of thermoplastic compound. Examples of suitable silicas include amorphous silica, and the like, and are utilized in sufficient amounts to provide processing control and usually from about 1 to about 20 parts by weight per 100 parts by weight of the thermoplastic compound. Examples of suitable fluxing agents include stearic acid, calcium stearate, or other lubricants, and the like in suitable amounts to provide for release of compounds from metal surfaces of processing equipment as from about a total of 1 to about 4 parts by weight per 100 parts by weight of the thermoplastic compound.
The slow release thermoplastic composition of the present invention is prepared in the following manner. The thermoplastic such as polyethylene is added to a mixer such as a ribbon blender along with all of the miscellaneous ingredients or compounding agents to form a preblend. Thus, the various pigments, lubricants, antioxidants, and processing aids such as stearic acid and talc are added to the ribbon blender. The various components are added dry in that it is imperative that dry blending occur to enable efficient mixing of the ingredients. The preblend is desirably mixed at ambient temperature.
The preblend is subsequently added to a temperature controlled mixer such as a Banbury. The surfactant of the present invention along with any silica is also added and mixer under heat at approximately 190° F. to about 280° F., such as about 220° F. High temperatures are avoided to minimize thermal degradation and permit better process control. The temperature controlled mixer incorporates the added ingredients into the preblend. Mixing continues until completed whereupon the composition is dumped or added to a two-roll mill or extruded. To obtain additional mixing, typically one of the rolls, for example the back roll, turns at a high rate of speed but is cool, that is has a temperature of from about 50° F. to about 100° F. with approximately 70° F. being preferred. The remaining roll turns at a lower or slow rate of speed, for example the front roll, but is heated to a higher temperature as from about 140° F. to about 200° F. with approximately 160° F. being preferred. Alternatively, the back roll can be hot and the front roll can be cool. The milling ensures that the various components are thoroughly mixed together albeit separate and distinct phases, that is different domains exist inasmuch as the surfactant is immiscible in the thermoplastic compound. After sufficient mixing has occurred, a portion of the material from the first two-roll mill, for example a ribbon of material is fed to a second two-roll mill which is operating under the same conditions as the initial two-roll mill. Hence, the second mill has a fast roll and a slow roll with one roll being operated at a lower temperature than the remaining roll. After a sufficient amount of time on the second mill to obtain uniformity, the heterogeneous immiscible but thoroughly mixed composition is fed as a ribbon of material into an extruder. The majority portion of the extruder is operated at a relatively low temperature as from about 80° F. to 150° F. with about 100° F. being preferred which is approximately the incoming temperature of the ribbon. Upon entering the extruder, the temperature of the composition is gradually heated as it passed therethrough until it reaches a face plate. In the preferred embodiment of the present invention, a hot melt die face plate pelletizer is utilized which is operated at a temperature of about 250° F., although it can be from about 180° F. to about 300° F. Upon passing through the die face plate pelletizer, it is sheared by rotating blades whereby pellets are formed. The pellet size is a function of the diameter of the apertures in the face plate, the ejection pressure of the extrudate, the flow rate of the extrudate, the extruder temperature, the rotational speed of the shearing blades, as well as the slow release formulation. The formed pellets are cooled and conveyed by water at a temperature of from about 60° F. to about 150° F. with approximately 85° F. being preferred. The preferred method of cooling however is by air.
The size of the pellets can generally range from about 0.1 inch to about 1.0 inch. A desirable pellet size with regard to slow release properties and sufficient surface area is a cylinder approximately 1/4" in diameter and 1/4" in length.
Another or alternative method of forming a slow release thermoplastic composition is to generally add all of the various components together and mix in the presence of heat at a temperature above the softening point of the thermoplastic compound and then to subsequently form a desired article. Thus, a porosity forming surfactant as set forth hereinabove in a suitable or effective amount can be added to a mixer such as a Banbury along with a thermoplastic compound, as noted hereinabove, along with the various compounding agents. It is noted that only one compounding agent need be utilized which is a lubricant processing aid such as stearic acid, calcium stearate, and the like. The temperature of the mixer, as noted, is above the softening point of the thermoplastic compound. Mixing under heat generally continues a suitable amount of time such that a uniformity of the various components is achieved. Thus, a porous forming network is formed by the surfactant throughout the thermoplastic matrix upon cooling of the mixture. That is, upon use of the thermoplastic composition, the surfactant will be removed thereby leaving a porous thermoplastic matrix. The molten mass from the mixer is then generally formed into a convenient article by any suitable forming apparatus. For example, the heated composition can be dropped or added to a compression molding machine wherein bricketts, pellets, and the like are formed. The amounts of the various components is as set forth hereinabove as is the desired release times of the formed article.
The invention will be better understood by reference to the following examples:
EXAMPLE I
Example I had the following formulation:
______________________________________MATERIAL AMOUNT______________________________________Sodium dodecylbenzene sulfonate; carbonchain C.sub.9 -C.sub.13 37.5 lbs.For example, NACCONOL 90G, fromThe Stepan Co.Polyethylene 100.0 lb.For example, PETROTHENE NA270-00,from U.S. Industrial Chem. Co.1,2-Bis(3,5-Di-Tert-Butyl-4-Hydroxyhydro-cinn-amoyl)Hydrazine 0.5 lb.For example, IRGANOX MD-1024, fromCiba-Geigy Corp.Petroleum Oil 1.0 lb.For example, SHELLFLEX 371, fromShell Oil Co.Amorphous Silica 8.0 lb.For example SYLOX 2, fromW. R. Grace & Co.TALC 2.0 lb.For example, MISTRON VAPOR TALCfrom Cyprus Mineral Co.Stearic Acid 1.0 lb.For example, EMERSOL-132, fromEmery Chem.Yellow Pigment 0.2 lb.For example, LR 6475, 80% yellow 42, 20%polyethylene, from LancerDispersion, Inc.______________________________________
The above formulation was prepared in pellets of approximately 1/4 inch by 1/4 inch in a manner as set forth hereinabove, which is hereby fully incorporated. That is, all of the ingredients with the exception of the silica and the sodium dodecylbenzene sulfonate were added to a ribbon blender and blended. Subvsequently, the silica and the sodium dodecylbenzene sulfonate were added and mixed. The pellets produced were added to distilled water and the number of hours to 50% extraction of the surfactant contained in the slow release composition is set forth in Table I as is the expected pellet life. The actual life in the earth's environment is much longer since release occurs at a much slower rate.
EXAMPLE II
Example II contained the following formulation:
______________________________________MATERIAL AMOUNT______________________________________Sodium dodecylbenzene sulfonate;carbon chain C.sub.9 -C.sub.13For example, NACCONOL 90G, fromThe Stepan Co.Polyethylene 100.00 lb.For example, PETROTHENE NA270-00,from U.S. Industrial Chem. Co.1,2-Bis(3,5-Di-Tert-Butyl-4-Hydroxy-hydrocinn-amoyl)Hydrazine 0.5 lb.For Example, IRGANOX MD-1024, fromCiba-Geigy Corp.Petroleum Oil 1.00 lb.For example, SHELLFLEX 371, fromThe Shell Oil Co.Amorphous Silica 8.00 lb.For example, SYLOX 2, fromThe W. R. Grace & Co.TALC 2.00 lb.For example, MISTRON VAPOR TALCfrom Cyprus Minerals Co.Stearic Acid 1.00 lb.For example, EMERSOL-132, fromEmery ChemicalsPhthalocyanine 0.052 lb.For Example, Q-5755 MUPCO 50% PHTHALOBlue RS, from Ciba-Geigy Corp.______________________________________
This above formulation was made into a slow release thermoplastic composition in a manner as set forth in Example I. When subjected to distilled water, the hours to 50% extraction of the surfactant and the expected release life are set forth in Table I.
RUBBER CONTROL
In a manner as set forth in U.S. Pat. No. 4,314,966 to Kleinmann, which is hereby fully incorporated by reference, a rubber matrix was prepared having the following formulation:
______________________________________MATERIALS PARTS BY WEIGHT______________________________________Natural Rubber 50 partsSBR 50 partsCarbon Black 10 partsSodium Lauryl Sulfate 40 parts______________________________________
The above rubber formulation when prepared into a slow release composition was tested in distilled water in the same manner as Examples I and II. The time to 50% extraction as well as expected life is set forth in Table I.
TABLE I__________________________________________________________________________ CONCENTRATION-PARTS OF HOURS TO 50% SURFACTANT PER 100 PARTS EXTRACTION EXPECTEDEXAMPLE OF POLYETHYLENE OF SURFACTANT LIFE__________________________________________________________________________I 37.5 478 hours Greater than 10 yearsII 48.3 85 hrs. 3-5 yearsRubber Control 40* 25 hrs. 6 mos.- 1 year**__________________________________________________________________________ *Based upon 100 parts of rubber **The rubber degraded (based upon actual field tests)
As readily apparent from Table I, the slow release compositions of the present invention containing a thermoplastic matrix and having a surfactant porosity network therein resulted in much slower release times. That is, release times of anywhere from at least 3 times to about 19 times as long as the rubber control. Moreover, from actual experience, it has been shown that a rubber matrix will not have a release life much beyond 6 months to 1 year since it substantially degrades, whereas the thermoplastic matrixes of the present invention can last up to 100 years or more. Thus, the porosity-forming network of the present invention within the thermoplastic matrix provides a much greater release life.
While in accordance with the patent statutes, a best mode and preferred embodiment has been set forth, the scope of the claims is not limited thereto, but rather by the scope of the attached claims.
|
Various chemolithotrophic bacteria such as Thiobacillus ferrooxidans by direct or indirect mechanisms catalyze the oxidation of metal sulfides and produce acid, i.e. sulfuric acid and soluble metal salts at a much faster rate than chemical oxidation. Elimination of such bacteria would inhibit the formation of the acid. The natural production of such acids is particularly troublesome in mines e.g. coal mines, since acid water is produced which is damaging to the environment. An effective method of abating or eliminating such acid water production is to apply a bactericide such as a biodegradable organic surfactant which at low pH values are bactericides and hence inhibit the bacteria from catalyzing the metal sulfides. The affected acid water site can thus be treated with the surfactant which provides a temporary or short term result usually for a few months. A long term solution, that is 1 year to several years, is provided through the use of a slow release composition of the present invention in which a heterogeneous matrix contains a thermoplastic domain and an organic surfactant domain. A suitable porosity is created when proper amounts of surfactant are utilized so that a long term slow release composition is formed. A method of making the heterogeneous matrix or slow release composition involves the dry blending of a thermoplastic compound and various processing aids, subsequently adding a bactericide thereto and mixing under shear and heat the resulting molten composition. A suitable slow release article can be formed such as pellets.
| 0
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to the synthesis of metal powders and films, and more specifically, to the continuous synthesis of nanostructured metal powders and coatings using a microwave waveguide, cavity or beam system.
[0003] 2. Description of the Related Art
[0004] Metallic powders have been prepared by physical vapor deposition, by mechanical blending and mixing, and by chemical routes. Vapor methods are not cost effective and make only small amounts of material. The mechanical blending route often introduces impurities into the final product. Fluidized beds have also been used to coat powders with metals, however, as in vapor methods, the initial equipment is expensive, and it is difficult to evenly coat powders and to handle powders of different sizes.
[0005] Metallic coatings have been prepared using electroplating and electroless plating. Electroless plating requires that the substrate be pretreated before plating and the substrate must also be an insulator. Using the polyol method, there does not need to be any chemical pretreatment of the surface and the substrates may be either conductive or insulators.
[0006] Nanostructured powders and films (with particle diameters of about 1-100 nm) have many potential electronic, magnetic, and structural applications such as catalysis, electromagnetic shielding, ferrofluids, magnetic recording, sensors, biomedical, electronics, and advanced-engineered materials.
[0007] Among the various preparative techniques, chemical routes offer the advantages of molecular or atomic level control and efficient scale-up for processing and production. Others in the art have prepared micron and submicron-size metallic powders of Co, Cu, Ni, Pb, and Ag using the polyol method. These particles were composed of single elements. Depending on the type of metallic precursors used in the reaction, additional reducing and nucleating agents were often used. The presence of the additional nucleating and reducing agents during the reaction may result in undesirable and trapped impurities, particularly non-metallic impurities.
[0008] These prior procedures have been unable to obtain nanostructured powders having a mean size of 1-25 nm diameter. These prior procedures have not been useful in producing nanostructured powders of metal composites or alloys or metal films.
[0009] U.S. patent application Ser. No. 10/113,651 to Kurihara et al. discloses the use of millimeter wave radiation to heat a polyol reaction mixture in a batch process. This process allows for the production of nanostructured metal powders and films via the polyol process.
[0010] Grisaru et al., “Preparation of Cd 1-x Zn x Se Using Microwave-Assisted Polyol Synthesis,” Inorg. Chem., 40, 4814-4815 (2001), discloses the use of low power microwave radiation to make small batches of metal nanoparticles. The yield of this process is less than single gram quantities per batch.
[0011] There remains a need for a process for making large quantities of nanostructured metal particles and films using the polyol process
SUMMARY OF THE INVENTION
[0012] The invention comprises a method of forming a nanocrystalline metal, comprising the steps of: providing a reaction mixture comprising a metal precursor and an alcohol solvent; continuously flowing the reaction mixture through a reactor; applying microwave or millimeter-wave energy to the reaction mixture; wherein the microwave or millimeter-wave energy is localized to the vicinity of the reaction mixture; and heating the reaction mixture with the microwave or millimeter-wave energy so that the alcohol solvent reduces the metal precursor to a metal; wherein the heating occurs in the reactor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] [0013]FIG. 1 schematically illustrates an apparatus for practicing the method of the invention as a continuous process in a traveling wave (waveguide) applicator;
[0014] [0014]FIG. 2 schematically illustrates an apparatus for practicing the method of the invention as a continuous process in a waveguide-based standing wave (resonant cavity) applicator; and
[0015] [0015]FIG. 3 schematically illustrates an apparatus for practicing the method of the invention as a continuous process with an 83 GHz millimeter-wave beam applicator.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0016] In the first step of the invention, a reaction mixture comprising a metal precursor and an alcohol solvent, such as a glycol, is provided. More then one metal precursor and/or glycol solvent may be used. Any glycol solvent that is liquid and dissolves the metal precursor or precursors, or allows the metal precursor or precursors to react, at the reaction temperature may be used. For example, the polyols described by Figlarz et al., in U.S. Pat. No. 4,539,041, or described by Chow et al., in U.S. Pat. No. 5,759,230, the entireties of which are incorporated herein by reference, may be used. Specifically, Figlarz et al. recites the use of aliphatic glycols and the corresponding glycol polyesters, such as alkylene glycol having up to six carbon atoms in the main chain, ethylene glycol, a propylene glycol, a butanediol, a pentanediol, a hexanediol, and polyalkylene glycols derived from those alkylene glycols. Additional suitable glycol solvents for use in the present invention include, but are not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, ethoxyethanol, butanediols, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, octanediol, and dodecanediol. Related solvents such as alcohols, e.g., ethanol, propanol, butanol may also be used if the appropriate reaction temperature can be reached without boiling of the solvent.
[0017] The reaction mixture may also comprise an additional organic solvent. Any organic solvent that is liquid or will become liquid at temperatures greater than 25° C., and dissolves the metal precursor so that it may react with the glycol solvent maybe used. The glycol solvent may then be added to the metal precursor in the organic solvent any time after dissolution of the metal precursor.
[0018] Suitable metal precursors include, but are not limited to, metal acetates, chlorides, hydrates, nitrates, oxides, oxalates, carbonyls, hydroxides, acetylacetonates, oxalates, and carbonates. Preferred precursors to use for the formation of nanostructured powders and films including any specific metal are known in the art and will depend upon the metal selected. Suitable precursors may be substantially soluble in the reaction mixture.
[0019] The concentration of the precursor in the reaction mixture may influence crystallite size. When this influence occurs, smaller precursor concentration may provide smaller crystallites and particles. If the concentration of the precursor is too small, few, if any precipitates may form. Too high of a concentration of the precursor may result in crystallites that are larger than sub-micron size. Additionally, sufficient glycol solvent can be present to completely reduce essentially all metal precursors in the reaction mixture. Otherwise, the unreacted precursor may prevent the formation of a pure or essentially pure nanostructured metal material. Suitable ranges of concentration of the precursors are about 0.001-2.00 M, depending on the solubility of the precursor in the solvent. Typically, solutions near the saturation concentration are used, about 0.01-0.1M.
[0020] At the time of mixing, the glycol and/or any other organic solvent present may be either heated or unheated. Heating may facilitate the dissolution of the metal precursor, but may controlled to temperatures that do not initiate the reduction process.
[0021] The method described here is performed as a continuous process. This is done by flowing the reaction mixture through a reactor. The reactor should allow microwave energy to enter the reactor to heat the reaction mixture. The reactor may comprise a material that is transparent to microwave energy.
[0022] The process can be performed at ambient pressure, in which case the process temperature is limited to the normal boiling point of the solvent. The process can also be performed at a pressure above ambient, which has the advantage of elevating the boiling point of the solvent and permits more rapid reaction and processing.
[0023] Microwave energy is then applied to the reaction mixture. This heats the reaction mixture so that the glycol solvent reduces the metal precursor to a metal. As used herein, the term metal includes both metal and metal oxide. The metal may be produced in the form of metallic particles or a metallic coating. In the continuous process, this occurs while the reaction mixture is flowing through the reactor. In a typical batch microwave process, the microwave energy is applied to the reaction mixture by means such as a microwave oven. This generally does not allow the energy to be localized to the vicinity of the reaction. In the case of a millimeter-wave beam driven batch process, the energy can be localized to the vicinity of the reactor. More than a hundred-fold increase in metal powder output can be achieved in this way in the continuous process. The microwave source permits greatly accelerating the polyol process with the result of production of powders of smaller particle size and greater particle size uniformity. The continuous microwave process permits production of powders at much higher rates than in any of the batch microwave or millimeter wave processes.
[0024] The continuous microwave polyol process can be performed with three different types of microwave systems, all of which can effectively localize the microwave power in the reactor. The first, described below, is in a single pass, traveling wave applicator, where microwave energy propagates down the length of a waveguide, where the maximum field and power is concentrated at the center of the waveguide where the reaction tube is located. The second type of system is a standing wave system where the microwaves are introduced into a tuned cavity, which concentrates the microwave energy at the location of the reaction tube. The third is a beam system, where microwave energy, typically at shorter wavelengths, is focused onto the reactor through which the polyol solution flows. Suitable sources or microwave or millimeter wave energy include, but are not limited to, a magnetron and a gyrotron. Suitable wavelengths include, but are not limited to 2.45 GHz and 83 GHz.
[0025] [0025]FIG. 1 schematically illustrates an apparatus for practicing the method of the invention as a continuous process. The apparatus consists of a microwave magnetron 10 capable of producing 2.45 GHz microwave power, a waveguide 20 , and a water load 30 . The waveguide 20 directs the microwave energy along a vertical path and into the water load 30 , which absorbs any microwave energy not coupled into the polyol solution flowing through the reactor. The water load does not take part in the reaction. Other means for removing excess microwave energy may also be used. The vertical portion of the waveguide 20 contains a reaction vessel 50 , which is 10 mm diameter silica tube. A suitable tube 50 has a reaction zone of, but not limited to, 20 to 40 cm. This tube 50 is transparent to microwave energy. A pump 40 pumps the reaction mixture into the bottom of the tube, through the tube 50 , and out of the outlet 60 at the top of the tube, where the mixture is collected. As the mixture passes through the tube 50 inside the waveguide 20 , it is exposed to the microwave energy, which produces the metallic particles. The pump speed is set to achieve the desired size and amount of metallic particles in the outlet stream 60 . A suitable reaction time is about 10 seconds. The waveguide 20 pictured is a single-pass waveguide. The waveguide 20 may also lead into a resonant cavity around the reaction vessel to intensify the microwave power. A suitable range of microwave power for this apparatus is from about 1000 to about 3000 W.
[0026] [0026]FIG. 2 schematically illustrates an apparatus for practicing the method of the invention as a continuous process in a waveguide-based standing wave (resonant cavity) applicator. The microwave energy 110 at 2.45 GHz enters waveguide 120 containing a resonant cavity 130 bounded by an iris 140 and an adjustable short 150 . The cavity 130 is 7.2 cm tall, which was determined by the frequency of the microwave energy 110 . The circled area 160 shows the region of highest power. A 1 cm ID silica reaction tube 170 passes through this region 160 . The reaction mixture enters at 180 , passes through the reaction tube 170 , and exits at 190 .
[0027] [0027]FIG. 3 illustrates an apparatus for practicing the method of the invention as a continuous process with a millimeter-wave beam heating the solution in a reaction tube. A beam of millimeter-wave energy 210 reflects off a focusing mirror onto a reaction tube 220 through which the reaction mixture 230 is flowing. The beam is polarized and the polarization direction may be used to enhance the coupling to the reactor. A radiation shield may also be placed around the reaction tube to further concentrate the microwave power in the reactor. A suitable range of microwave power for this process, with a 1 cm diameter reaction tube is about 2000-4000 W, and the reduction process takes place in 1-2 seconds over a length of about 10 cm in the reaction tube. The effluent 240 contains the nanoparticles.
[0028] The efficacy of such rapid heating, for production of nanophase materials and the processing of such materials into useful components, has been demonstrated. Some of the advantages of using microwave energy as the heat source include rapid heating and cooling, volumetric heating, elimination of thermal inertia effects, and spatial control of heating. A microwave beam system at a wavelength of about 83 GHz, can be focused to a spot size as small as 0.5 cm if necessary, and, being a beam source, can also be steered, defocused, and shaped as necessary to direct microwave energy into a reactor. In a traveling wave system, with a reaction tube along the center of the waveguide, the microwave power is concentrated along the axis of the waveguide, with most of the power within the central 1-2 cm in a 2.45 GHz S-Band waveguide, and couples very well into the reaction mixture within the tube. In a standing wave system, using a resonant cavity, similar concentration of power is obtained, with most of the power concentrated within a few cubic centimeters in the center of an S-Band waveguide resonant cavity. The microwave energy provides a very effective heating source in the polyol process in production of nanophase metal and metal alloy powders. This source allows for very short processing times and high heating rates, due to bulk heating of the solution. This results from direct coupling of the microwave energy to the polyol solution. 2.45 GHz microwave energy is particularly effective for heating ethylene glycol as this frequency is near that at which the peak absorption occurs in ethylene glycol. Rapid heating of solutions is possible because the heating rate is not limited by the requirement to transport heat to the reaction vessel, through the walls of the reaction vessel, and through the interior of the solution.
[0029] The microwave source allows for very short processing times, high heating rates, the ability to selectively coat substrates, and the ability to work in a superheated liquid region. Direct coupling of the microwave energy to the solution elements results in high heating rates due to bulk heating. Bulk heating also permits superheating, since boiling is normally nucleated at asperities on surfaces of containers. The ability to focus a beam allows for the ability to selectively coat substrates, by driving the reduction reaction in the immediate vicinity of the substrate.
[0030] Other advantages of microwave heating to drive the polyol process include faster reaction time, more uniform thermal heating, and thermal history. These result in smaller particle sizes, if desired, from the shorter reaction times, and a more narrow distribution of particle size (from the more uniform temperature distribution and thermal history.
[0031] The reaction mixture is reacted at temperatures sufficiently high to dissolve, or allow the reaction of, the metal precursor or precursors and form precipitates of the desired metal. Usually, refluxing temperatures are used. The mixture can be reacted at about 85° C.-350° C., or at about 150° C.-220° C., in the case of ethylene glycol solutions. The preferred temperature depends on the reaction system used, i.e., the solvents and precursor salts.
[0032] The pH may influence the method of the present invention. For examples, changing the pH during the reaction may be used to alter the solubility of the reaction product in the reaction mixture. By altering the solubility of the smallest crystallites during the reaction, the average size of the crystallites obtained may be controlled. If a constant pH is desired throughout the reaction, the reaction mixture may be modified to include a buffer.
[0033] During the reaction, the reaction mixture may, but need not, be stirred or otherwise agitated, for example by sonication. The effects of stirring during the reaction depend upon the metal to be formed, the energy added during stirring, and the form of the final product (i.e., powder or film). For example, stirring during the production of a magnetic material would most likely increase agglomeration (here, the use of a surfactant would be beneficial), while stirring during the formation of a film would most likely not significantly affect the nanostructure of the film. Stirring during the formation of films, however, will probably influence the porosity of the formed films and thus maybe useful in sensor fabrication. Stirring is most feasible with the beam system, where the presence of the stirring probe does not affect the process.
[0034] The continuous process is generally used to produce metal or metal oxide particles. The process can also produce a metal film coated on a substrate, by transporting the substrate through the solution in the continuous system, e.g., on a belt carrying substrates through a flowing precursor solution heated locally by a millimeter-wave beam. To produce a nanostructured film, the substrate upon which the film is to be provided is contacted with the reaction mixture during the reaction. Unlike electrochemical deposition methods, which require an electrically conductive substrate, the present invention can provide thin, adherent (as determined by the adhesive tape test) nanostructured films on any surface, including electrically insulating substrates. Also, unlike aqueous electroless plating methods, the process of the present invention can produce thin, adherent nanostructured metal films on surfaces that should not be processed in aqueous environments.
[0035] After the desired precipitates form, the reaction mixture may be cooled either naturally (e.g., air-cooling) or quenched (forced cooling). Because quenching provides greater control over the reaction time, it is preferred to air-cooling. For quenching to be useful in the deposition of a conductive metal film upon a substrate, however, the substrate and the film/substrate interface must be able to withstand rapid thermal changes. If the substrate and/or film/substrate interface cannot withstand these rapid thermal changes, then air-cooling should be used.
[0036] The method of the present invention may be used to form various metals and alloys or composites thereof. For example, nanostructured films or powders of transition metals such as Cu, Ni, Co, Fe, Mn, or alloys or composites containing these metals, may be made according to the present invention. Further examples include Cr, Zn, Ga, Ru, Rh, Pd, Ag, Cd, Sn, Sb, W, Re, Ir, Pt, Au, and Pb. Still further examples are alloys of any of the above, such as CoNi, AgNi, FeCu, FePt, FeNi, FeCo, CuCo, etc. Metal/ceramic composites and metal oxides, such as CoAl 2 O 3 and CoFe 2 O 3 are also possible. As explained above, the precursor form for the metal will depend upon the metal itself. Generally, the precursor may be any metal-containing compound that, under the reaction conditions, is reduced to the elemental metal and by-products that are soluble in the reaction mixture. In the present invention, typical reaction times, at processing temperatures, extend from about 1 to 20 seconds, and more often from about 2 to 10 seconds. The method can produce metal particles having a mean diameter of about 100 nm or less.
[0037] The method of the present invention can produce nanostructured powders and films in the absence of a nucleating agent or catalyst. The resulting nanostructured films can thus be free or essentially free of impurities that would deleteriously alter their properties. If desired, surfactants and/or dispersants may be added to the reaction mixture to avoid the agglomeration of nanoparticles. If a highly pure product is desired, these surfactants and dispersants should be essentially free of insoluble materials, or capable of being burnt out of the final product. Where a surfactant is used, the best choice of surfactant will depend upon the desired metal. Steric stabilization, using a nonionic surfactant (e.g., a high temperature polymeric surfactant), is preferred, since ionic surfactants may undesirably alter the pH of the reaction system during reduction of the metal precursor. If desired, however, a mixture of ionic and nonionic surfactants can be used. If desired, high boiling point organics or capping agents may be added to the reaction mixture to avoid agglomeration. Examples of capping agents include any of the carboxylic acids of triglycerides such as: oleic acid, linoleic acid, linolenic acid and other high molecular weight acids, stearic acid and caprioc acid, and other agents such as trialkylphosphines.
[0038] The method of the present invention may also be used to produce nanostructured composite metal films and powders. As defined herein, a composite metal film includes at least one metal component and at least one other component that is intentionally included in amounts that significantly enhance the desirable properties of the film or powder. The other component, which is also nanostructured, is usually, but not necessarily, a metal. Where the other component is a metal, the metal may be any metal, not just those metals that could be deposited as a pure film according to the method of the present invention. Throughout the present specification and claims, the term “complex substance” is defined as a composite or an aloy that includes at least two different components. Throughout the present specification and claims, the term “alloy” applies to intermetallic compounds and solid solutions of two or more metals. The term “composite” applies to phase-separated mixtures of a metal with at least one other component. Where the other component of the final product is a chemically stable ceramic, the present invention provides a nanostructured metal/ceramic composite. Generally, a metal/ceramic composite includes at least 50 volume percent metal, in the form of a single-phase material or an alloy. Throughout the present specification and claims, the term “composite” includes alloys, and metal/ceramic composites.
[0039] To produce the complex substances, a precursor(s) for the at least one metal component and precursors for the other component or components are atomically mixed in the reaction mixture before heating the mixture to the reaction or refluxing temperature. Otherwise, the process proceeds as described above in the case of powders and films, respectively.
[0040] In producing composite substances according to the present invention, the initial molar ratios of the components to each other may not be reflected in the final product. Additionally, the ability of precursors for the components to atomically mix in the reaction solution does not assure that the components will form a composite substance final product. For this reason, the correct starting ratios of the precursors of each component for any composite substance must be determined empirically. The relative reduction potentials of each component can provide some guidance in making this empirical determination.
[0041] The solvent in the process may be recyclable. The powder feedstock can be any size or shape. The process of the present invention can also allow for the following aspects: the deposition of magnetic materials; the preparation of colloidal metals; the deposition of single elements, alloys and multicomponent elements; bulk heating of the solution which results from direct coupling of the beam energy to the solution elements; the alloying of immiscible metals; and the control of coating thickness and very rapid heating and control of solution kinetics.
[0042] Having described the invention, the following example is given to illustrate a specific application of the invention. This example is not intended to limit the scope of the invention described in this application.
EXAMPLE
[0043] Continuous production of Cu nanoparticles—Cu nanoparticles were produced using the apparatus of FIG. 1. The reaction mixture was 0.025 M copper acetate in ethylene glycol. The microwave energy source was Cober Model S6F Industrial Microwave Generator magnetron producing 2.0 kW of 2.45 GHz microwave energy. The pump speed was set to 3 cm 3 /s, which produced a residence time in the silica tube of 10 s. The temperature in the tube was maintained at 205-210° C.
[0044] Cu particles were present in the effluent from the tube. The particles were kept suspended in the solvent for subsequent particle size measurement. The average particle size was 50 nm, with a bimodal distribution with peaks at 10 and 100 nm, determined by light scattering. The continuous process was operated for 300 s, producing a total of 1.5 g Cu powder.
|
A method of forming a nanocrystalline metal, comprising the steps of: providing a reaction mixture comprising a metal precursor and an alcohol solvent; continuously flowing the reaction mixture through a reactor; applying microwave or millimeter-wave energy to the reaction mixture; wherein the microwave or millimeter-wave energy is localized to the vicinity of the reaction mixture; and heating the reaction mixture with the microwave or millimeter-wave energy so that the alcohol solvent reduces the metal precursor to a metal; wherein the heating occurs in the reactor.
| 2
|
[0001] This application claims priority under 35 USC § 119(e) to U.S. patent application Ser. No. 60/602,865, filed on Aug. 20, 2004, the entire contents of which are hereby incorporated by reference.
BACKGROUND
[0002] This description relates to pumps and motors, for example, hydraulic pumps and motors.
[0003] In some hydraulic pumps, rotary motion is translating into reciprocating motion of a piston, which pumps the hydraulic fluid. Conversely, in some hydraulic motors, a pressurized fluid causes reciprocating motion of the piston, which is translated into rotary motion.
SUMMARY
[0004] In one aspect, a hydraulic device includes a rotatable drum, at least one piston, a transition arm, and at least one compensating piston. The rotatable drum defines a cylinder that houses the piston. The transition arm is coupled to the piston to translate between linear motion of the piston and rotation of the rotatable drum. The compensating piston is in fluidic communication with the cylinder and is configured to counteract a force caused by an inlet or an output pressure during operation.
[0005] Implementations may include one or more of the following features. For example, the hydraulic device may include a shaft and a member, such as a plate, mounted on the shaft. The shaft may be connected to the rotatable drum such that the rotatable drum does not move axially along the shaft. The compensating piston then may be configured to counteract the force caused by at least one of the inlet pressure and the output pressure during operation by applying a force to the member. A flanged nut and a spring also may be mounted to the shaft, with the spring between the member and the flanged nut such that the spring applies a force to the flanged nut in the same direction as the force applied to the member by the compensating piston. The member may be mounted on the shaft such that the member moves axially along the shaft. The compensating piston may be configured to counteract the force caused by at least one of the inlet pressure and the output pressure during operation by applying a force to the member such that the member moves axially along the shaft to compress the spring, resulting in an increase in the force applied to the flanged nut by the spring.
[0006] Alternatively, the shaft maybe connected to the rotatable drum such that the rotatable drum moves axially along the shaft. The member, such as a support, may be mounted to the shaft such that the member does not move axially along the shaft. The compensating piston then may be configured to counteract the force caused by at least one of the inlet pressure and the output pressure during operation by applying a force to the member. The compensating piston applying a force to the member may result in a force being applied to the rotatable drum in a direction opposite to the force caused by the inlet or outlet pressure. The hydraulic device may include a U-joint coupled to the member and the transition arm. A spring may be mounted between the member and the rotatable drum such that the spring applies a force to the rotatable drum in the opposite direction of the force caused by the inlet or output pressure during operation.
[0007] The hydraulic device may be a hydraulic motor or a hydraulic pump. The hydraulic device may include a bulkhead that defines an inlet or outlet manifold, a cylinder housing the compensating piston, and a port between the inlet or outlet manifold and the cylinder housing the compensating piston. The port may provide the fluidic communication between the compensating piston and the cylinder defined by the rotatable drum. Alternatively, or additionally, the bulkhead may define a port between the cylinder housing the compensating piston and the cylinder defined by the rotatable drum to provide the fluidic communication.
[0008] The hydraulic device may include a face valve between the bulkhead and the rotatable drum. The compensating piston may be configured to counteract the force caused by at least one of the inlet pressure and the output pressure during operation to maintain a seal between the face valve and the bulkhead or the face valve and the rotatable drum. A spring may be coupled to the compensating piston such that the spring applies a force to the rotatable drum in the opposite direction of the force caused by the inlet or output pressure during operation. The compensating piston may be configured to counteract the force caused by at least one of the inlet pressure and the output pressure during operation by creating a force that acts on the rotatable drum in a direction opposite to the force caused by the inlet or output pressure.
[0009] The hydraulic device may include a non-rotating member coupled to the transition arm. A radial position of the non-rotating member relative to an axis of rotation of the rotatable drum may be adjustable to change an angle between the transition arm and the axis of rotation of the rotatable drum. The transition arm may be coupled to the piston and the non-rotating member such that a change in the angle between the transition arm and the axis of rotation of the rotatable drum changes a stroke of the piston. The non-rotating member may include teeth that mesh with a gear such that rotation of the gear adjusts the radial position of the non-rotating member relative to the axis of rotation of the rotatable drum.
[0010] The hydraulic device may include a piston joint assembly coupling the transition arm to the piston. The piston joint assembly may be configured to reduce centrifugal forces acting on the piston as a result of rotation of the rotatable drum and piston. The piston joint assembly may include a casing that defines a hole through which a portion of the piston extends. The hole may have a diameter larger than the portion of the piston extending through the hole. The portion extending through the hole of the casing may terminate in a head piece. The head piece may have a diameter larger than the hole defined by the casing and the casing may be dimensioned to provide a spacing between an inner surface of the casing and the head piece.
[0011] In another aspect, a method for counteracting a force in a hydraulic device caused by at least one of an inlet pressure and an outlet pressure during operation may include adjusting a counteracting force as at least one of the inlet pressure or the outlet pressure changes during operation.
[0012] In another aspect, a method for counteracting a force in a hydraulic device caused by at least one of an inlet pressure and an outlet pressure may include rotating a drum that defines a cylinder; reciprocating a piston in the cylinder; and communicating a pressure in the cylinder to a compensating piston such that the compensating piston creates a force that counteracts the force caused by at least one of an inlet pressure and an outlet pressure during operation.
[0013] Implementations may include one or more advantages. For example, the compensating piston may be able to produce a variable force to counteract the force cause by the inlet or output pressure. The varying force may increase as the inlet or output pressure increases, and decrease as the inlet or output pressure decreases. This may allow the friction between the between the drum and the face valve and between the face valve and bulkhead to be low at low output or inlet pressures, while increasing to maintain a seal between the drum and the face valve and between the face valve and the bulkhead at higher pressures. This may improve efficiency, particularly when the pump or motor is operating at low inlet or output pressures.
[0014] In addition, the use of a spring may provide an initial force that is appropriate to counteract the force from the pressure during start-up conditions. The initial force from the spring may be designed so as to maintain the seal between the drum and the face valve and between the face valve and bulkhead during low start-up pressure, without being greater than necessary to maintain the seal by completely or partially counteracting the force generated by the low start-up pressure. In this way, friction during start-up may be decreased, which may improve pump efficiency and may reduce wear.
[0015] The details of one or more implementations are set forth in the accompanying drawings and the description below. Other features, objects, and advantages will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
[0016] FIG. 1A illustrates a combination hydraulic motor/pump.
[0017] FIG. 1B is an end view of the combination hydraulic motor/pump taken along line 1 B of FIG. 1A .
[0018] FIG. 2A and 2B show a face valve of the combination hydraulic motor/pump of FIG 1 A and 1 B.
[0019] FIG. 3 is an end view of the valve cylinder of the combination hydraulic motor/pump of FIGS. 1A and 1B .
[0020] FIG. 4 is a side view of the valve cylinder of the combination hydraulic motor/pump of FIGS. 1A and 1B .
[0021] FIG. 5A illustrates a hydraulic assembly with reduced centrifugal force effects.
[0022] FIG. 5B is a cross-sectional view taken along line 5 B of FIG. 5A .
[0023] FIG. 5C is a cross-section taken along line 5 C in FIG. 5A .
[0024] FIG. 5D shows a piston assembly of the hydraulic assembly of FIG. 5A .
[0025] FIG. 5E is a cross-sectional view of a piston assembly taken along line 5 E of FIG. 5C .
[0026] FIG. 5F is a view of the piston assembly and support members taken along line 5 F in FIG. 5C .
[0027] FIG. 6A illustrates a hydraulic assembly.
[0028] FIG. 6B is a cross-sectional view of the hydraulic assembly of FIG. 6A taken along line 6 B of FIG. 6A .
[0029] FIG. 7A illustrates an alternate implementation of the hydraulic assembly of FIGS. 6A and 6B .
[0030] FIG. 7B is a view of a variable pressure mechanism of the hydraulic assembly of FIG. 7A .
[0031] FIG. 7C is a view of an alternate implementation of the variable pressure mechanism of the hydraulic assembly of FIG. 7A .
DETAILED DESCRIPTION
[0032] Referring to FIGS. 1A and 1B , a combination hydraulic motor/pump 30 particularly useful, e.g., in deep well applications, includes a first side 31 that acts as a hydraulic motor and a second side 32 that acts as a hydraulic pump. The motor side 31 is designed to operate with a high pressure/low volume fluid input and directly drives the pump side, which is designed for higher volume/lower pressure fluid output. Motor/pump 30 is placed within a well or borehole and the space between motor/pump 30 and casing 47 of the well is sealed with a seal 1 . Accordingly, when placed below the liquid level of the well or borehole, a low volume/high pressure fluid is pumped into the motor side 31 , which then directly drives the pump side 32 to pump the fluid in the well or borehole to the surface at a lower pressure, but higher volume than the fluid pumped into the motor side 31 .
[0033] Specifically, combination hydraulic motor/pump 30 includes stationary housing parts 2 , 9 , 13 , and 14 that define an open region 35 within motor/pump 30 . Located within open region 35 is a transition arm 22 . Transition arm 22 is mounted on, e.g., a universal joint (U-joint) 23 . For example, U-joint 23 is a cardon type U-joint, however, other types of U-joints can be used. Transition arm 22 includes a nose pin that is coupled to a rotating member 21 via a self-aligning nose pin bearing such that transition arm 21 is at an angle β with respect to assembly axis A. The nose pin is axially fixed within rotating member 21 .
[0034] Piston assemblies 5 (e.g., three piston assemblies 5 ) are mounted circumferentially about transition arm 22 via drive pins coupled to piston joint assemblies 6 , such as, e.g., one of the piston joint assemblies described in FIGS. 14-16, 23-23A or 56-56F in PCT Application WO 03/100231, filed May 27, 2003, incorporated herein by reference in its entirety, or, e.g., the piston joint assembly described below with respect to FIGS. 5C-5E . Piston assemblies 5 include double-ended pistons having a first piston 7 (the drive piston) on one end and a second piston 3 (the pump piston) on the other end. Pistons 7 are received in cylinders 36 a formed in stationary housing part 9 on motor side 31 , while pistons 3 are received in cylinders 36 b formed in stationary housing part 2 on pump side 32 . Pistons 7 are centered in cylinder 36 a by seals 8 such that they do not touch the sides of cylinders 36 a. Similarly, pistons 3 are centered in cylinders 36 b by seals 4 such that they do not touch the sides of cylinders 36 b. In an exemplary implementation, the distance between the end face 43 of pistons 3 and end wall 42 of cylinders 36 a when pistons 3 are at the end of their intake stroke (i.e., when pistons 3 are moving in the direction of arrow D) is the same as the distance between the end face 44 of pistons 7 and the end wall 45 of cylinders 36 a when pistons 7 are at the end of their power stroke (i.e., moving in the direction of arrow C). The area of the end face 43 of pistons 3 , however, is larger than the area of the end face 44 of pistons 7 (for reasons described further below).
[0035] Transition arm 22 is supported on U-joint 23 , which is connected to stationary housing part 2 such that U-joint 23 does not rotate. U-joint 23 acts as a pivot point for transition arm 22 such that linear movement of pistons 3 and 7 results in the nose pin of transition arm 22 moving in a generally circular fashion about assembly axis A. Because the nose pin is connected to rotating member 21 , the circular movement of the nose pin causes the rotating member 21 to rotate about assembly axis A. Rotating member 21 is connected to a shaft 33 , which rotates with rotating member 21 .
[0036] Referring also to FIGS. 2A, 2B , 3 , and 4 , mounted on shaft 33 is a face valve 10 and a valve cylinder 11 that control the flow of fluid in motor half 31 . Face valve 10 and valve cylinder 11 are mounted on shaft 33 such that face valve 10 and valve cylinder 11 rotate with shaft 33 . For instance, shaft 33 has a splined end that mates with splined holes 37 and 40 defined in face valve 10 and valve cylinder 11 , respectively.
[0037] Shaft 33 is attached to valve cylinder 11 via a bolt 18 . Between the bolt head and valve cylinder 11 is a spring washer 19 , such as a Belleville washer. Spring washer 19 provides a force against valve cylinder 11 so that valve cylinder 11 and face plate 10 remain in contact during operation, thereby maintaining a seal between the two to limit the possibility of leakage of the drive fluid.
[0038] Face valve 10 includes an inlet section 38 that is connected to an inlet tube 16 through a port 12 and space 41 in valve cylinder 11 . Inlet tube 16 extends from space 41 in valve cylinder 11 through stationary housing part 14 . Valve cylinder 11 rotates about inlet tube 16 during operation and o-rings 17 seal the area between valve cylinder 11 and inlet tube 16 . Face valve 10 also includes an outlet section 39 connected to a port 20 of valve cylinder 11 . Port 20 is connected to holes 34 located about stationary housing part 13 such that the drive fluid is exhausted from motor side 31 into the well.
[0039] During operation, fluid is delivered from the surface via a low volume/high pressure line to inlet tube 16 and delivered to inlet section 38 via port 12 in valve cylinder 11 . Inlet section 38 is in fluidic contact with some of cylinders 36 a (e.g., two of the cylinders 36 a ) at a time as valve cylinder 11 and face valve 10 rotate. Thus, the fluid from the surface enters the aligned cylinders 36 a and causes the corresponding pistons 7 to move along piston axis P in the direction of arrow C ( FIG. 1A ). The movement of the aligned pistons 7 results in movement of the nose pin of transition arm 22 in a generally circular fashion about assembly axis A, which cause rotating member 21 and shaft 33 to rotate. As a result, face valve 10 and valve cylinder 11 also rotate about assembly axis A, which brings other cylinders 36 a and corresponding pistons 7 into alignment with inlet section 38 , thereby allowing the delivered fluid to cause those pistons 136 a to move along piston axis P in the direction of arrow C.
[0040] For simplicity of illustration, port 12 is shown as aligned with cylinder 36 a in FIG. 1B while drive piston 7 is at the end of its power stroke and getting ready to enter an exhaust stroke. During operation, however, valve cylinder 11 is rotated 90° from the position shown when the stroke of drive piston 7 is at this point. That is, cylinder 36 a is aligned with one of the ends 46 a or 46 b (depending on the direction of rotation) of inlet section 38 .
[0041] At the same time that some of the pistons 7 are moving along piston axis P in the direction of arrow C, the piston(s) 7 not aligned with inlet section 38 are moving along piston axis P in the opposite direction, i.e., in the direction of arrow D. The cylinders 36 a corresponding to the piston(s) 7 moving in the direction of arrow D are aligned with outlet section 39 . Thus, as the pistons 7 aligned with outlet section 39 move in the direction of arrow D, fluid contained in their corresponding cylinders 36 a (which entered those cylinders through inlet section 38 ) is expelled through outlet section 39 to port 20 and out of motor/pump 30 through holes 34 .
[0042] In this manner, motor half 31 acts as a hydraulic motor. Delivery of the drive fluid to inlet tube 16 causes the pistons 7 to reciprocate along piston axis P. The reciprocation of pistons 7 results in pistons 3 also reciprocating along piston axis P in cylinders 36 b.
[0043] Cylinders 36 b are in fluidic communication with inlet ports 28 located on pump half 32 . Inlet ports 28 open to one side of seal 1 such that they are in fluidic communication with the fluid to be pumped. Inlet ports 28 include a check valve 27 (e.g. a poppet valve) that only allows fluid to flow through inlet ports 28 in the direction of arrow D. Consequently, as pistons 3 move in the direction of arrow D, fluid is pulled into inlet ports 28 and cylinders 36 b; however, as pistons 3 move in the direction of arrow C, fluid does not flow out of pump half 32 through inlet ports 28 .
[0044] Instead, the fluid in cylinders 36 b are output via output ports 24 , which are in fluidic communication with inlet ports 28 via a port 26 . Outlet ports 24 are open to the opposite side of seal 1 than inlet ports 28 such that the fluid is pumped towards the top of the well or borehole. The fluid is guided towards the top of the well or borehole by the well casing 47 . Outlet ports 24 also include a check valve 25 that only allows fluid to flow in the direction of arrow D. Consequently, as pistons 3 move in the direction of arrow C, fluid is pumped out of cylinders 36 b, through ports 26 , and out of outlet ports 24 ; however, as pistons 3 move in the direction of arrow D, fluid is not pulled into pump half 32 through outlet ports 24 .
[0045] Accordingly, fluid from the surface entering cylinders 36 a that are aligned with inlet section 38 of face valve 10 causes the corresponding pistons 7 and 3 to move in the direction of arrow C. This results in fluid being pumped out of the corresponding cylinders 36 b through ports 26 and out outlet ports 24 . At the same time, the pistons 7 on the motor half 31 not aligned with inlet section 38 and the corresponding pistons 3 on the pump side 32 are moving in the direction of arrow D. This results in the fluid in the corresponding cylinders 36 a being pumped into outlet section 39 of face valve 10 , through outlet port 20 of valve cylinder 11 , and out of holes 34 , along with fluid in the well or borehole being pulled into the corresponding cylinders 36 b on the pump side 32 via inlet ports 28 .
[0046] Thus, during operation, a high pressure/low volume down line is connected to the inlet port 16 on motor side 31 , and combination hydraulic motor/pump 30 is placed below the liquid level in the well or borehole such that inlet ports 28 on pump side 32 are in fluidic communication with the fluid in the well or borehole to be pumped (the pump fluid). A high pressure/low volume drive fluid is pumped to the inlet tube 16 on motor side 31 via the down line. The drive fluid enters some of cylinders 36 a by port 12 of valve cylinder 11 and inlet section 38 of face valve 10 and cause pistons 7 to move linearly within cylinders 36 a, which causes rotating member 21 and, consequently, face valve 10 and valve cylinder 11 to rotate. As face valve 10 and valve cylinder 11 rotate, the drive fluid causes other of pistons 7 to move linearly within cylinders 36 a, and pistons 136 a begin reciprocating in cylinders 36 a. This expels the drive fluid in cylinders 36 a out through outlet section 39 in face valve 10 , port 20 in valve cylinder 11 , and holes 34 .
[0047] The movements of pistons 7 also directly drive pistons 3 , thereby causing pistons 3 to reciprocate. The reciprocating motion of pistons 3 pumps the fluid in the well or borehole into cylinders 36 b through inlet ports 28 , and out ports 26 to outlet ports 24 . Because the area of the end faces 43 of pistons 3 is greater than the area of end faces 44 of pistons 7 , pumped fluid at a lower pressure than the drive fluid, but a higher volume than the drive fluid, is pumped back up. The ratio of the area of the end faces 43 of pistons 3 to the area of end faces 44 of pistons 7 determines the ratio of the volume pumped to the volume delivered and can be, e.g., in the range of 3:1 to 10:1.
[0048] Ideally, the ratio of volume pump to volume delivered would be exactly equal to the ratio of the area of the end faces 43 of pistons 3 to the area of end faces 44 of pistons 7 . Absent friction and with an incompressible fluid, the product of the pressure times fluid capacity of the drive fluid would be the same as the pumped fluid. The combined area of end faces 43 , in FIGS. 1A and 1B , is three times that of the combined area of end faces 44 . Thus, the volume of drive fluid supplied to motor part 31 through inlet port 16 ideally produces three times the volume of pump fluid out of ports 24 at one-third the pressure. For example, if the drive fluid is supplied at a rate and pressure of 10 gallons per minute and 9,000 PSI respectively, the combined output of output ports 24 is ideally 30 gallons per minute at 3,000 PSI.
[0049] But, since the friction and the volumetric efficiency is unlikely to be zero, this ideal is unlikely to be achieved. However, the efficiency of hydraulic motor/pump 30 can be in the mid-ninety percent range. This is because the force provided by pistons 7 is transferred directly to pistons 3 , without passing through the rotating parts of hydraulic motor/pump 30 , which instead serve simply to control the timing of pistons 7 and 3 so that they are evenly spaced in time for proper motoring and pumping purposes. In addition, pistons 7 and 3 are moving in straight lines and generate little or no side load on cylinders 36 a and 36 b. Consequently, the frictional losses are low.
[0050] Accordingly, for example, if the ratio of the area of end faces 43 to the area of end faces 44 is 3:1 and efficiency is ninety percent, then for every gallon of drive fluid delivered to motor half 110 a, approximately 2.7 gallons of pump fluid would be returned (in addition to the one gallon of drive fluid).
[0051] Combination hydraulic motor/pump 30 advantageously allows the drive fluid to be the same or compatible with the pumped fluid, such that a return hydraulic line is not needed. Rather, both fluids are returned up the well or borehole. For instance, if potable water is being pumped, then high pressure water can be used as the drive fluid. Similarly, if the fluid being pumped is crude oil, then a fluid such as cleaned up crude oil, semi-refined oil, or even water can be used to drive the motor so that the drive fluid and pumped fluid are able to be returned along the same up line. In the event an application requires that the drive fluid and pumped fluid not mix, the combination hydraulic motor/pump 30 can be implemented with a hydraulic return line for the drive fluid.
[0052] The fluid pressure needed to run combination hydraulic motor/pump 30 is generated at the top of the well, for example, by an electric motor or internal combustion engine used to run a hydraulic pump that provides a high pressure fluid flow. The ratio of fluid pressure into the well to the fluid pressure out of the well is roughly the inverse of the respective flow rates into and out of the well, with allowances for losses in the pipes owing to viscosity and other mechanical forces. Because the fluid/power source is located at the top of the well or borehole, it is easily serviced, resulting in low maintenance costs. The power source may be a combination internal combustion engine/hydraulic pump similar to combination hydraulic motor/pump 30 (with motor side 31 implemented as an internal combustion engine, such as is described with respect to FIGS. 32 and 32a in PCT Application WO 03/100231, filed May 27), which provides high energy efficiency and low power costs. Similarly, a combination electric motor/hydraulic pump similar to that described with respect to FIGS. 65 and 67 in PCT Application WO 03/100231, filed May 27, 2003, can be employed.
[0053] Changing the pressure or rate of flow of the drive fluid in the high pressure drive line changes the rate of flow of the pumped fluid in the low pressure return. When a combination engine and hydraulic pump are used as the power source, changing the engine speed varies the rate of flow of the drive fluid. Alternatively, the hydraulic pump portion of the power source can be a variable stroke pump (such as the ones described with respect to FIG. 50 and 54 in PCT Application WO 03/100231, or described below with respect to FIGS. 5A and 5B ), which allows the flow rate to be changed without varying the engine speed. This provides a simple mechanism for controlling the rate of pumping.
[0054] A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made. For example, the flow of fluid can be controlled on pump side 32 through a second face valve whose rotation is synchronized with face valve 10 , instead of through the check valves 28 and 25 . In addition, a variable stroke mechanism can be included in combined motor/pump 30 , such as the ones described with respect to FIG. 50 and 54 in PCT Application WO 03/100231, or described below with respect to FIGS. 5A and 5B . Furthermore, while three double ended pistons and corresponding cylinders have been shown, more or less pistons and cylinders can be used.
[0055] Referring to FIGS. 5A-5C , a hydraulic assembly 500 (e.g., hydraulic pump or motor) designed to reduce misalignments caused by centrifugal forces includes a stationary housing 502 defining a chamber 504 , and a rotating drum 506 located within chamber 504 . Drum 506 is mounted on a shaft 508 . Application of torque to shaft 508 rotates drum 506 about assembly axis A in housing 502 , and rotation of drum 506 causes rotation of shaft 508 . Drum 506 includes a first section 506 a, a second section 506 b, and support members (e.g., cylindrical tie rods) 506 c that connect first section 506 a and second section 506 b so that the first and second sections rotate together (and for other reasons further described below).
[0056] First section 506 a and second section 506 b define an open region 512 between them. Located within open region 512 is a transition arm 514 . Transition arm 514 is mounted to, e.g., a universal joint (U-joint) 516 . For example, U-joint 516 is a cardon type U-joint, however, other types of U-joints can be used. Transition arm 514 includes a nose pin 518 that is coupled to a bearing block 520 via a self-aligning nose pin bearing 558 such that transition arm 514 is at an angle β with respect to assembly axis A. Nose pin 518 is axially fixed within bearing block 520 .
[0057] Bearing block 520 is received in an arced channel 560 defined in housing 502 such that bearing block does not rotate, and includes a gear-toothed surface 562 that mates with a pinion gear 564 within housing 502 . A mechanism (not shown), such as an external knob with a shaft engaged with pinion gear 564 , is used to turn pinion gear 564 . Turning pinion gear 564 causes bearing block 520 to slide in arced channel 560 to and away from assembly axis A, thereby changing the angle β. Changing the angle β changes the piston stroke and, consequently, the motor/pump capacity. This allows an operator to adjust the piston stroke of assembly 500 . In other implementations, other mechanisms of controlling the angle β are employed, such as the mechanisms described with respect to FIG. 50 and 54 in PCT Application WO 03/100231, filed May 27, 2003.
[0058] Transition arm 514 also includes drive pins 522 coupled to piston assemblies 524 (e.g., seven piston assemblies 524 ) via piston joint assemblies 526 , such as, e.g., piston joint assemblies described below with respect to FIGS. 5C-5E or, e.g., the piston joint assemblies described in FIGS. 56-56F in PCT Application WO 03/100231, filed May 27, 2003. Piston assemblies 524 include single ended pistons having a piston 556 on one end. Pistons 556 are received in cylinders 530 formed in first section 506 a.
[0059] During operation as a hydraulic pump, shaft 508 is rotated, causing drum 506 to rotate, which results in pistons 556 and transition arm 514 rotating with drum 506 . Because nose pin 518 is fixed and transition arm 514 is at an angle β with respect to assembly axis A, rotation of drum 506 causes pistons 556 to reciprocate in cylinders 530 along piston axis P. As pistons 556 reciprocate, fluid is pumped from an inlet 582 to an outlet 538 . Inlet 582 connects to an inlet manifold 584 , while outlet 538 connects to an outlet manifold 570 .
[0060] Pump/motor 500 includes a face valve 536 to control the fluid pumping during operation. Face valve 536 allows fluid to be pulled from the inlet 582 through inlet manifold 584 into a cylinder 530 when the cylinder's corresponding piston 556 is on an intake stroke (moving in the direction of arrow F), while directing fluid from a cylinder 530 through outlet manifold 570 to outlet 538 when the cylinder's corresponding piston 556 is on a pump stroke (moving in the direction of arrow G).
[0061] During operation as a hydraulic motor, the operation is reversed. A pressurized stream of fluid is provided to inlet 582 . This fluid causes some of the pistons 556 to move in the direction of arrow F. This movement causes drum 506 and transition arm to 514 to rotate, which causes the other pistons 556 to move in the direction of arrow G. The movement of these pistons expels any drive fluid in their corresponding cylinders 530 out of outlet 538 . As this process continues, pistons 556 reciprocate in cylinders 530 as drum 506 rotates. Rotation of drum 506 causes shaft 508 to rotate.
[0062] Referring to FIGS. 5D-5F , piston joint assemblies 526 include a spherical or cylindrical bearing 540 that is coupled to drive pin 522 . Bearing 540 is seated between bearing pads 542 a and 542 b located in a casing 544 . Casing 544 includes a piston end 544 a and an end 544 b opposite the piston end. A hole 546 is formed in piston end 544 a. In addition, piston end 544 a and bearing pad 542 a define a space 534 therebetween.
[0063] Piston 556 has a circular head 548 that is received in space 534 and abuts against a face of bearing pad 542 a, while piston 556 projects through hole 546 . Circular head 548 has a diameter larger than hole 546 such that circular head 548 can not pass through hole 546 . Hole 546 has a diameter larger than the outer diameter of piston 556 passing through hole 546 . In addition, there is spacing 554 between the inner surface of the sides of casing 544 and circular head 548 . The larger diameter of hole 546 and the spacing 554 between the inner surface of casing 544 and circular head 548 allows casing 544 , bearing 540 , and bearing pads 542 a and 542 b to slide relative to circular head 548 and piston 556 in the direction of arrow E for reasons described further below. The faces of circular head 548 are polished to minimize friction.
[0064] Referring to FIGS. 5B, 5E , and 5 F, each side 544 a, 544 b of casing 544 includes two extensions 550 , each having, e.g. half circle, cutouts 552 that mate with support members 506 c on either side of the piston joint assemblies 526 , as shown in FIG. 5B , so that piston joint assemblies 526 ride along support members 506 c. Support members 506 c are polished and extensions 550 have a low friction surface to reduce friction as piston joint assemblies 526 ride along support members 506 c.
[0065] Support members 506 c, extensions 550 with cutouts 552 , and the sliding of piston 556 relative to casing 544 act to reduce the effects of centrifugal force. During operation as a pump, the rotation of drum 506 and piston assemblies 524 results in transition arm 514 (through drive pins 522 ) driving piston joint assemblies 526 back and forth along piston axis P (i.e., causing piston joint assemblies 526 to reciprocate along piston axis P). Piston joint assembly 526 applies this drive force to piston 556 through circular head 548 . On the pump stroke, this force is applied to circular head 548 by bearing pad 542 a. On the intake stroke, this force is applied to circular head 548 by the inner surface of piston end 544 a of case 544 . Similar forces are applied during operation as a motor.
[0066] The rotation of drum 506 and piston assemblies 524 produces centrifugal force on piston joint assemblies 526 , causing them to move outward (i.e., radially away from assembly axis A). This movement of piston joint assemblies 524 can cause misalignment of pistons 556 in cylinders 530 if the movement also acts on pistons 556 . The attachment of piston joint assemblies 524 to support members 506 c via cutouts 552 reduces the magnitude of this movement by transferring the centrifugal force of the piston joint assemblies 526 to support members 506 c. In addition, the ability of piston 556 to slide relative to piston joint assembly 526 isolates piston 556 from any outward movement of piston joint assembly 526 that does occur. Thus, any movement of piston joint assembly 526 that does occur is prevented from being applied to pistons 556 , particularly if the diameter of hole 546 and spacing 554 are designed such that circular head 548 and piston 556 can slide without contacting casing 544 for the expected amount of movement of piston joint assembly 526 .
[0067] As a result, the centrifugal force acting on pistons 556 is reduced to the centrifugal force generated by the mass of pistons 556 , rather than the centrifugal force generated by the mass of pistons 556 and piston joint assemblies 526 . The mass of pistons 556 can be kept relatively small, in the range of one-sixth to one-eighth of the mass of piston joint assemblies 526 . Consequently, pistons 556 are able to have a closer fit to their respective cylinders 530 because the frictional heating and resulting size change is lower than when the centrifugal force acting on pistons 556 is the result of the mass of pistons 556 and piston joint assemblies 526 . When the centrifugal force acting on pistons 556 is the result of the mass of pistons 556 and piston joint assemblies 526 , pistons 556 experience greater misalignment and, therefore, rubbing against the cylinder sidewalls. This results in frictional heating that increases the size of pistons 556 , which causes a greater surface area of pistons 556 to touch the cylinder sidewalls if not enough spacing is providing between pistons and the cylinder sidewalls.
[0068] A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made. For example, other mechanisms to control fluid flow can be used; for example, poppet valves such as those shown in FIG. 1 can be used. Support members 506 c, extensions 550 with cutouts 552 , and the sliding of piston 556 relative to casing 544 can be implemented in other types of assemblies that use rotating pistons and cylinders. In addition, while seven single ended pistons 556 and corresponding cylinders 530 have been shown, more or less pistons and cylinders can be used and the pistons can be double-ended, rather than single ended, as shown, for example, in the assembly described with respect to FIG. 1 .
[0069] Referring to FIGS. 6A and 6B , a hydraulic assembly 600 (e.g., hydraulic pump or motor) designed to counteract forces that tend to move the face valve 636 away from the rotating drum 606 or bulkhead 684 , similar to pump/motor 500 , includes a stationary housing 602 defining a chamber 604 , and a rotating drum 606 located within chamber 604 . Drum 606 is mounted on a shaft 608 such that drum 606 does not slide along shaft 608 . For example, shaft 608 fits through a hole in drum 608 and a pin is used to prevent sliding and causes drum 606 to rotate with shaft 608 . Alternatively, a hole in drum 606 can be press fit to shaft 608 . Drum 606 includes a first section 606 a, a second section 606 b, and connecting members 606 c that connect first section 606 a and second section 606 b so that the first and second section rotate together.
[0070] First section 606 a and second section 606 b define an open region 612 between them. Located within open region 612 is a transition arm 614 . Transition arm 614 is mounted to, e.g., a universal joint (U-joint) 616 . For example, U-joint 616 is a cardon type U-joint, however, other types of U-joints can be used. Transition arm 614 includes a nose pin 618 that is coupled to a bearing block 620 via a self-aligning nose pin bearing 658 such that transition arm 614 is at an angle β with respect to assembly axis A. Nose pin 618 is axially fixed within bearing block 620 . Bearing block 620 is mounted in an arced channel 660 such that bearing block 620 does not rotate and allows the angle β to be adjusted as described above with respect to FIG. 5A .
[0071] Transition arm 614 also includes drive pins 622 coupled to piston assemblies 624 (e.g., seven piston assemblies 624 ) via piston joint assemblies 626 , such as, e.g., piston joint assemblies described above with respect to FIGS. 5D-5F (and assembly 600 may include support members 506 c ) or, e.g., the piston joint assemblies described in FIGS. 56-56F in PCT Application WO 03/100231, filed May 27, 2003. Piston assemblies 624 include single ended pistons having a piston 656 on one end and a guide rod 628 on the other end. Pistons 656 are received in cylinders 630 formed in first section 606 a. Guide rods 632 are received in a sleeve-bearing 688 held by second section 606 b.
[0072] During operation as a pump, as shaft 608 is rotated, drum 606 rotates, which results in pistons 656 and transition arm 614 rotating with drum 606 . Because nose pin 618 is fixed and transition arm 614 is at an angle β with respect to assembly axis A, rotation of drum 606 causes pistons 656 to reciprocate in cylinders 630 along piston axis P. As pistons 656 reciprocate, fluid is pumped from an inlet (not shown, but similar to inlet 582 ) to an outlet 638 . Pump/motor 600 includes a face valve 636 (like face valve 10 ) to control the fluid pumping during operation. Face valve 636 allows fluid to be pulled from the inlet through an inlet manifold (not shown, but similar to inlet manifold 584 ) when the cylinder's corresponding piston 656 is on an intake stroke (moving in the direction of arrow F), while directing fluid from a cylinder 630 to through outlet manifold 670 to outlet 638 when the cylinder's corresponding piston 656 is on a pump stroke (moving in the direction of arrow G).
[0073] During operation as a hydraulic motor, the operation is reversed. A pressurized stream of fluid is provided to the inlet. This fluid causes some of the pistons 656 to move in the direction of arrow F. This movement causes drum 606 and transition arm to 614 to rotate, which causes the other pistons 656 to move in the direction of arrow G. The movement of these pistons expels any drive fluid in their corresponding cylinders 630 out of outlet 638 . As this process continues, pistons 656 reciprocate in cylinders 630 as drum 606 rotates. Rotation of drum 606 causes shaft 608 to rotate.
[0074] The pressure of the hydraulic fluid through face valve 636 , whether from the inlet when operated as a motor or from outlet 638 and pistons 656 when operated as a pump, causes face valve 636 to separate from drum 606 or bulkhead 684 , which can result in leakage and valve failure. To counteract this force, a variable force mechanism 682 is included. The variable force mechanism 682 includes compensating pistons 662 (e.g., two compensating pistons 662 ) located in cylinders 664 defined by bulkhead 684 , a plate 666 , a washer spring 668 , and a nut 678 with flange 680 . Compensating pistons 662 and cylinders 664 are situated parallel to and on opposite sides of assembly axis A. Cylinders 664 are connected via ports 672 to the inlet or output manifold 670 that leads from face valve 636 to outlet 638 . When assembly 600 is operated as a pump, cylinders 664 are connected to outlet manifold 670 . Conversely, when assembly 600 is operated as a motor, cylinders 664 are connected to the inlet manifold.
[0075] Heads 674 of compensating pistons 662 contact plate 666 . Plate 666 is mounted around shaft 608 such that plate 666 does not rotate when shaft 608 rotates, but plate 666 can slide linearly along assembly axis A. For example, the outer diameter of plate 666 may be sized such that it has a close fit with the inner diameter of casing 602 in the space 686 so that plate 666 is supported and can slide linearly along assembly axis A. Plate 666 then has a hole (not shown) through which shaft 608 passes. The hole's diameter is a sufficient amount so that shaft 608 may pass through a hole in plate 666 without touching plate 666 . A tang (not shown) extends from plate 666 and fits into a groove (not shown) in the inner wall of casing 602 in space 686 to prevent plate 666 from spinning.
[0076] Also mounted on shaft 608 next to plate 666 is a thrust bearing 676 , spring washer 668 , and nut 678 with flange 680 . Nut 678 and spring washer 668 are situated on shaft 608 such that they rotate with shaft 608 , but do not slide along shaft 608 . For example, a portion of shaft 608 is threaded. After spring washer 668 is placed onto shaft 608 , nut 678 is screwed onto the threaded portion. Nut 678 is screwed onto shaft 608 to a position that partially compresses spring 668 , thereby exerting a force in the direction of arrow G on nut 678 through flange 680 .
[0077] In addition, as compensating pistons 662 exert a force on plate 666 (as described below), plate 666 moves in the direction of arrow G. Movement of plate 666 applies the force exerted on plate 666 to spring washer 668 through thrust bearing 676 , which results in spring washer 668 being further compressed, thereby increasing the force exerted in the direction of arrow G on nut 676 through flange 680 . Because drum 606 is mounted on shaft 608 such that drum 606 does not slide along shaft 608 , and nut 678 does not slide along shaft 608 , the force from spring 668 on nut 678 is exerted on drum 606 through shaft 608 , thereby urging drum 606 towards face valve 636 . This force acts to counteract the force in the direction of arrow F caused by the hydraulic pressure.
[0078] When there is no inlet or output pressure (e.g., before pump/motor 600 begins operation), spring 668 provides an initial force on drum 606 in the direction of arrow G because spring 668 is partially compressed as described above. This initial force maintains a seal between drum 606 and face valve 636 , and between face valve 636 and bulkhead 684 , thereby preventing the leakage of fluid when pump/motor 600 begins operating. The initial force exerted by spring 668 depends on the amount spring 668 is initially compressed, which depends on the position nut 678 is mounted on shaft 608 . The amount of the initial force is sufficient to maintain a seal between drum 606 and face valve 636 and between face valve 636 and bulkhead 684 during start-up conditions.
[0079] During operation, a force proportional to the input pressure, when operated as a motor, or output pressure, when operated as a pump, is exerted on drum 606 in the direction of arrow F. This force tends to urge face valve 636 away from bulkhead 684 in the case of a motor, and drum 606 away from face valve 636 in the case of a pump. To compensate for this force, the pressure is communicated from inlet (for a motor) or output manifold 670 (for a pump) to compensating pistons 662 by ports 672 . The pressure causes compensating pistons 662 to move in the direction of arrow G, thereby exerting a force on plate 666 , which is transferred to drum 606 through bearing 676 , spring 668 , nut 678 , and shaft 608 . This compensating force counteracts the force acting on drum 606 and/or face valve 636 in the direction of arrow F so as to maintain the seal between drum 606 and face valve 636 , and between face valve 636 and bulkhead 684 .
[0080] The amount of compensating force exerted by one of the compensating pistons 662 on plate 666 (and hence drum 606 ) is proportional to the input or output pressure times the area of the end face of compensating piston 662 . Thus, as the input or output pressure increases, the force exerted on drum 606 in the direction of arrow F increases, and the compensating force exerted by compensating pistons 662 in the direction of arrow G also increases. The total compensating force exerted on drum 606 depends on the total compensating force exerted by compensating pistons 662 and the spring force of spring 668 . Accordingly, spring 668 , the number of compensating pistons 662 , and the area of the compensating pistons 662 are designed to exert an additional force for a given pressure that, when added to the initial force provided by spring 668 , is sufficient to counteract the force in direction F that results during operation.
[0081] The use of spring 668 to provide an initial force and compensating pistons 662 to provide additional compensating force proportional to the input or output pressure allows the friction between drum 606 and face valve 636 and between face valve 636 and bulkhead 684 to be low at low inlet or output pressures, while increasing to maintain a seal between drum 606 and face valve 636 and between face valve 636 and bulkhead 684 at higher pressures. This improves efficiency when the pump or motor is operating at low input or output pressures and also reduces the friction and wear during start-up conditions.
[0082] Referring to FIGS. 7A and 7B , an alternate implementation of a hydraulic assembly 700 (e.g., hydraulic pump or motor) designed to counteract forces that tend to move the face valve 736 away from the rotating drum 706 or bulkhead 784 , which is designed and operated similar to pump/motor 600 , includes a variable force mechanism 782 having compensating pistons 762 located in cylinders 764 defined in drum 706 . Cylinders 764 are positioned parallel to cylinders 730 and circumferentially spaced about assembly axis A. Cylinders 764 are fluidically connected to cylinders 730 (and, hence, the input or output pressure) by ports 772 . There are, for example, the same number of compensating pistons 762 as there are pistons 756 . However, the same number of compensating pistons 762 as pistons 756 does not need to be used. For instance, for an even number of pistons 756 , half the number of compensating pistons 762 can be used (e.g., 4 compensating pistons 762 for 8 pistons 756 ).
[0083] A first end portion 774 of pistons 762 contact a support portion 780 of U-joint 716 , which is mounted to shaft 708 such that it rotates with, but does not slide along shaft 708 . Furthermore, because U-joint 716 is connected to transition arm 714 , which is connected to bearing block 720 located in an arced channel (not shown in FIG. 7 ), when pistons 762 exert a force on support portion 780 , U-joint 716 does not move linearly along assembly axis A.
[0084] In addition, drum 706 is mounted to shaft 708 such that drum 706 can slide along shaft 708 and rotate with shaft 708 . For example, shaft 708 has a splined end that mates with a splined hole in drum 706 . A spring washer 768 (e.g., a Belleville washer) is mounted on shaft 708 between drum 706 and support portion 780 . Spring washer 768 is partially compressed.
[0085] As with pump/motor 600 , when there is no input or output pressure (e.g., before pump/motor 700 begins operation), spring 768 provides an initial force on drum 706 in the direction of arrow G because spring 768 is partially compressed as described above. This initial force maintains a seal between drum 706 and face valve 736 and between face valve 736 and bulkhead 784 , thereby preventing the leakage of fluid when pump/motor 700 begins operating. The initial force exerted by spring 768 depends on the amount spring 768 is initially compressed.
[0086] During operation, as the pistons are reciprocating, a force proportional to the inlet or output pressure is exerted on drum 706 in the direction of arrow F, which is compensated for by compensating pistons 762 . The inlet or output pressure is communicated from cylinders 730 to compensating pistons 762 by ports 772 . The pressure in cylinders 730 causes a force to be exerted at a second end 774 b of compensating piston 762 , which results in compensating piston 762 applying the force to support portion 780 , causing an equal but opposite force to be exerted on an end wall 764 a of cylinder 764 in the direction of arrow G. Because support portion 780 does not move linearly along assembly axis A, but drum 706 does slide along shaft 708 , the forces cause drum 706 to be urged in the direction of arrow G. The force acting on drum 706 from the pressure counteracts the force acting on drum 706 in the direction of arrow F so as to maintain the seal between drum 706 and face valve 736 .
[0087] The amount of compensating force exerted on drum 706 is proportional to the inlet or output pressure times the cross-sectional area of the compensating piston 762 . Thus, as the inlet or output pressure increases and, consequently, the force exerted on drum 706 in the direction of arrow F increases, the compensating force exerted in the direction of arrow G increases. The total compensating force exerted on drum 706 thus depends on the cross-sectional area of the pistons 762 and the number of pistons 762 . Accordingly, the number of compensating pistons 762 and the cross-sectional area of the compensating pistons 762 are designed to exert an additional force for a given pressure that, when added to the initial force provided by spring 768 , is sufficient to counteract the force in direction F that results during operation.
[0088] As with pump/motor 600 , the use of spring 768 to provide an initial force and compensating pistons 762 to provide additional compensating force proportional to the input or output pressure allows the friction between drum 706 and face valve 736 to be low at low input or output pressures, while increasing to maintain a seal between drum 706 and face valve 736 at higher pressures. This improves efficiency when the pump is operating at low pressures and also reduces the friction and wear during start-up conditions. In addition, the design of pump/motor 700 allows pump/motor 700 to be more compact in design than pump/motor 600 .
[0089] Referring to FIG. 7C , in an alternate implementation of the assembly of FIGS. 7A and 7B , rather than spring washers 768 , an assembly 700 includes springs 784 , such as coil springs, coupled to the compensating pistons 762 , to provide an initial compensating force. Compensating piston 762 includes a pin 762 a at end portion 774 b near port 772 . Pin 762 a has a smaller diameter than the rest of piston 762 . Coil spring 784 is seated in cylinder 764 between an end face 764 a of cylinder 764 and an end face portion 774 d of piston 762 , with pin 762 a of received within coil spring 784 to center coil spring 784 in cylinder 764 .
[0090] Each of the coil springs 784 are partially compressed, which causes springs 784 to exert a force on end face portion 774 d of compensating pistons 762 in the direction of arrow F and an equal but opposite force on an end wall 764 a of cylinder 764 in the direction of arrow G. Because support portion 780 does not move linearly along assembly axis A, but drum 706 does slide along shaft 708 , the forces cause drum 706 to be urged in the direction of arrow G. The compensating force exerted on drum 706 in direction G by springs 784 is sufficient to maintain a seal between drum 706 and face valve 736 and between face valve 736 and bulkhead 784 during start-up conditions, thereby preventing the leakage of fluid when pump/motor 700 begins operating. Then, as described above with respect to FIGS. 7A and 7B , during operation, the compensating pistons 762 result in an additional force that depends on the input or output pressure, which maintains the seal between drum 706 and face valve 736 and between face valve 736 and bulkhead 784 .
[0091] A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made. For example, other mechanisms to control fluid flow can be used, such as poppet valves as described with respect to FIG. 1 . In addition, other numbers of pistons and cylinders can be used, and the pistons can be double ended, rather than single ended, as shown in FIG. 1 .
[0092] Furthermore, elements of one or more implementations described above may be combined, deleted, supplemented, or modified to form further implementations. For example, the variable force mechanisms of FIGS. 6A-6B or 7 A- 7 B may be incorporated into assembly 500 , and supports 506 c and piston joint assemblies 526 may be used in assemblies 600 or 700 . Accordingly, other implementations are within the scope of the following claims.
|
A hydraulic device includes a rotatable drum, at least one piston, a transition arm, and at least one compensating piston. The rotatable drum defines a cylinder that houses the piston. The transition arm is coupled to the piston to translate between linear motion of the piston and rotation of the rotatable drum. The compensating piston is in fluidic communication with the cylinder and is configured to counteract a force caused by an inlet or an output pressure during operation.
| 5
|
[0001] This application is a national stage completion of PCT/EP2006/003514 filed Apr. 18, 2006, which claims priority from German Application Serial No. 10 2005 023 246.9 filed May 20, 2005.
FIELD OF THE INVENTION
[0002] The present invention relates to a method for controlling the driving operation of motor vehicles or other vehicles.
BACKGROUND OF THE INVENTION
[0003] Methods for controlling the driving operation of motor vehicles are known, according to specific driving conditions which are detected by way of rotation sensors and evaluated in a control unit to control ABS, ASC or similar systems. Such rotation sensors provide the number of revolutions but not the corresponding rotational direction. If the rotational direction of the wheels or specific sub-assemblies of the power train is needed, it must be calculated by way of a determination algorithm based on different values in a relatively complex manner.
[0004] with this as a background, it is the object of the present invention to furnish a method for controlling the driving operation of motor vehicles or the like in which a complex determination algorithm for the calculation of the relevant number of revolutions can be ascertained.
DETAILED DESCRIPTION OF THE INVENTION
[0005] Rotation sensors as such are known, but they have so far not been used for controlling the driving operation of motor vehicles. The present invention is based oh the knowledge that the use of rotation sensors not only make complex determination algorithms for the determination of the number of revolutions dispensable, but facilitate additional useful functions for the operation of a motor vehicle.
[0006] Thus, the present invention is based on a method for controlling the driving operation of motor vehicles or the like, for example wheel and/or track vehicles, according to which specific driving conditions are detected by way of rotation sensors that are assigned to individual wheels and/or sub-assemblies in the power train, are evaluated in a control unit and are converted into commands for specific functions of the vehicle or warning signals. In the present description, warning signals are understood to be general optic or acoustic signals as well as visual displays.
[0007] To realize the objective posed, this method additionally provides that rotation sensors are used as rotational direction sensors.
[0008] The present invention takes advantage of the further knowledge that the information about the current rotational direction also implies knowing whether there is rotary motion at all. The information “there is a rotary motion” is usually derived from the information on the number of revolutions. If the number of revolution equals zero, there is not rotary motion. If the number of revolutions is larger than zero (or larger than a defined threshold value), there is rotary motion. When using rotation sensors, this determination whether there is rotary motion or not can be replaced by the determination whether a rotary motion was detected or not.
[0009] When using rotation sensors according to the present invention, functions for which the knowledge whether there is rotation or not is relevant, as well as functions for which the knowledge of the current rotational direction is relevant, can be implemented.
[0010] At this point, some expressions used in the present description should be defined in more detail:
the expression “driving status” describes the motion of the vehicle up to standstill. It thus comprises the statuses “vehicle driving”, “vehicle stopped”, “vehicle driving forward” and “vehicle reversing”; the expression “operating status” describes the motion of individual elements of the vehicle, comprising statuses such as “rotating wheel”, “non-rotating wheel”, “rotating sub-assembly”, etc.; the expression “driving conditions” should be understood as the conditions specified by the driver according to the desired driving scheme, for example “accelerator activated”, “brake not activated”, “switched gear”, etc.; the expression “stop condition” should be understood as the conditions specified by the driver according to the desired stop scheme, for example “brake activated”, “accelerator not activated”, etc.
[0015] According to a variation of the method, it is provided that the current rotational direction of at least one wheel and/or one sub-assembly in the power train is detected and evaluated for the determination of the operating statuses “rotating wheel or sub-assembly” or “non-rotating wheel or sub-assembly”, and/or of the driving statuses “vehicle driving” or “vehicle stopped”. As already explained in the present case, it is not the current rotational direction that is relevant, but the determination whether there is rotary motion or not.
[0016] Taking advantage of these properties, it is provided that on determination of the driving status “driving vehicle” and the simultaneous presence of the specified stop conditions (e.g., a certain brake pressure; accelerator not activated), the brake pressure is increased automatically until reaching the driving status “stopped vehicle” or the emission of a warning signal. This way, the vehicle is either stopped automatically or the driver is alerted so that he may take measures to secure the vehicle and prevent rolling when stopping is desired.
[0017] According to the present invention, the current rotational direction of various driven wheels is detected where, on determination of the operating status, “at least one rotating wheel and at least one non-rotating wheel” and the simultaneous presence of specified driving conditions (e.g., gear engaged; accelerator activated), a traction control system is activated, which redistributes the driving power of the spinning wheel to the fixed wheels in the usual way.
[0018] Similarly, the current rotational direction of various braked wheels can be detected where, on determination of the operating status, “at least one rotating wheel and at least one non-rotating wheel” and the simultaneous presence of specified driving conditions (e.g., gear engaged; brake pedal activated), an anti-locking system is activated, which reduces the brake pressure on the locking wheel in the usual way until it rotates again.
[0019] In a further embodiment of the present invention, the current rotational direction of both wheels of a pair of driven wheels is detected where, on determination of the operating status “at least one rotating wheel and at least one non-rotating wheel” and the simultaneous presence of specified driving conditions (e.g., gear engaged; accelerator activated), a differential lock is automatically connected.
[0020] A further advantageous use of the method of the present invention results for vehicles with a lifting axle and/or raising axle. In this case, it is provided that the current rotational direction of at least one wheel of the lifting axle is detected and that on determination of the operating status “rotating wheel of the lifting axle” as well as the presence of the driving condition “lifted lifting axle” and/or on determination of the operating status “non-rotating wheel of the lifting axle” and the driving status “driving vehicle” as well as the simultaneous presence of the driving condition “lowered lifting axle”, a warning signal is emitted.
[0021] This allows checking whether a lifting axle was actually lifted or lowered. If the sensors on the wheels of the lifting axle indicate that there is no rotary motion, the lifting axle can be assumed to be lifted while driving. The comparison with the nominal condition, that is, with the driving conditions specified by the driver, provides confirmation or information on any malfunction.
[0022] As already mentioned above, there are functions to which the current rotational direction of the wheels or sub-assemblies in the power train are relevant. This is provided by the employed rotation sensors according to the present invention.
[0023] Taking advantage of these properties, a further embodiment according to the present invention provides that the current rotational direction of at least one wheel or one sub-assembly in the power train is detected and evaluated for the determination of a driving status “vehicle driving forward” or “vehicle reversing” and/or “wheel or sub-assembly rotating forward” or “wheel or sub-assembly rotating backward”. This function allows checking whether the motion of the vehicle corresponds to the driving conditions specified by the driver or not. In the latter case, corresponding countermeasures can automatically be started or warning signals be generated.
[0024] Hence, a further refinement of the present invention provides that if there is a specific driving condition (for example, forward gear engaged and/or reverse gear engaged) and a driving status that opposes one of these driving statuses (for example, vehicle reversing and/or vehicle driving forward) is determined, a brake is automatically activated. If the driver of a vehicle selects a forward gear and wants to start the vehicle and a rotation sensor detects the vehicle is rolling backward, a brake that prevents this can be activated. On the contrary, if the vehicle starts rolling in the direction desired by the driver, an activated brake could be released. Rolling down a mountain would be possible this way.
[0025] In contrast to the function described above, a further embodiment of the present invention provides that on determination of a certain driving status (e.g., vehicle driving forward and/or vehicle driving backward) without the presence of a corresponding driving condition (e.g., forward gear engaged and/or reverse gear engaged), a brake is automatically activated. If a driver coasts his vehicle downhill, a brake could be activated that would stop the vehicle as soon as a rotation sensor detects that the vehicle is changing direction.
[0026] When rocking a vehicle free, it is important to detect when a vehicle's motion out of the hole starts rolling in the opposite direction and to react rapidly by switching to the opposite direction or actually contributing to it, According to an embodiment of the present invention, a control function “rocking free” is provided where, on determination of the driving status “vehicle stopped” after “vehicle driving forward”, the forward gear is automatically switched to the reverse gear, and with the driving status “vehicle stopped” after “vehicle reversing” a forward gear is engaged.
[0027] On the other hand, a simplified procedure provides that a control function “rocking free” is provided in which, on determination of the driving status “vehicle stopped” after an active forward motion and/or backward motion, the vehicle clutch is disengaged and on determination of the driving status “vehicle stopped” after a respective passive motion in the opposite direction, the vehicle clutch is again engaged for an active motion phase. The function “rocking free” is preferably discontinued automatically and thus ends when the vehicle has covered a predetermined distance in one direction, that is, does not stop immediately. The expression “active” indicates that there is a drive connection to the engine, whereas the expression “passive” indicates that the vehicle is rolling powerlessly.
[0028] A critical and in some situations difficult maneuver is driving in reverse. Therefore, modern vehicles offer functions that are activated especially in reverse in order to facilitate this and/or make it more uncritical. Such systems are again de-activated on subsequent forward driving.
[0029] The present invention also offers the possibility of automating these functions. Therefore, it is provided that the driving status “vehicle reversing” and/or “vehicle driving forward” is performed automatically for the adjustment of the vehicle relevant to the respective driving direction. Thus, the reverse light, a reverse drive warning signal (e.g., warning lights and/or acoustic signal), a reverse drive camera or the like could be activated in reverse. At present, engaging a reverse gear is generally the necessary condition to be detected by a related sensor. But the cases in which the vehicle is rolled backward without engaging a reverse gear are not included.
[0030] Further functions to facilitate driving in reverse could additionally be implemented, namely, adjusting the rear-view mirror for reverse driving, removing pane blinds and rocking to and fro, folding away and/or retracting parts attached to the bodywork, like spoilers and the like. Upon detection of forward driving, the vehicle could be returned automatically to a status that is appropriate for this driving direction.
[0031] In multi-axle vehicles, it can occur that on a strong steering impact, e.g., when the vehicle is driving forward, at least one wheel rotates backward. By detecting the rotational direction of the vehicle wheels this way, such a situation can easily be identified. According to a further development of the present invention, it is provided that on determination of the driving status “vehicle driving forward” and/or “vehicle reversing” and simultaneous determination of the respective operating status “at least one wheel rotating backward” and/or “at least one wheel rotating forward”, a warning signal is emitted, which calls the driver's attention to the excessively strong steering impact.
[0032] If rotational directions are detected on the wheels when the vehicle is stopped, this may suggest that the driver is changing the steer angle of the stopped vehicle. In this case it is provided that on determination of the driving status “vehicle stopped” and the operating state “at least one wheel rotating”, a warning signal is emitted. Depending on which wheel is rotating in which direction, the steering direction can be derived. If the rotational direction of one wheel changes, the amplitude of the steer angle can be derived. Excessively large steer angles can be excluded in specific operating situations, when the vehicle has to be rocked out of a pothole.
[0033] In modern automatic transmissions, it can occur that, in a transmission comprising 16 gears, the software was inadvertently programmed for a transmission with 12 gears. This may result in the vehicle starts driving in an opposite direction to the selected driving direction. This situation can be identified by way of the rotational direction detection and de-activated with adequate interventions in the control of the power train and/or brakes.
[0034] Furthermore, the parameters of the involved data array of the gearbox control can be changed automatically so that after a one-time occurrence of the situation, the correct gearbox parametrization is always active. Specifically applied, automatic hardware detection can also be implemented this way.
[0035] In a further refinement of the present invention, it is provided for a vehicle with multi-speed automatic gearbox and programmable gear control that the current rotational direction of at least one wheel or one sub-assembly in the power train is detected and compared with the respective nominal rotational direction corresponding to the engaged gear and that on lacking coinciding, a warning signal is emitted.
[0036] In modern automatic gearboxes it is not possible to switch the range change group when a vehicle has exceeded a limit speed while in reverse. This is related to the construction of the range change group synchronization. If a driver lets his vehicle roll backward and accelerates beyond a certain limit speed, the gearbox tries to shift the gear change group. This results in considerable sub-assembly stress. Such or similar situations can be prevented or de-activated by way of the rotational direction detection. The rotational direction detection can thus contribute to the protection of the sub-assemblies.
[0037] Hence, according to a further embodiment of the present invention, for a vehicle with a gearbox arranged in the power train it is provided that the current rotational direction of at least one sub-assembly of the gearbox is detected, and that on shifting, activation or deactivation procedures of the range change groups of the gearbox not corresponding to the detected rotational direction, automatic closure of the range change group shifting is carried out and/or a warning signal is emitted.
[0038] In conventional vehicles, the sub-assemblies in the powertrain of a vehicle (e.g., in the gearbox) do not have rotational direction detection. In this case, a specific rotational direction is derived on the basis of different parameters by way of a determination algorithm. The result of the calculation algorithm can be checked by way of rotational direction detection via rotation sensors. For this purpose, according to a further embodiment of the present invention, the current rotational direction of at least one sub-assembly in the powertrain can be detected and compared with the result of an algorithm for the calculation of the rotational direction.
[0039] According to a further variation of the present invention, the current rotational directions of various sub-assemblies in the power train are detected and compared to one another. The malfunction of a sensor can be determined by comparing the individual signals of several rotation sensors.
[0040] A further embodiment of the present invention provides that the current rotational direction of the gearbox output shaft is detected and compared with the nominal rotational directions at different shifting states of the gearbox. If a position sensor that should detect the position of a gearbox shifting element, that is relevant to the driving direction of the vehicle and hence the rotational direction of the gearbox output shaft fails, the rotational direction detection may show if the corresponding gear has been shifted. If the nominal specification and detected rotational direction match, it should be assumed that the shifting element has switched through. If the nominal specification and rotational direction do not match, a malfunction should be assumed.
[0041] If the position sensor, which detects the position of the gearbox shifting element relevant to the driving direction of the vehicle and hence of the gearbox output shaft, provides a valid, but wrong signal, this would be noticed on rotational direction detection in the power train because the actual rotational direction, the nominal specification and the measured position of the shifting element would not match. Thus, validation of the function of the gearbox position sensor can be achieved.
[0042] The use of rotation sensors in the power train also allows a rotational direction calculation algorithm to be completely dispensed with.
[0043] Modern rail vehicles can, in general, be equally used in both driving directions. As such rail vehicles carry a white light at the front in the direction of travel and a red light at the rear end, the lights have to be switched on inversion of the direction of travel. For this purpose, a further embodiment for such rail vehicles, according to the present invention, provides that on determination of the driving state “vehicle traveling in a first forward direction” and/or “vehicle traveling in a second forward direction”, train lights corresponding to one of the travel directions is respectively switched automatically.
[0044] A further special use of the core of the present invention is possible to refuse collection vehicles or the like with a footboard for the riding workers. In order not to put them at risk, there is a regulation stating that driving in reverse is not allowed if the footboard is occupied. This protection function against reverse driving is currently dependent on engaging the reverse gear. Rolling in reverse in such vehicles with occupied footboard could be detected and prevented by way of rotational direction detection. For this purpose, a further refinement for refuse collection vehicles or the like with a footboard for riding workers, according to the present invention, provides that on determination of the driving status “vehicle driving and/or rolling backward”, a reverse driving lock is automatically activated and/or a warning signal emitted when the footboard is occupied.
|
A method for controlling the driving operation of motor vehicles in which specific driving conditions are detected by rotational sensors located at individual wheels and/or sub-assemblies in the power train, and are then evaluated in a control unit and converted into control commands for specific functions of the vehicle or into warning signals. ABS, ASC or EBS systems as well as automatic gearboxes are controlled in this manner. Rotational sensors detect the current rotational direction and additionally determine of the presence of a rotary motion. The rotation sensors permit numerous functions of the vehicle to be controlled in a simple manner and with the aid of various parameters obviate the need for the calculation of the rotational direction by way of the determination algorithms.
| 1
|
BACKGROUND
[0001] 1. Field of Invention
[0002] This invention relates to the field of snowplow with articulated blades, provided with fortified knives inserted and maintained in place into the blades to offer a greater durability during passages over altered roads in frequent uses. This patent proposes a modification to the blade to increase the resistance by providing a complete system of inserted wear knives replacing the known thin carbides and by also offering a device preventing blades from breaking up, by providing a skate mean for the sake of a fluid deflection of snow.
[0003] This invention belongs to the maintenance of the road system particularly the ones using snowplow, and particularly snowplow provided with articulated blades for scraping the snow by means of blades containing fortified wear knives inserted and locked in place by particular means of retention inside. This patent proposes a modification to the blade to increase the durability and the quality of the snow removal and to diminish the use of salt and sand used for removing ice on roads particularly on altered and damaged roads revealing difficulty in cleaning.
[0004] Furthermore, the invention comprises a modification to a blade by offering a mean of skate gauging the depth of the blade movement permitting the articulated blade to follow the irregularities of altered roads.
[0005] 2. Description of the Prior Art
[0006] The present invention is an improvement over an invention from one of the present inventors so being utilized by other articulated snowplow scraper comprising some of the present characteristics: namely an articulated. The prior patent from one of the present inventors refers to the following:
CA 2,423,830; Articulated scraper blade system.
[0008] Other searches of the prior art revealed the following patents:
U.S. Pat. No. 2,282,298; Vogel, 1942 CA 2,242,278; Daniels, 1998 U.S. Pat. No. 5,865,997; Isaacs, 1997 U.S. Pat. No. 3,906,577; Brucher, 1973 FR 2,539,438; Kueper, 1984 U.S. Pat. No. 4,258,797; Mckenzie, 1978
[0015] The patents seen do not offer the same particularities as the present invention: wherein an articulated blade system provided with fortified knives and a skate mean increasing the durability and preventing the blade break during frequent passages on altered roads fulfilled with holes.
OBJECTIVES
[0016] In use the removal of snow on the road system is effectuated by means of a snowplow provided with at least a shovel comprising a scraper blade and sometimes articulated blades which the invention refers to. The articulated blades can be provided with fortified inserted knives increasing resistance according to their hardness, determined by the material used in their conception. The articulated blades move slightly vertically to adapt to the irregularities of altered roads by means of shock absorbers. The pressure of the snow and the abrasion against the road surface increase correspondently while the snowplow moves and removes the snow. The snow removal depends then on the quality of the material used in the conception, particularly in the blade quality and the assembly of the components. The advantages of the present invention lie in the method of inserting wear knives between two blades, so to lock the knives in place, to prolong the life expectancy and the durability of the blades. These knives being made of a more resistant alloy composition than the blades themselves limit and slow down the wear. The knives endorse the wear, when positioned between blades, touching the ground at the same level as the blades themselves. Furthermore, comparatively to the prior invention a thickened conception of the blades and the knives replacing the prior thin carbide contribute equally to increase a durability of the device. The inserted knives in the blades are maintained in place by means of retention as notches or catches and hems similar to small excrescences and a side retaining plate to prevent the release of the knives from their locked position in the blades and limiting their movement. As well, another important modification intervenes by incorporating means for preventing the breaking up of the blade, by installing skate means at an attack corner being more exposed slightly at the front, during passages over declivities, avoiding the blade digging a the road way and letting slide the blade following irregularities of the same road ways. The articulated blades are moved vertically according to the rolling of the road by means of shock absorbers disposed on each blade and mounted on a shovel by attach means. The sliding of the blades procured by means of a skate preventing the digging of the blades into the road is preferably molded at the attack corner of each blade but could be placed in another location on the blade or could be added to the blade as a separate piece.
[0017] This device is casual but nevertheless not essential and does not limit the invention; the blades provided with fortified knives could be used without the intake of the shock absorbers neither the skate means but only used by itself: the fortified knives inserted into the blades.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present invention will be further understood from the following description with reference to the drawings in which:
[0019] FIG. 1 is a side view of the device in action.
[0020] FIG. 2A is a side view of the blade.
[0021] FIG. 2B is a side view of the knife.
[0022] FIG. 3A shows a perspective of the blade.
[0023] FIG. 3B shows a perspective of the knife.
[0024] FIG. 3C shows a perspective of the plate.
[0025] FIG. 3D shows a perspective of the blade support.
[0026] FIG. 4 is a bottom view of the blade showing the inside.
[0027] FIG. 5 is a view of the prior art showing a snowplow.
[0028] FIG. 6A-6B are views of the prior art showing a shovel.
[0029] FIG. 7A is a view of the prior art seen from the back.
[0030] FIG. 7B is a view of the prior art seen from the front.
[0031] FIG. 8A is a view of FIG. 7 .A the rear being in upward position.
[0032] FIG. 8B . is a view of FIG. 7 .A the rear being in downward position.
[0033] FIG. 9 is an exploded view of the prior art showing the device.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0034] Preferred embodiments of the invention are illustrated in the figures wherein the same numbers identify the same characterizing elements.
[0035] FIG. 1 , shows a snowplow shovel 105 wherein is fixed a shovel plate 104 provided with a front support 107 and with a rear support 109 ; in between is inserted an articulated blade 20 held by an attach 80 fixed to the supports 107 - 109 and to the shovel plate 104 . One sees the blade overhung by a shock absorber 40 permitting a slightly vertical movement, the shock absorber being held by a seat 110 . One sees also the blade resembling a hand 21 having two twin blades 23 and an inclined part 29 . The twin blades integrate a wear knife 22 comprising a rear hem 24 and a front hem 25 fixing the knives into the blade at a front notch 125 of FIG. 2A opposite the front hem and at a rear notch 124 of FIG. 2A opposite the rear hem; the knife comprises also an excess 29 . The blade comprises a front inferior face 128 and a skate 129 meant to help the following of irregularities of the road while the blade is pushed downward by the shock absorber. The blades and the knives touch the road 108 to remove the snow 106 .
[0036] FIG. 2A shows a blade 20 comprising a front superior face 126 , an inclined front face 127 , a front inferior face 128 , a skate 129 , a blade top 130 , a rear superior face 131 , an inclined rear face 132 , a rear inferior face 133 and a blade bottom 136 . The blade comprises also an interior 135 serving to insert the wear knife 22 of FIG. 2B , a front notch 125 and a rear notch 124 retain the wear knife of the following figure.
[0037] FIG. 2B shows a wear knife 22 comprising a knife front 32 , a knife back 30 , a knife foot 34 , and a knife head 27 , a front hem 25 and a rear hem 24 ; both serving to retain the knives for they are inserted in the two notches of the blade.
[0038] FIG. 2C shows a shovel plate 104 , a blade spring hand 48 , a maximal ark 50 and a minimal ark 51 .
[0039] FIG. 2D shows a blade spring 46 .
[0040] FIG. 3A shows a blade 20 comprising holes 44 permitting the slightly vertical movement of the blade, one sees also a shock absorber axes 42 , the blade interior 135 and the skate 129 on a blade attack corner 139 .
[0041] FIG. 3B shows a rear knife 22 .
[0042] FIG. 3C shows a retaining plate 36 meant to lock in place the knife in the blade interior so to seal tight the aperture of the blade interior once the knives are inserted.
[0043] FIG. 3D shows a front support 107 an a rear support 109 positioned on each side of the blades for maintaining the blades in place against the snowplow plate 104 shown in FIG. 1 , by attach means 80 and support attach 82 .
[0044] FIG. 4 shows a blade 20 comprising a blade interior 135 and a knife separator 137 .
[0045] FIG. 5 shows a snowplow 200 provided with an articulated blade device 20 .
[0046] FIG. 6A-6B shows a snowplow shovel 105 and an articulated blade device 20 , provided with a shock absorber 40 and attach means 80 .
[0047] FIG. 7A-7B shows an articulated blade device 20 provided with a shock absorber 40 and a shock absorber seat 110 , furnished also of holes 44 which pass attaches 80 .
[0048] FIG. 8A-8B shows in use the vertical movement of the articulated blade 20 in its upward and downward positions, in the upward position the spring being compressed.
[0049] FIG. 9 shows an embodiment comprising the preferred components mentioned above.
SUMMARY
[0050] A snowplow shovel 105 provided with at least a blade 20 comprising; at least a hand 21 in U, comprising a blade interior 135 creating twin blades 23 , 23 ′ and an adapted part 140 to the shovel, at least a wear knife 22 fortified, inserted in the interior blade 135 , means of retention of the knives to the blades 23 in a way so the knives take preferably the wear instead of the blades.
[0051] The blade 20 is articulated and the means of retention comprise; at least means of notching 125 , 124 , in a hand 21 , the knife comprises means of hem 25 , 24 meant to insert and lock in place the knife correspondingly to the blade interior.
[0052] The articulated blade may have an attack corner 139 comprising at least a skate 129 .
[0053] A snowplow shovel comprises at least one articulated blade 20 having a hand in U 21 moving along a shock absorber 40 on an inclined part 28 following the irregularities of the road to clean, the shock absorber being either hydraulic, mechanical or pneumatic; the hand in U comprises at least a knife 22 blade comprising support means 107 , 109 , and means of at least an attach 80 to the snowplow shovel 105 or to snowplow plate ( 104 ) mounted on the snowplow.
[0054] In the articulated blade the blade interior is of at least ¼″ thick and up. The knife is at least of ¼″ thick and up and is inserted into the blade, knife could be of infinite sizes as long as it corresponds to the size of the blade interior. The blade is closed once the knife is inserted by means of a plate. The blade comprises a shock absorber which permits a slight vertical movement, slightly inclined to follow the irregularities of the road to clean.
[0055] The shock absorber may be of various types, hydraulic, mechanical and pneumatic.
[0056] A method to improve the durability of snowplows provided with at least a blade and a wear knife, the method comporting at least the following step:
[0057] Create at least an open interior 135 into a blade opposite a wear knife to let it enter and then lock it in place by retention means, the blade grabbing the knife as a hand.
[0058] A snowplow shovel 105 provided with at least a blade, the blade being provided with a front inferior face 128 disposed beyond a front superior face 126 on which is positioned a front support 107 producing a thickness differential 39 generating snow deflection.
[0059] The blade 20 has a thickness differential 39 of a ¼″ to ½″.
[0060] The blade has an excess 29 of 0 to ¼″.
[0061] In a snowplow shovel 105 a shock absorber 40 is a leaf spring 46 placed longitudinally on an inclined plane 28 , the hand in U comprising oppositely a U adapted to insert a knife, a second U meant to act as a sheath to receive a shovel plate 104 .
[0062] An adapted part 140 has an I shape 141 , support means 109 , 107 being exposed externally to the I. The I may be disposed in continuation along the blades 23 , 23 ′ defining the hand 21 as an L shape. The adapted part 140 may have a H shape 142 , a shovel plate 104 being inserted into the H shape 142 , the H shape being the result of a reversed U attach to the wear knife 22 and of a straight U attach to the shovel plate 104 superposed to the reversed U.
[0063] It is well accepted that the embodiment of the present invention which was described above, in reference to the matched drawings, was given indicatively and certainly not limitative, and that modifications and adaptations could be brought without moving away from the object of the present invention. Other embodiments are possible and limited only by the scope of the appended claims.
LEGEND
[0000]
20 —Articulated blade
21 —Hand
22 —Wear knife
23 —Twins blades
24 —Rear hem
25 —Front hem
27 —Knife head
28 —Inclined part
29 —Excess
30 —Knife back
32 —Knife front
34 —Knife foot
36 —Retaining plate
38 —Blade point
39 —Thickness differential
40 —Shock absorber
41 —Compressed spring
42 —Shock absorber axis
44 —Holes
46 —Blades springs
48 —Blades springs end
50 —Maximum ark
51 —Minimum ark
80 —Attach
82 —Attach support
104 'Shovel plate
105 —Snowplow shovel
106 —Snow
107 —Front support
108 —Road
109 —Rear support
110 —Shock absorber seat
124 —Rear notch
125 —Front notch
126 —Front superior face
127 —Inclined front face
128 —Front inferior face
129 —Skate
130 —Blade top
131 —Rear superior face
132 —Inclined rear face
133 —Rear inferior face
135 —Blade interior
136 —Blade bottom
137 —Knife separator
139 —Blade attack corner
140 —Adapted part
141 —Straight I
142 —Reversed U
200 —Snowplow
|
The present invention relates to snowplow ( 200 ) systems provided with a shovel ( 105 ) utilized generally for scraping snow ( 106 ). Articulated blades ( 20 ), resembling a hand ( 21 ) having a Y or a H shape, wherein wear knives ( 22 ) are inserted and locked in place between twin blades ( 23 ), by particular means of retention, permitting to increase the longevity of the blades during frequent passages over altered roads. The blades are provided also with a skate ( 129 ) system at an attack corner ( 139 ) preventing the breaking of the blade and allowing the blade to follow the irregularities of the road. The blades are installed lengthwise along the snowplow.
| 4
|
CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERAL SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
FIELD OF THE INVENTION
The present invention relates to the allocation and usage of processor resources in the performance of processing tasks that have time-varying changes in resource requirements. More specifically, the present invention concerns monitoring the processor resources and determining or estimating the current needs for these resources so that they may be allocated by the processor in an optimally efficient way, no matter what kind of event may happen in the future.
BACKGROUND OF THE INVENTION
A software developer has a limited number of resources to allocate to a processor for use in performing one or more executable functions. These resources may include the memory, processing speed, millions of instructions per second (MIPS), processing time, etc., that can be allocated to one or more functions or multiple states of a function. Because of the limited processor resources, a programmer must attempt to write programming that most efficiently utilizes the resources of the processor.
Another concern for the programmer is the dynamically varying usage of the resources over time. In a real-time embedded system, the signal input characteristics determine which functions will run. Therefore, resource consumption depends on the signal input. Also, adaptive algorithms change the mode of task execution in accordance with the signal environment and the achieved performance, thereby changing the amount of resource consumption. Unfortunately, programmers do not have the benefit of real-time information indicating the dynamic usage of processor resources, when designing and implementing a program function. For example, determining the dynamic utilization of the MIPS resource by a previously known method requires that the software function toggle an output pin of the processor each time the function begins and finishes.
Existing methods for minimizing a processor's performance degradation include time slicing and background processing. For example, when the available memory capacity of a digital signal processor (DSP) is nearly used up or overloaded, processing operations become prioritized. Prioritizing the operations allows those having a high priority to be performed in the foreground and lower priority operations performed in the background. Channels are allocated MIPS for calculations whether the channel uses the MIPS or not.
SUMMARY OF THE INVENTION
The invention relates to a resource management agent (Agent) used to manage resources in a processor. This Agent serves to monitor, determine, and control resource consumption. Real-time resource management within a processor allows far more tasks to be performed in a particular time period. For example, such resource management used with a communication processor may increase the number of communication channels that may be supported simultaneously by a digital signal processor.
The resource management Agent controls the allocation of processing resources assigned to discrete parts of a decomposed algorithm, when these parts are capable of being managed (i.e., turned on and off) by the Agent. In other words, the Agent dynamically reassigns processing resources so that they are efficiently used to satisfy the time-varying requirements of the decomposed algorithm parts. Resources are assigned to parts of the algorithm as they are needed. The amount of resource used by a part of the algorithm is estimated by the Agent, based on the current mode of execution.
A preferred embodiment of the above-described invention relates to a method of allocating the processor MIPS to tasks in a queue 20 waiting to be executed. This method includes the steps of:
(1) determining the number of processor MIPS available to be assigned; (2) determining an estimate of the number of MIPS needed for each task waiting in the queue to execute at a maximum intended speed for the processor; and (3) allocating the available MIPS to the tasks based on a hierarchical priority scheme, where the priorities are based on environmental conditions and the achieved performance.
To control peak MIPS consumption, the Agent stores an estimate of peak MIPS usage by specific software functions locally and updates the estimate whenever the state of the function changes. The estimates are subsequently used in a queuing scheme to determine how many and which of the executing software instances may enable the functions available to them, without exceeding a maximum resource threshold. When an algorithm is broken into separate parts and the parts are manageable such that they can be turned on and off, the Agent controls the way processing resources are used by the algorithm. Processor resources are applied where they are needed and are most effectively used.
Prior to managing processing resources, the agent determines the resource usage of each part of an algorithm. Based on internal information passed from the algorithm to the Agent, external resource allocation limits of the software and processor design, environmental conditions, and achieved performance, the Agent distributes processing resources to the parts of an algorithm that have the greatest need while taking resources from parts that can operate with less resource allocation or no allocation at all. As opposed to allocating a certain amount of resources to certain tasks, the Agent is dynamic and can reallocate processing resources to parts of algorithms as they need more processing power and reduce the allocation when the processing can be reduced.
The Agent has alarms set at high and low resource usage thresholds. When the processor's resource is running low or completely allocated and another part of the algorithm requires the resource, the Agent analyzes the subroutines within the algorithm and the input channels to prioritize the allocation of the resource among the competing algorithm parts, based on the environmental conditions and achieved performance. Lower prioritized resource allocations are redirected to the parts of the algorithm that have greater priority. Even if all channels of a processor require a large allocation of the resource simultaneously, the Agent limits the consumption of the resource through graceful degradation of performance. The degradation does not cause the processor to lose information or cause the processor to crash. Some compromise in software performance may occur to the user but is corrected as the Agent frees and reallocates the resource on a dynamic basis.
The Agent is similar to a flow control. It directs more resource to modules and channels that have the most instant resource needs while removing the resource from those modules that have an over-allocation of the resource. The Agent can dynamically update scheduling priorities based on various performance measures for the algorithms it controls. The Agent uses both internal and external controls. Each module contains an estimate of its resource needs and supports the ability to have its resource consumption reduced by the processor. The external controls slow down all processing or perform performance-degrading reallocation of resources when a greater amount of the resource is needed by an algorithm than is available at that time.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are discussed hereinafter in reference to the drawings, in which:
FIG. 1 —illustrates a set of software processes operating for the corresponding set of active instances;
FIG. 2 —illustrates a communication processor interfaced with a plurality of communication channels through its communication ports; and
FIG. 3 —illustrates a representative round robin allocation of a resource to the functions of four concurrently executing instances.
FIG. 4 —illustrates a representative block diagram of an apparatus used to measure the amount of time the processor actually uses to execute a function, as the function is applied to a particular instance and time period.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to FIG. 2 , a communication processor 20 is interfaced with a plurality of communication channels 22 through its communication ports 21 . Each of the communication channels 22 is capable of conveying an analog signal between the communication processor 20 and a channel terminating device. Upon receipt of an analog signal, the communication processor 20 creates a digital representation of the analog signal using numerous digital signal processing functions. Each channel port 21 is continuously monitored by the communication processor 20 to determine when a channel link has been established or extinguished on the communication channels 22 . While a channel link exists, the communication processor 20 assigns its resources to functions that digitize and improve the digital representation of the analog signal. The assigned resources may be MIPS, memory, and other resources of the communication processor 20 .
Referring now to FIG. 1 , a software process 1 – 3 is executed by the communication processor 20 for each instance of a channel link. The instance is created when the link is established and extinguished when the link terminates. FIG. 1 illustrates a set of software processes 1 – 3 operating for the corresponding set of active instances identified by the instance index pointer j. The instances illustrated are those identified by the instance index values of j={1, 2, . . . , m}.
Each software process 1 – 3 operates in the same manner. Therefore, for simplicity, the invention will be described in reference to only one instance of the software process and this description will apply equally well to every other instance of the software process. Moreover, each software process 1 – 3 completes its execution within a period of time t. Though the software process 1 is completed in the time period t, it is serially repeated for each incremental period of time that the instance remains active. The time period t is minimally bounded the amount of time required to completely execute any one of the processing functions operating on the channel link instance. It may be a uniform or varying period, but is assumed to be a uniform period for the purpose of describing the invention. The processing functions are discrete parts of a decomposed algorithm that may be executed independently of other parts of the algorithm.
After the software process 1 begins, as indicated by reference numeral 4 , two index pointers, j and k, are initialized 5 . The instance index pointer j is set to point to the next unused instance value available in the instance index. A function index pointer k is initialized to point to the first value in the index of processing functions that may be executed by the software process in connection with the channel link instance. For the first instance of a channel link, the instance index pointer j is given a value of 1, as indicated by reference numeral 5 . Similarly, the instance index pointer j is given a value of 2, as indicated by reference numeral 18 , for the second instance of a channel link and a value of m for the m th instance, as indicated by reference numeral 19 .
For each time period t, the communication processor 20 determines the number of instances in existence. The processor 20 makes a determination of the amount of resources that each instance needs to execute the functions that are appropriately performed on the instance in its present state. If adequate resources are available to perform the appropriate functions on every existing instance, then these resources are distributed accordingly. However, if inadequate resources are available, then the communication processor 20 must prioritize the allocation of resources to the pending functions of each instance, based on the environmental conditions and achieved performance. The allocation is implemented such that some functions of an instance may be executed and others may not. Those that are executed receive processor 20 resources for their execution. Each of the functions within the process may be assigned a separate priority within the hierarchical priority scheme. Similarly, each instance of each function may be assigned a separate priority within the hierarchical priority scheme, based on the environmental conditions and achieved performance.
The amount of a resource allocated by the processor 20 to execute the pending functions of an instance, for the current time period, may be expressed by the equation:
R j = m 0 + ∑ k = 1 N a jk × f k ( e n v i r o n m e n t a l i n p u t s j , a c h i e v e d p e r f o r m a n c e j )
where,
R j =the amount of a resource allocated to the j th instance;
N=the number of pending functions for the j th instance;
m 0 =the amount of a resource required to execute the background processing of the j th instance, excluding the resource allocated to the pending functions of the j th instance;
f k (environmental-inputs j , achieved-performance j )=the amount of a resource required to execute the k th pending function, based upon the current state of the environmental inputs and the achieved performance of the j th instance;
a jk =0, if no resource is to be allocated to the k th pending function of the j th instance; and
a jk =1, if resource is to be allocated to the k th pending function of the j th instance.
The amount of resource required by the k th function, f k , in the j th instance is variable and depends upon the state conditions of the j th channel link. The state conditions vary in accordance with the environmental inputs of the channel link and its achieved performance, during the current time period t. Priorities are assigned to the pending functions based on the environmental inputs of the channels, the achieved performance of the channels, and the amount of resources recently consumed by the active channel instances. The assignment of priorities to the k pending functions of the j instances may be expressed by the equations:
p jk =g k (environmental inputs j , achieved performance j ,recently consumed resource j )
where
0≦p jk ≦1;
and,
p jk =the priority assigned to the k th function of the j th instance; and
g k =is a function that assigns a priority to the k th function of the j th instance based on the environmental inputs of the j th channel instance, achieved performance of the j th channel instance, and the amount of resource recently consumed by the j th instance.
To achieve the prioritized implementation of a set of functions, f k , in the j th instance, the communication processor 20 assigns a binary value of either zero or one to the a jk of each k th pending function of the j th instance. Reference numeral 6 identifies the point in the process flow 1 where the value assigned to the a jk associated with the first pending function of the j th instance is evaluated to determine whether this function will be executed in the current time period. If the value of a jk is zero, the function will not be executed in the current time period t and the process flow 1 will continue with the next step of the process, identified by reference numeral 8 . If the value of a jk is one, then the first function will be executed in the current time period, as indicated by reference numeral 7 and the process flow 1 will continue with the step identified by reference numeral 8 .
Next, the function index pointer is incremented by a value of one to point to the next function in the index, as indicated by reference numeral 8 . Again, the process flow 1 evaluates the value assigned to a jk for the k th pending function of the j th instance, as indicated by reference numeral 9 . In this case, if the value of a jk associated with the second pending function of the first instance is one, the second function for this instance will be executed in the current time period, as indicated by reference numeral 10 . If the value of a jk is zero in this instance, then the second function will not be executed in the current time period and the process flow continues at the step identified by reference numeral 11 . Similarly, the process flow continues at the step identified by reference numeral 11 after the second function is executed.
Reference numerals 11 – 13 identify the steps of the process flow 1 where the function index pointer is incremented, the value assigned to a jk for the third pending function of the j th instance is evaluated, and this third function is executed in the current time period, if the value of a jk is one for the indexed values of j and k. This process of incrementing k, evaluating a jk , and executing the k th function of the j th instance, for the indexed values, is repeated until it has been applied to all of the N functions of the j th instance, as indicated by reference numerals 14 – 16 . Thereafter, the process flow 1 for the j th instance, of the current time period, is terminated, as indicated by reference numeral 17 .
Referring now to FIG. 3 , imagine, for the purpose of describing the invention, that a separate communication link is received on each of four communication ports 21 of the processor 20 . Each communication link creates a separate instance for the processor 20 to execute for every period t throughout the duration of the communication link. These instances are identified as instance one 30 , instance two 31 , instance three 32 , and instance four 33 . Each instance 30 – 34 has two functions, f 1 34 and f 2 35 , that may be applied to its respective communication link. The horizontal axis of FIG. 3 has been sub-divided into 7 distinct time periods t 0 –t 6 36 – 42 , respectively. For each time period, the processor 20 assigns a value of zero or one to the a jk associated with the functions of each instance.
For the purpose of describing FIG. 3 , assume that each function uses a fixed amount of a particular resource and the resource of concern is the millions of instructions per second (MIPS) that a function needs to execute in an instance. Further assume that the communication processor 20 has a maximum of 100 MIPS to allocate, all of the processor MIPS may be allocated to the processing functions f 1 and f 2 , and the functions require the following numbers of MIPS: f 1 =25 MIPS and f 2 =50 MIPS. Though all four instances of the communication links need to be acted upon by the processing functions, there are insufficient MIPS for the functions f 1 34 and f 2 35 to execute on each instance 30 – 33 , in a single time period. Therefore, a round-robin scheme may be used to apply the two functions 34 and 35 to each of the instances 30 – 33 equivalently. In the case of a round-robin scheme, all of the priorities p jk for the pending functions are equal and remain fixed.
In general, the number instances to which a function may be applied is given by the equation:
∑ j = 1 C a jk = C 0 k ≤ C
where:
C is the number of instances (i.e., communication links); and C 0k is the maximum number of instances to which the k th function may be applied, during a single time period t, and identifies the maximum number of slots for the k th function.
Referring again to FIG. 3 , a 11 , a 12 , and a 21 have been assigned a value of one by the processor 20 and all other a jk for the first time period, t 0 36 , have assigned a value of zero. Since each instance of function f 1 34 consumes 25 MIPS and each instance of function f 2 35 consumes 50 MIPS, the 100 MIPS available to the processor 20 have been allocated. In the illustrated case, the maximum number of slots, C 0k , available to function f 1 34 is one and the number available to function f 2 35 is two, for each time period t.
No further prioritization of the functions f 1 34 and f 2 35 , within the four instances, is provided in the example of FIG. 3 . The processor 20 simply provides the MIPS resources to each instance in a round-robin fashion over multiple time periods t. This may be seen by the diagonal movement of the values assigned to the a jk as time progresses from t 0 to t 6 . Notice the value assigned to the a jk for both functions of the first instance, in time period t 0 , moves progressively to the a jk of the two functions assigned to the other instances with each incremental time period. The value of a jk in the tabular cell position identified by reference numeral 43 , in period t 0 , moves through the matrix of a jk in the manner tabulated in Table 1.
TABLE 1 Item Period a jk Referenced Cell 1 t 0 a 11 43 2 t 1 a 21 45 3 t 2 a 31 47 4 t 3 a 41 49 5 t 4 a 11 51 6 t 5 a 21 53 7 t 6 a 31 55
Similarly, the value of a jk in the tabular cell position identified by reference numeral 44 , in period t 0 , moves through the matrix of a jk in the manner tabulated in Table 2.
TABLE 2
Item
Period
a jk
Referenced Cell
1
t 0
a 12
44
2
t 1
a 22
46
3
t 2
a 32
48
4
t 3
a 42
50
5
t 4
a 12
52
6
t 5
a 22
54
7
t 6
a 32
56
Although the estimated amount of a resource needed to execute a function may be known a priori, the actual amount of the resource needed for a particular application of the function to an instance may not be known. Recall that the amount of a resource required to execute the k th pending function is variable and is based upon the current state of the inputs and performance of the j th instance.
When estimating the amount of resource needed for the function to execute, the processor 20 bases the estimate on the maximum amount of the resource that the function can use. Often, the function uses less than the maximum amount of the resource that it is capable of consuming. To optimize the efficient use of the resource, the processor 20 will attempt to over-allocate the resource based upon the maximum consumption rate. The processor 20 then monitors the actual consumption of the resource by the function. If, collectively, the executing functions consume an amount of the resource exceeding a high threshold value, then the processor 20 begins to reduce the amount of the resource allocated. On the other hand, if the executing functions collectively consume less of the resource than the value indicated by a low threshold, the processor 20 attempts to maximize the allocation of the resource. Another way of describing this feature is in terms of a consumption alarm. If the actual consumption of the resource exceeds the high threshold value, then the consumption alarm is set and the allocation of the resource is reduced. If the actual consumption of the resource falls below the low threshold value, an existing alarm condition is removed and the processor allocates resources normally.
There are two ways of reducing the amount of the resource allocated. First, the processor can reduce the number of instances during which a particular sub-set of the functions execute. Essentially, this is accomplished by reducing the queue sizes of the executing functions. The queue size identifies the number of instances of a function that may execute concurrently. A queue size may be varied between a minimum size of one and the maximum number of instances that exist. Second, the processor 20 can reduce the amount of the resource allocated to a sub-set of the executing functions. In this second way, the processor 20 reduces (i.e., throttles) the amount of the resource that an executing function may consume.
As mentioned before, the resources controlled by the processor 20 may be MIPS, memory, and other resources of the communication processor 20 . Continuing with the example where the resource is the processor MIPS, a way of regulating the allocation of MIPS in response to their actual consumption is described. For some period of time, τ, a measurement is made of the processor's 20 idle durations. These idle durations are summed to generate the total idle time, t idle , for the period τ. The amount of MIPS actually used by the processor 20 during this period may be derived using the equation:
Total Number of MIPS Used = ( 1 - t idle τ ) × Total Processor MIPS
where,
total processor MIPS=the maximum number of MIPS that is achievable by the processor.
Once the processor determines the MIPS actually consumed by the totality of executing functions, it may compare this amount to the high and low threshold values. If the measured value exceeds the high threshold value, the processor 20 instructs the Agent to reduces the allocation of MIPS over all active instances and functions that are considered for execution. If the measured value is less than the low threshold, then the processor 20 attempts to increase the allocation of MIPS. The process of measuring the actual MIPS, comparing the measured value to threshold values, and adjusting the allocation of MIPS as necessary is performed serially in time period and may be performed periodically or intermittently. Allocation of the available MIPS to the functions waiting in the queue may be conducted to optimize the number of MIPS assigned to these functions, to optimize the number of instances of the functions concurrently being executed, or according to some other scheme.
Because many varying and different embodiments may be made within the scope of the inventive concept herein taught, and because many modifications may be made in the embodiments herein detailed in accordance with the descriptive requirements of the law, it is to be understood that the details herein are to be interpreted as illustrative and not in a limiting sense.
|
A method is disclosed for allocating processing resources, such as instruction execution which can be measured in MIPs or memory capacity, or other resources of a processor itself or resources used in the process of performing operations, such as memory resources, busses, drivers and the like, to functions in a queue waiting to be executed. This method includes the steps of determining the amount of processor resources available to be assigned, determining an estimate of the amount of resources needed for each function waiting in the queue to execute, and allocating the available resources to the functions using a hierarchical priority scheme. The hierarchical priority scheme assigns priority based on the environmental conditions, the achieved performance, and the amount of resource recently consumed by the function.
| 6
|
CROSS REFERENCE TO RELATED APPLICATION(S)
[0001] This application is related to and claims priority from U.S. Provisional Patent Application Ser. No. 60/904,130, filed Feb. 27, 2007.
BACKGROUND
Hydrogen Production
[0002] Hydrogen has been touted as an environmentally friendly wonder fuel that can be used in vehicles and burns to produce only water as a by product. Hydrogen production is a large and growing industry. Globally, some 50 million metric tons of hydrogen, equal to about 170 million tons of oil equivalent, were produced in 2004. The growth rate is around 10% per year. Within the United States, 2004 production was about 11 million metric tons (MMT), an average power flow of 48 gigawatts. As of 2005, the economic value of all hydrogen produced worldwide is about $135 billion per year.
[0003] There are two primary uses for hydrogen today. About half is used to produce ammonia (NH 3 ) via the Haber process, which is then used directly or indirectly as fertilizer. The other half of current hydrogen production is used to convert heavy petroleum sources into lighter fractions suitable for use as fuels. This latter process is known as hydrocracking. Hydrocracking represents an even larger growth area, since rising oil prices encourage oil companies to extract poorer source material, such as tar sands and oil shale. The scale economies inherent in large-scale oil refining and fertilizer manufacture make possible on-site production and “captive” use. Smaller quantities of “merchant” hydrogen are manufactured and delivered to end users as well.
[0004] Additionally, it is possible that fuel cells, using hydrogen as a fuel, will be able to replace most internal combustion engines and at the same time will solve most grid load balancing needs. It will do this by allowing “storage” of electrical energy in a grid of plug-in automobiles, which will be available to store excess energy as hydrogen, and offering it to the electrical grid as needed, after conversion in fuel cells. Hydrogen in this sense would act like a chemical battery and would essentially replace battery technology in electrical hybrid cars.
[0005] Although hydrogen fuel cells do not emit harmful gases into our atmosphere but other hazardous conditions exist due to the extremely explosive properties of hydrogen. Also, it is not economically efficient to completely modify our infrastructure to make our society dependent on hydrogen, since present technology requires costly energy consumption to liquify the hydrogen.
Carbon Capture
[0006] About 85% of the world's commercial energy needs are currently supplied by fossil fuels. Carbon capture and storage is an approach to mitigate global warming by capturing carbon dioxide from large point sources such as fossil fuel power plants and storing it instead of releasing it into the atmosphere. Although CO 2 has been injected into geological formations for various purposes, the long term storage of CO 2 is a relatively untried concept and as yet no large scale power plant operates with a full carbon capture and storage system.
[0007] CCS applied to a modern conventional power plant could reduce CO 2 emissions to the atmosphere by approximately 80-90% compared to a plant without CCS. Capturing and compressing CO 2 requires much energy and would increase the fuel needs of a plant with CCS by about 11-40%. These and other system costs are estimated to increase the cost of energy from a new power plant with CCS by 21-91%. These estimates apply to purpose-built plants near a storage location: applying the technology to preexisting plants or plants far from a storage location could be more expensive.
[0008] Consequently, the technology of CCS would enable the world to continue to use fossil fuels but with much reduced emissions of CO 2 , while other low-CO 2 energy sources are being developed and introduced on a large scale. In view of the many uncertainties about the course of climate change, further development and demonstration of CCS technologies is a prudent precautionary action.
SUMMARY
[0009] Varying embodiments of the present invention include a self-contained electrolysis process and an apparatus associated therewith. In an embodiment, a cryogenic cogeneration process is employed in conjunction with an atmospheric medium to separate desired chemical compounds via electrolysis for storage and/or future use. Consequently, through the use of the present inventive concepts, desired chemical compounds (e.g. hydrogen, CO 2 ,) can be capture in an effective and cost efficient manner.
[0010] A first aspect of the present invention is a self-contained electrolysis process. The process includes utilizing a cryogenic cogeneration process to extract a liquid from an atmospheric medium, passing a current through the liquid, and separating at least one chemical element from the liquid.
[0011] A second aspect of the present invention is a self-contained electrolysis apparatus. The apparatus includes cryogenic cogeneration means for extracting a liquid from an atmospheric medium, electrical means for passing a current through the liquid and separating means for separating at least one chemical compound from the liquid.
[0012] A third aspect of the present invention is a method and system of removing at least one element from a chemical compound. The method and system include utilizing a cryogenic cogeneration process to remove the at least one element from the chemical compound.
[0013] Other aspects and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, illustrating by way of example the principles of the invention.
BRIEF DESCRIPTION OF DRAWINGS
[0014] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate varying embodiments of the inventive concepts and, together with a general description given above and the detailed description of the varying embodiments given below, serve to explain the principles of the invention.
[0015] FIG. 1 shows a cryogenic cogeneration system in accordance with an embodiment of the present invention.
[0016] FIGS. 2-1 and 2 - 2 shows the system in conjunction with varying embodiments of the present invention.
[0017] FIG. 3 show an overview of the integrated electrochemical and thermochemical renewable energy production, storage, distribution and recycling system in conjunction with an automated computer control network.
DETAILED DESCRIPTION
[0018] The following description is presented to enable one of ordinary skill in the art to make and use the invention and is provided in the context of a patent application and its requirements. Various modifications to the embodiments and the generic principles and features described herein will be readily apparent to those skilled in the art. Thus, the present invention is not intended to be limited to the embodiment shown but is to be accorded the widest scope consistent with the principles and features described herein.
[0019] Varying embodiments of the present invention include a self-contained electrolysis process and an apparatus associated therewith. In an embodiment, a cryogenic cogeneration process/system is employed in conjunction with an atmospheric medium to separate desired chemical compounds via electrolysis for storage and/or future use. Consequently, through the use of the present inventive concepts, desired chemical compounds (e.g. hydrogen, CO 2 ,) can be capture in an effective and cost efficient manner.
Hydrogen Production
[0020] FIG. 1 shows a cryogenic cogeneration system 1 in conjunction with an embodiment. The system 1 includes a liquid receiver 8 , a liquid subcooler 14 , a super heater compressor 22 , a condenser 35 and an expansion engine 150 . In an embodiment, the system 1 converts energy from an external heat source medium 1000 into mechanical and/or electrical energy. For a further description of this exemplary system, reference may be had to U.S. patent application Ser. No. 11/100,197, filed Apr. 5, 2005, entitled “Cryogenic Cogeneration System”, which is incorporated herein by reference.
[0021] Please refer now to FIGS. 2-1 and 2 - 2 . Accordingly, the electrolysis process preferably begins by chilling heat source medium 1000 , via the superheater compressor 22 . Once chilled, the medium 1000 is piped through distribution valve 1059 via supply piping route 1003 and piping and apparatuses 1025 , into optional atmospheric vapor extraction coil 1002 . Vapor extraction coil 1002 preferably absorbs desired electrolyte from vapor 1001 via thermally conductive contact with vapor 1001 . The condensed/frozen vapor 1001 is then stored as ice and/or as liquid (e.g. water) via gravity flow into liquid electrolyte supply tank 1007 .
[0022] A liquid electrolyte pressure pump 1026 draws the ice and/or liquid 1001 to central electrolyte supply distributor 1004 . Here a conductive solvent injection system 1013 and a vaporized electrolyte steam Supply tank 1005 collaborate to distribute negatively charged anions to ion supply 1012 in anode tank 1018 and positively charged cations to ion supply 1006 in cathode tank 1020 . Here, the desired element gas (e.g. hydrogen) can be separated from the liquid molecule/compound (e.g. water).
[0023] Accordingly, the hydrogen gas exits cathode tank 1020 via discharge exit 1008 and distribution valve 1051 to a gas turbine 1066 via valve 1067 and/or to a storage tank 1022 via supply line 1009 . Hydrogen gas is subsequently discharged from storage tank 1022 via discharge exit 1010 to a heat rejection coil 1011 to condense/freeze/sublime the hydrogen and fill storage tank 1014 at supply tank entrance 1016 . The hydrogen can then be removed from storage tank 1014 via discharge exit 1015 .
[0024] In an embodiment, expansion engine 150 provides power to turn drive shaft 1030 that is coupled to an electrical generator 1032 and rectifier 1071 . The electrical generator 1032 can be a direct current (DC) generator or an alternating current (AC) generator. The negatively charged (electron excessive) pole 1034 of generator 1032 (or Optional Rectifier 1071 ) feeds the line side of electrolysis cell 1072 to polarize electrolytic cathode electrode 1040 . The positively charged (electron deficient) pole 1036 of generator 1032 (or Optional Rectifier 1071 ) feeds the line side of electrolysis cell 1072 to polarize electrolytic anode electrode 1038 to facilitate the correlated above-described electrolysis process.
Voltaic Process
[0025] In an alternate embodiment, a self-contained voltaic process is implemented. Here, the hydrogen from storage tank 1009 and/or cathode tank 1020 are routed by the distribution valve 1051 to anode fill tank 1047 via anode electrode 1046 of voltaic fuel cell 1045 . The voltaic fuel cell 1045 also includes a cathode fill tank 1049 for storing cathodes routed to the cathode electrode 1048 via storage tank 1018 . The pertinent re-dox reaction with the voltaic fuel cell electrolyte 1050 takes place and desired ions/reactant(s)/element (e.g. oxygen) from the cathode fill tank 1049 re-bond and form gas and/or liquid (e.g. steam/water) that can exit via piping 1025 through valves 1055 and 1056 to be distributed per demand conditions.
[0026] Alternatively, the steam/water can be recycled back into original reduced forms via re-entering the electrolysis system as a gas through a steam supply tank 1005 and/or the steam reforming tank 1037 as distributed by steam feeder valve 1056 and/or as a liquid via the bottom exit of 1050 and re-entering supply tank 1007 through piping 1025 . Steam can optionally travel via supply distribution valve 1066 and perform work output via steam expansion engine turbine 1065 .
Liquefaction
[0027] Liquefaction of gases includes a number of processes used to convert a gas into a liquid state. The processes are used for scientific, industrial and commercial purposes. Many gases can be put into a liquid state at normal atmospheric pressure by simple cooling; a few, such as carbon dioxide, require pressurization as well. Liquefaction is used for analyzing the fundamental properties of gas molecules (intermolecular forces), for storage of gases and in refrigeration and air conditioning.
[0028] Accordingly, in an alternate embodiment, a liquefaction process can be implemented. The process begins whereby the desired element e.g. Hydrogen, exits hydrogen production tank 1029 through distribution valve 1054 via hydrogen outlet 1035 . The hydrogen then proceeds through to gas turbine 1066 via valve for 1067 and/or storage tank 1009 . Next, the hydrogen exits storage tank 1009 via discharge exit 1010 to become in thermally conductive contact with heat rejection coil 1011 . Once in thermally conductive contact with the heat rejection coil 1011 , the hydrogen liquefies to fill storage tank for 1014 through supply entrance 1016 .
[0029] Although the above-described embodiments are described in the context of hydrogen production, one of ordinary skill in the art will readily recognize that a variety of different chemical elements can be produced with this system while remaining spirit and scope of the present inventive concepts.
[0000] Self Contained Electricity Generation, Distribution and/or Storage Process
[0030] In an alternate embodiment, a self-contained electricity generation, distribution and storage process is implemented. The process begins whereby expansion engine 150 from cryogenic cogeneration system 1 provides power to turn drive shaft 1030 that is coupled to electrical generator 1032 with or without the option of utilizing rectifier 1071 . The negatively charged (electron excessive) pole 1034 and the positively charged (electron deficient) pole 1036 of rectifier 1071 feed the line sides of electrical switching to battery storage 1073 through switch 1042 to facilitate the charging of storage battery(s) 1041 .
[0031] In an alternate process, expansion engine 150 from cryogenic cogeneration system 1 provides power to turn drive shaft 1030 that is coupled to electrical generator 1032 with rectifier 1071 . The negatively charged (electron excessive) pole 1034 and the positively charged (electron deficient) pole 1036 of rectifier 1071 feed the line sides of switch 1073 through switches 1076 and 1077 to facilitate the alternating and/or direct current power load to/from Supplemental Refrigeration/Thermalelectric System 1078 ( a,b . . . ) within a parallel array of Supplemental Refrigeration/Current Generation System(s) 1079 . This array can include but is not be limited to Dilution Cryocooler(s), Adiabatic Demagnetization Refrigerators, Pulse Tubes, Brayton Cycles, Claude Cycles, Thermal Electric Refrigerators, Vortex Tubes, Dry Ice Refrigerators, and Stirling Engines which could include the utilization of Optional Sequenced Inverter 1093 ( a,b . . . ).
[0032] Direct Current
[0033] In another embodiment, expansion engine 150 from cryogenic cogeneration system 1 provides power to turn drive shaft 1030 that is coupled to electrical generator 1032 with rectifier 1071 . The negatively charged (electron excessive) pole 1034 and the positively charged (electron deficient) pole 1036 of rectifier 1071 feed the line sides of switch 1073 through power distribution switch 1074 to supply direct current to electrical power demand load 1075 (e.g. electric motor, transformer, etc).
[0034] Alternating Current
[0035] In another embodiment, expansion engine 150 from cryogenic cogeneration system 1 provides power to turn drive shaft 1030 that is coupled to electrical generator 1032 with rectifier 1071 . The negatively charged (electron excessive) pole 1034 and the positively charged (electron deficient) pole 1036 of rectifier 1071 feed alternating current to the line sides of switch 1073 through power distribution switch 1074 to supply alternating current to electrical power demand load 1075 (e.g. electric motor, transformer, etc).
[0036] Voltaic Fuel Cell
[0037] In another embodiment, Voltaic (Fuel) Cell anode electrode 1046 and Voltaic (Fuel) Cell cathode electrode 1048 feed direct current power via switch 1044 through switch 1074 for supply of direct current demand load 1075 or via inverter 1070 for supply of alternating current to demand load 1075 . Additionally, Voltaic (Fuel) Cell anode electrode 1046 and Voltaic (Fuel) Cell cathode electrode 1048 feed direct current power via switch 1044 to facilitate the charging of Storage Battery(s) 1041 .
[0038] Furthermore, the distribution of electrical power demand load 1075 can be cryogenically cooled to reduce/eliminate resistance attributed to counter electromotive force via thermal contact with Superconducter Cryogenic Cooling Medium/Heat Exchanger 1064 contained within Superconducter Cryogenic Cooling Loop for Electrical Power Distribution Line Feeders 1063 . After Medium 1064 absorbs heat from load 1075 , the medium returns as a heat source medium 1000 via valve 1062 . The medium then rejects heat and becomes re-chilled via superheater compressor 22 to be re-supplied via valves 1061 and 1090 back to complete Loop 1063 .
[0000] Integration of the Cryogenic Cogeneration System with a Parallel Array of Supplemental Refrigeration and/or Thermal Electrical Current Generation System(s)
[0039] This integration process begins by chilling heat source medium 1000 , via superheater compressor 22 , from cryogenic cogeneration system 1 . The medium 1000 is discharged though distribution valve 1059 , where the chilled medium 1000 is routed to piping route 1003 via distribution valves 1090 and 1061 . Chilled medium 1000 then proceeds through distribution valve 1088 to the calculated pertinent thermal energy exchanger 1084 ( a,b . . . ) which will absorb thermal energy from the thermal energy exchanger for supplemental refrigeration system 1081 ( a,b . . . ). Medium 1000 then returns back to superheater compressor 22 via distribution valves 1087 , 1062 and 1052 to complete the integration loop.
[0040] Additionally, temperature and/or thermal differentials between 1081 ( a,b . . . ) and 1080 ( a,b . . . ) at least partially attributed to the aforementioned integration process may generate a current that can travel via switching 1076 , 1077 , and 1042 to supplement the charging of battery storage systems 1041 and/or other appropriate electrical power load demands.
[0000] Cryogenic Cogeneration System Interaction with Supplemental Refrigeration/Current Generation System
[0041] Condenser to Subcooler
[0042] In an embodiment, the cryogenic cogeneration system 1 can interact with the Supplemental Refrigeration/Current Generation System(s) 1080 ( a,b . . . ) to create a temperature difference in order to supplement the efficient operation thereof. Here, the condenser 35 rejects heat to heat sink medium 1094 which will exit condenser 35 through distribution valve 1089 via distribution valve 1085 to enter the calculated pertinent thermal energy exchanger 1080 ( a,b . . . ) which will absorb heat from medium 1094 as it circulates through the calculated pertinent thermal energy rejecter coil 1083 ( a,b . . . ). It then exits as a chilled/sub-cooled medium via distribution valve 1086 and then proceeds through distribution valve 1091 to feed liquid sub-cooler 14 and/or liquid receiver 8 .
[0043] Receiver to Subcooler
[0044] In an alternate embodiment, liquid receiver 8 rejects heat to heat sink medium 1094 which exits receiver 8 through distribution valve 1089 via distribution valve 1085 to enter the calculated pertinent thermal energy exchanger 1080 ( a,b . . . ) which will absorb heat from medium 1094 as it circulates through the calculated pertinent thermal energy exchanger rejecter coil 1083 ( a,b . . . ) to exit as a chilled/subcooled medium via distribution valve 1086 then through distribution Valve 1091 to feed liquid sub-cooler 14 and/or liquid receiver 8 .
Carbon Capture
[0045] In another embodiment, the cryogenic cogeneration system 1 can be employed to remove carbon from fossil fuel. This can be accomplished pre-combustion or post-combustion.
Pre-Combustion
[0046] In the pre-combustion embodiment, the process begins whereby fossil fuel 1031 and/or discharge for desired gas element (e.g. Oxygen) 1021 flows via valve 1108 and/or distribution valve 1110 to gas emission capture tank 1027 where waste gas separator coil 1028 is employed to remove undesired elements through thermally conductive contact with carbon emission extraction coil 1024 . Fuels 1031 and 1021 can then re-circulate back via valve 1106 to supply burners 1095 for cleaner combustion. This process can be applied to all types of combustion systems.
Post-Combustion
[0047] In the post-combustion embodiment, make up steam from boiler 1033 enters and supply steam reforming tank via 1037 as distributed by feeder valve 1056 to mix with fossil fuel 1031 via steam reforming tank entrance 1039 within steam reforming (Hydrogen Production) tank 1029 .
[0048] Harmful emissions (e.g. carbon) can be captured from Steam Reforming Tank 1029 and/or Optional Steam Boiler 1033 and/or Burners 1095 preferably with extraction hood 1057 to be exhausted via distribution piping 1058 to injector 1028 and extraction coil 1024 . The extraction coil 1024 then transfers absorbed heat into external heat source medium 1000 , via thermally conductive contact. The medium 1000 then returns via circulation through distribution valve 1052 back to the superheater compressor 22 .
[0049] Here, the medium 1000 is re-chilled and re-circulated via distribution valve 1059 to be routed back through loop 1060 and again through capture tank 1027 . Processed product (e.g. liquid CO 2 and Dry Ice) can then be removed from capture tank exit 1069 and/or Dry Ice Dispenser door 1092 .
[0050] It should be noted that an automated computer control network may be implemented to control part and/or all of the aforementioned processes via the use of an indefinite number of electronic and/or electromechanical and/or pneumatic and/or hydraulic actuators, relays, and all other pertient parts and accessories of a complete control system. FIG. 3 show an overview of the integrated electrochemical and thermochemical renewable energy production, storage, distribution and recycling system 1096 in conjunction with an automated computer control network 1097 .
[0051] Without further analysis, the foregoing so fully reveals the gist of the present inventive concepts that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute the characteristics of the generic or specific aspects of this invention. Therefore, such applications should and are intended to be comprehended within the meaning and range of equivalents of the following claims. Although this invention has been described in terms of certain embodiments, other embodiments that are apparent to those of ordinary skill in the art are also within the scope of this invention, as defined in the claims that follow.
|
A first aspect of the present invention is a self-contained electrolysis process. The process includes utilizing a cryogenic cogeneration process to extract a liquid from an atmospheric medium, passing a current through the liquid, and separating at least one chemical element from the liquid. A second aspect of the present invention is a self-contained electrolysis apparatus. The apparatus includes cryogenic cogeneration means for extracting a liquid from an atmospheric medium, electrical means for passing a current through the liquid and separating means for separating at least one chemical compound from the liquid. A third aspect of the present invention is a method and system of removing at least one element from a chemical compound. The method and system include utilizing a cryogenic cogeneration process to remove the at least one element from the chemical compound.
| 8
|
FIELD OF THE INVENTION
The invention relates to a washing machine and a washing method, especially a washing method for washing machine and a washing machine capable of even overturn and washing free of intertwining.
BACKGROUND OF THE INVENTION
Currently, washing method of an impeller washing machine is to achieve cleaning by special water flow generated from impeller rotation or simultaneous rotation of the impeller and inner tub to overturn the clothing and pose force on it during overturn so that the clothing can be washed repeatedly through self friction and friction with impeller and inner tub wall. Impeller of the impeller washing machine has various shapes such as plate, bar, bowl shapes, etc.; regardless of shape change, ultimate goal of the impeller is to improve cleanliness and reduce clothing intertwining. However, high cleanliness and low intertwining rate are contradictory. Usually, the cleanliness will increase with high intertwining rate, or the cleanliness decrease with low intertwining rate. Existing impeller washing machine has such disadvantages as large water and detergent consumption, long washing time, clothing intertwining and knotting, uneven washing and deformation; or, clothing washing is realized via impact force of water flow formed by centrifugal force generated by inner tub rotation. Usually, clothing is washed as a whole. Although water flow has an effect on washing, clothing cannot be dispersed while will be intertwined as a whole.
In order to improve cleanliness, the impeller is required to rotate rapidly at large angles during washing. Clothing will be driven by water flow generated by centrifugal force to move along the same direction rapidly. Eventually, clothing will be intertwined, torn and damaged, especially high-end clothing which is more readily damaged; moreover, in case of simply relying on water flow during washing, the mode of movement is simple and fixed, resulting in low overturn efficiency of clothing in the tub. Hence, more times of washing is required to be conducted to achieve washing effects of the clothing.
Besides, when the washing machine is running, impeller rotates or oscillates to generate ring-shaped water flow, and movement of clothing in the tub depends on fluid motion or fluidic power. In order to realize required ring-shaped overturn mode, it is also necessary that automatic washing machine with impeller at the bottom is filled with washing liquid. Height of the washing liquid shall be able to completely submerge fabrics put into the washing drum. Hence, it will consume large quantity of water. In addition, since the quantity of washing liquid is large, more detergent must be used to achieve enough concentration. As a result, the washing cost is high and water resources will be polluted to a certain extent.
China Patent Publication No. CN2898085Y discloses an impeller of washing machine, comprising a round underpan and water string set on the underpan, which is characterized in that the underpan has high circumference and low center, forming a concave curved sphere. The water string comprises a central water string, a primary water string and a secondary water string, and the central water string is positioned in the middle of the underpan; the primary water string is arranged radially on the underpan, on both sides thereof, a bevel tilting outwards is positioned; the secondary water string is also arranged radially on the underpan, on both sides thereof, a bevel tilting outwards is positioned; the primary water string is spaced from the secondary water string, the central water string is higher than the primary water string which is higher than the secondary water string.
US Patent Publication No. U.S. Pat. No. 1,704,932A discloses a washing machine, comprising a dolly or agitating member operative from and by means of a shaft passing up through the bottom of the tub or container fins, integrating with radially arranged blades or baffle members and an intermediate surface inclined or curved upwardly from its peripheral edge, that the resultant action of the dolly or agitator; as it is alternately oscillated is to cause the articles being washed to be moved toward the center of the dolly or agitating member and upwardly and thence outwardly and downwardly; or in other words impart to such articles a slow whirl like motion radially of the dolly or agitator and thereby more effectively cleanse the articles, by constant agitation and the forcing of air and water through the articles. This invention has reference to washing machines, and it has for its principal object to improve the dolly or agitating means, whereby to produce a more effective and improved washing action on the articles deposited in the tub or container thereof.
EP Patent No. EP0837171B1 discloses an automatic washer for washing clothes, the automatic washer comprising: an imperforate wash tub, a perforated wash basket having a cylindrical side wall, provided within and rotatable relative to the wash tub, a rotatable washplate with a bottom plate, a peripheral wall and a centrally disposed annular mounting collar, provided within and rotatable relative to the wash basket, a drive system connected to the wash basket and the wash tub for rotating the wash basket and the wash plate, and a least two diametrically opposed ripples provided on and extending upwardly from the bottom plate of the wash plate, characterised in that each ripple has a saddle shaped surface contour defining opposing sloped walls which extend respectively radially inwardly and radially outwardly form a low point substantially midway between the peripheral wall and the outer edge of the annular collar and in that the peripheral wall is substantially perpendicular to the bottom plate. The radially outwardly extending sloped wall of the ripples rising to meet the upper part of the peripheral wall, and in that an annular sealing lip is provided around the outside of the peripheral wall, extending outwardly substantially perpendicularly from the top edge of the peripheral wall to the cylindrical side wall of the wash basket.
US Patent Publication No. U.S. Pat. No. 4,068,503A discloses an improved agitator means for use with an automatic washer having a clothes washing receptacle and drive means for driving an agitator in an oscillatory fashion. The improved agitator means of the present invention is a double action agitator and includes a lower agitator element which is engageable with the drive means for oscillation about an axis in the usual manner and an upper agitator element which is coaxial with the lower element and is coupled to the drive shaft by means of a one-way clutch for unidirectional rotation about the axis of the agitator. The upper agitator element is provided with auger-like vane means for urging clothes within the receptacle downwardly toward the lower agitator element where they are contacted by a set of generally vertically-extending vanes disposed about the skirt portion of the lower agitator element. In effect, therefore, the upper agitator element acts to continuously feed clothes downwardly along the barrel of the agitator where they come under the influence of the oscillating vertically positioned vanes of the lower agitator element which direct the clothes radially outwardly toward the periphery of the basket, and eventually upwardly and back to the barrel of the upper agitator element, completing a repeating rollover cycle which is extremely efficient for securing a uniform scrubbing contact of the clothes with the wash liquid.
In witness whereof, the invention is provided.
SUMMARY OF THE INVENTION
Technical problems to be solved by the present is to overcome existing technical deficiencies and provide a washing method for washing clothes by using less washing water and driving clothing to overturn evenly up and down to minimize intertwining, and improving clothing cleanliness rate and evenness degree.
Another object of the invention is to provide a washing machine with the washing method.
In order to solve the technical problems, the basic idea of technical scheme for the invention is: a washing method for washing machine which contains a wash tub and an impeller placed at the bottom of the tub, including:
Putting the clothing into the tub;
Detecting the load and inflooding water according to the load capacity;
Washing, that different water flows generated by controlling rotation-stop ratio of the impeller perform single sequential coordination or repeatedly alternating cycle coordination, so as to break the balance of the load to disperse the clothing, and realize even overturn and washing, and keep the load evenly overturning.
During washing, three types of water flows are generated by controlling rotation-stop ratio of the impeller: agitating flow, enhancing flow, and balancing flow; at first, the agitating flow will break the balance of the load to disperse the clothing, then the enhancing flow will overturn the clothing for washing, at last, the balancing flow will maintain the circulation path for the load evenly overturning; agitating flow, enhancing flow, and balancing flow will perform single sequential washing or repeatedly alternating cycle washing.
During washing, overturn path of the clothing comprises: the clothing at the bottom being dragged to the center of the impeller by enhancing flow generated by impeller rotation, and the clothing uprushing, overturning outwardly and descending on the center of the impeller, then the clothing moving to the center of the impeller again after falling down to the bottom. The said overturn process will be repeated.
Furthermore, an inlet water level is lower than or equal to a height of the load.
Preferably, the inlet water level meets water quantity by which the clothing can be completely wetted and contact with upper surface of the impeller during overturn.
Action time of the enhancing flow is at least shorter than that of the agitating flow. i.e., the action time of the enhancing flow is only shorter than that of the agitating flow, or, the action time of the enhancing flow is shorter than that of both the agitating flow and the balancing flow. Furthermore, action time of the agitating flow is the same with that of the balancing flow.
Rotation-stop ratio of the impeller corresponding to the agitating flow can be the same with or different from that corresponding to the balancing flow.
The intensity of the enhancing flow is stronger than that of the agitating flow. The intensity relates to corresponding rotation-stop ratio of the impeller. The stronger the rotation-stop ratio is, the stronger the flow intensity is.
When drive unit of the washing machine is a frequency direct drive motor, the intensity of the agitating flow is adjusted for load capacity. The larger the load capacity is, the stronger the intensity is.
Rotation-stop ratios of the impeller corresponding to the agitating flow, the enhancing flow and the balancing flow are adjusted according to load capacities. The larger the load capacity is, the larger the rotation-stop ratios of the impeller corresponding to the agitating flow, the enhancing flow and the balancing flow are.
On the washing machine, different gears are set according to different ranges of load capacities, which at least includes the first load indicating the minimum range of load capacity. During washing with the enhancing flow corresponding to the first load, within the set working time of enhancing flow, the impeller rotates and stops multiple times in the same direction as per corresponding rotation-stop ratio and then repeats the rotation and stop in the opposite direction; during washing with the agitating flow and the balancing flow corresponding to any load capacity and the enhancing flow corresponding to any load capacity excluding the first load, the impeller performs forward and reverse alternative rotation as per corresponding rotation-stop ratio.
For rotation-stop ratio of the impeller corresponding to the agitating flow, the enhancing flow and the balancing flow, time of each rotation is 0.2-3.0 s and that of each stop is 0-3.0 s. Any time within the two ranges will combine to form the rotation-stop ratio corresponding to the agitating flow, the enhancing flow and the balancing flow.
In specific, as for the rotation-stop ratios of the impeller corresponding to the agitating flow and the balancing flow, time of each rotation is 0.2-2.0 s and that of each stop is 0.2-2.0 s. The time of each rotation and that of each stop within the two ranges will combine to form the rotation-stop ratios corresponding to the agitating flow and the balancing flow.
As for the rotation-stop ratio of the impeller corresponding to the enhancing flow, time of each rotation is 0.2-3.0 s and that of each stop is 0.2-3.0 s. The time of each rotation and that of each stop within the two ranges will combine to form the rotation-stop ratio corresponding to the enhancing flow.
After washing, the drive motor rotates and stops intermittently within the set time for dewatering and drainage. Then execute spraying and rinsing with no drainage, and the drive motor rotates and stops intermittently.
In the drainage stage during rinsing, the drive motor simultaneously rotates and stops intermittently for dewatering; during dewatering, the washing machine will perform dewatering by utilizing the method of no drainage or drainage alternation. After dewatering, the wash tub stops from rotating and drainage begins. The most water in the clothing is thrown away and drained out in the drainage stage during rinsing. During dewatering, since water quantity in the clothing is reduced, the water thrown away from the clothing does not need to be drained within a certain time period during which more water thrown away from the clothing will be accumulated. Then entering the next set time period, start the drainage, and then stop the drainage (repeat the drainage start and stop). Finally, realize drainage when the wash tub stops from rotating. The dewatering method of alternation of drainage start and stop can save energy of drainage equipment.
An washing machine of the invention is used for the washing method comprises an impeller which contains an impeller disk and multiple groups of water spinning blades arranged on the surface of the impeller disk, the impeller disk being of basin-shaped structure with a bulge on the center, each group of water spinning blades extending from the center of the impeller disk to the edge, the water spinning blade mainly consisting of at least two convex ribs which incline to both sides in extension direction of the water spinning blade respectively to form twisted structure of the water spinning blade.
The water spinning blade is of linear or curved shape in extension direction. When the water spinning blade is of curved shape in extension direction, the water spinning blade have at least two convex ribs with rates of curve or slope projected on the impeller disk surface being different, or, the water spinning blade at least consists of curved convex rib and linear convex rib.
The water spinning blade contains a first convex rib close to the center of the impeller disk and a second convex rib close to the edge of the impeller disk. The first convex rib and the second convex rib incline to the surfaces of the impeller disk on different sides respectively. Slope angles between the convex rib and vertical surface of the impeller disk where the water spinning blade intersects with the surface the impeller disk is less than or equal to 35°. Smooth transition can be realized between both sides of the water spinning blade and the surface of the impeller disk.
Projections of the first convex rib and the second convex rib on the surface of the impeller disk are two arches whose centers of circle are on both sides of the water spinning blade respectively.
Central angle between two ends of the water spinning blade is 15°-90°, with 30°-60° preferred.
A height change of an upper surface of the water spinning blade in extension direction from the center of the impeller disk to the edge is: at first rising to a maximum height, then falling to a minimum height and finally rising to realize smooth transition with inner circumferential wall of basin-shaped impeller disk. Height difference between the maximum height and the minimum height of the water spinning blade is 1-1.5 times of a depth of impeller disk. Height difference between the maximum height of the water spinning blade and the center of the impeller disk is 0-0.2 times of the depth of the impeller disk. Position of smooth transition between the water spinning blade and inner circumferential wall of the impeller disk is located on ⅓-⅔ of the impeller disk depth.
Multiple decoration areas are set on the surface of the impeller disk between two water spinning blades, and small water penetrating holes are arrange on these decoration areas. The decoration areas are water-mark-shaped shallow slots with different sizes, with depth range of 1-5 mm. Multiple small water penetrating holes are distributed evenly in the shallow slots.
After adopting the technical scheme, the invention has the following beneficial effects, compared with the prior art.
The invention adopts washing modes corresponding to the agitating flow, the enhancing flow and the balancing flow. The enhancing flow can increase overturn amplitude of the clothing, and the clothing at the tub bottom overturns upwardly and the clothing around the top overturns downwardly. The agitating flow can help to realize even washing and untwining of the clothing overturned by the enhancing flow. The balancing flow keeps the load evenly overturning. Coordination with the impeller of the washing machine can help to realize even washing and up-down overturn of the clothing, so as to achieve better washing effects; the adopted overturn washing makes the clothing evenness degree more than 90% and cleanliness rate more than 0.85. Generally, cleanliness rate of existing washing machine ranges from 0.7 to 0.8, with maximum evenness degree of 80%; as for the washing machine in the invention, the structure of water spinning blade of the impeller can apply certain force to the clothing during forward and reverse rotation washing, resulting in lower water consumption and stronger friction between the impeller and the clothing. Hence, wash buffer with the same concentration needs less detergent. Water saving and detergent saving (relatively) can be achieved simultaneously. Pollution caused by drainage can be eased. About 20%-40% water can be saved for each washing.
In combination with the drawings, the following contents provide further description of the preferred embodiments of the invention in detail.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of center-upward overturn trace of the clothing for washing machine in the invention;
FIG. 2 is a schematic diagram of outward overturn state of the clothing for washing machine in the invention;
FIG. 3 is a schematic diagram of up-down cycle overturn trace of the clothing for washing machine in the invention;
FIG. 4 is a structure diagram of the impeller in the invention;
FIG. 5 is a schematic diagram of cross-section structure of the impeller in the invention;
FIG. 6 is a sequence diagram of rotation-stop ratios corresponding to water flows during the first load washing for washing machine in the invention;
FIG. 7 is a sequence diagram of rotation-stop ratios corresponding to water flows during the second and third load washing for washing machine in the invention;
FIG. 8 is a sequence diagram of dewatering and drainage in drainage stage during rinsing and during dewatering.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A washing machine in the invention contains a wash tub, a rotatable impeller and a motor. The motor drives the impeller to realize forward and reverse rotation during washing. According to FIG. 3 and FIG. 4 , the impeller 1 contains an impeller disk 2 and multiple groups of water spinning blades 3 arranged on the surface of the impeller disk. In this embodiment, three groups of water spinning blades are used, or, four or five groups can be used as well. The impeller disk 2 is of basin-shaped structure with a bulge on the center. The edge of the basin-shaped structure is an inner circumferential wall 4 extending upwardly. Each group of water spinning blades 3 extends toward the edge from the center 5 of the impeller disk. The water spinning blade 3 mainly consists of at least two convex ribs which incline to both sides in extension direction of the water spinning blade respectively to form twisted structure of the water spinning blade.
Furthermore, the water spinning blade 3 is of linear or curved shape in extension direction, when the water spinning blade is of curved shape in extension direction, the water spinning blade have at least two convex ribs with rates of curve or slope projected on the surface of the impeller disk being different. Or, the water spinning blade at least consists of curved convex rib and linear convex rib.
Embodiment 1
Shown as FIG. 3 , in this embodiment, the water spinning blade 3 contains a first convex rib 31 close to the center of the impeller disk 5 and a second convex rib 32 close to the edge of the impeller disk. The first convex rib and the second convex rib incline to the surface of the impeller disk on different sides respectively. Slope angle between the first convex rib 31 and a vertical surface is within 5-10°. The vertical surface is perpendicular to the surface of the impeller disk on the intersection between the water spinning blade and the surface of the impeller disk and the inclination direction is clockwise rotation direction of the impeller. Slope angle between the second convex rib 32 and the vertical surface is within 10-15°, and the inclination direction is clockwise rotation direction of the impeller (referred to FIG. 3 ). Both sides of the water spinning blade 3 realize smooth transition with the impeller disk surface. Projections of the first convex rib 31 and the second convex rib 32 on the surface of the impeller disk are two arches whose centers of circle are on both sides of the water spinning blade 3 respectively. Smooth transition can be realized between the first convex rib 31 and the second convex rib 32 . Central angle α between end A and end B of the water spinning blade 3 is 45°-60°.
Embodiment 2
According to FIG. 4 , in this embodiment, A height change of an upper surface of the water spinning blade 3 in extension direction from the center 5 of impeller disk to the edge is: rising to the maximum height, falling to the minimum height and then rising to realize smooth transition with the inner circumferential wall 4 of basin-shaped impeller disk. Height difference H 1 between the maximum height and the minimum height of the water spinning blade is 1.2-1.3 times of the depth H of impeller disk. Height difference between the highest point of the water spinning blade and the center of the impeller disk is 0.1 times of the depth of the impeller disk. Point C of smooth transition between the water spinning blade 3 and the inner circumferential wall 4 of the impeller disk is located ⅓-⅔ of the depth H of the impeller disk. i.e., height difference h between point C and the lowest point of the impeller disk is ⅓-⅔ times of the depth H of the impeller disk, with ½ times preferred.
Embodiment 3
According to FIG. 3 , multiple decoration areas 6 are set on the surface of the impeller disk between two water spinning blades 3 , and these decoration areas are provided with small water penetrating holes 7 . The decoration areas are water-mark-shaped shallow slots with different sizes, with depth of 2 mm. Multiple small water penetrating holes are distributed evenly in the shallow slots.
The washing machine in the invention contains fully-automatic machine and double-tub washing machine. During washing, putting the clothing into the tub and detecting the load; inflooding water to reach the water level corresponding to the load capacity. The water level is lower than or equal to the load height; during washing, different types of water flows generated by controlling rotation-stop ratio of the impeller perform single sequential coordination or repeatedly alternating cycle coordination, so as to break the load balance to disperse clothing, and realize even overturn and washing, and keep the load evenly overturning.
Further more, during washing, three types of water flows are generated by controlling rotation-stop ratio of the impeller: the agitating flow, the enhancing flow and the balancing flow. At first, using the agitating flow for washing and completely wet the clothing to realize even overturn and washing. After a certain time period for washing by the agitating flow, using the enhancing flow for washing and opening the clothing to increase the overturn amplitude and achieve adequate washing. At last, using the balancing flow to keep the load evenly cycle overturning; single sequential control or repeatedly alternating cycle control of the three types of water flows is adopted for the washing.
In the invention, rotation-stop ratio of the impeller corresponding to the agitating flow can be the same with or different from that corresponding to the balancing flow. Besides, action time of the agitating flow and the balancing flow can be the same with or different from each other as well. The agitating flow breaks the load balance initially to disperse the clothing, and then the enhancing flow overturns the clothing, so the clothing has been distributed evenly and begins to overturn for washing. As a result, when rotation-stop ratio of the impeller corresponding to the agitating flow is the same with that corresponding to the balancing flow, the function of the balancing flow whose rotation-stop ratio of the impeller is the same with that corresponding to the agitating flow, do not break the load balance instead of keeping the load evenly overturning. Hence, if rotation-stop ratio corresponding to the agitating flow is the same with that corresponding to the enhancing flow, they belong to two different functions while share the same running mode. After a certain time period for keeping evenly overturning to wash, the washing is completed or needs to be continued to wash. At this moment, the intertwinement of the clothing may occur. In order to better even wash and to avoid any possible intertwining, cycle mode of the agitating flow, the enhancing flow and the balancing flow for washing is adopted. During washing in the alternating cycle of the said water flows, when the balancing flow joins to the agitating flow for each cycle, the driven modes of rotation-stop ratios corresponding to the two flows combine into one mode, and driven time is the sum of driven time of the two flows.
After washing, the drive motor rotates and stops intermittently within the set time for dewatering and drainage. Then executing spraying and rinsing with no drainage, And the drive motor rotates and stops intermittently.
In the drainage stage during rinsing, the drive motor simultaneously rotates and stops intermittently for dewatering; during dewatering, the washing machine will perform dewatering by utilizing the method of no drainage or drainage alternation. After dewatering, the wash tub stops from rotating and drainage begins. In the drainage stage during rinsing, most water in the clothing is thrown away and drained out. During dewatering, since of water quantity in the clothing is reduced, the water thrown away from the clothing does not need to be drained within a certain time period during which more water thrown away from the clothing will be accumulated. Then entering the next set time period, start the drainage, and then stop the drainage (repeat the drainage start and stop). Finally, realize drainage when the wash tub stops from rotating. The dewatering method of alternation of drainage start and stop can save energy of drainage equipment. Preferably, at the beginning of the dewatering process, the drive motor rotates and stops intermittently.
Further more, the inlet water level meets water quantity by which the clothing can be completely wetted and will not float or separate from upper surface of the impeller. The water level is lower than the clothing height, so as to increase friction between the impeller and the clothing and drag the clothing to the impeller center during washing.
The agitating flow, the enhancing flow and the balancing flow in the invention are controlled by the different rotation-stop ratios of the impeller generated by driving the impeller to rotate. The intensity of the enhancing flow is stronger than that of the agitating flow. Strong intensity of the enhancing flow can increase the overturn amplitude of the load.
The intensity of the enhancing flow is stronger than that of the agitating flow. When drive unit of the washing machine is a frequency direct drive motor, the intensity of the agitating flow is adjusted for load capacity. The larger the load capacity is, the stronger the intensity is.
On the washing machine, different gears are set according to different ranges of load capacities, which at least include the first load indicating the minimum range of load capacity. During washing with the enhancing flow corresponding to the first load, within the set working time of enhancing flow, the impeller rotates and stops multiple times in the same direction as per corresponding rotation-stop ratio and then repeats the rotation and stop in the opposite direction; during washing with the agitating flow and the balancing flow corresponding to any load capacity and the enhancing flow corresponding to any load capacity excluding the first load, the impeller performs forward and reverse alternative rotation as per corresponding rotation-stop ratio.
In specific, when rated load of the washing machine is M, the first load is set to be more than 0 and less than or equal to 0.3M. The second load is more than 0.3M and less than or equal to 0.7M. The third load is more than 0.7M and less than or equal to M. The division method is different according to different models and rated loads.
For rotation-stop ratio of the impeller corresponding to the agitating flow, the enhancing flow and the balancing flow, time of each rotation is 0.2-3.0 s and that of each stop is 0-3.0 s. Any time within the two ranges will combine to form a rotation-stop ratio corresponding to the agitating flow, the enhancing flow and the balancing flow,
In specific, as for rotation-stop ratios of the impeller corresponding to the agitating flow and the balancing flow, time of each rotation is 0.2-2.0 s and that of each stop is 0.2-2.0 s. Any rotation time and stop time within the two ranges will combine to form the rotation-stop ratios corresponding to the agitating flow and the balancing flow.
As for rotation-stop ratio corresponding to the enhancing flow, time of each rotation is 0.2-3.0 s and that of each stop is 0.2-3.0 s. Any rotation time and stop time within the two ranges will combine to form the rotation-stop ratio corresponding to the enhancing flow.
Embodiment 4
FIGS. 6 and 7 refer respectively to a sequence diagram of rotation-stop ratios corresponding to all kind of water flows during the first load washing, the second load washing, and third load washing, wherein, t 1 , t 2 and t 3 indicate the single washing time for the agitating flow, the enhancing flow and the balancing flow respectively. A 1 , A 2 and A 3 indicate the rotation time of the impeller for the agitating flow, the enhancing flow and the balancing flow respectively. S 1 , S 2 and S 3 indicate the stop time of the impeller for the agitating flow, the enhancing flow and the balancing flow respectively. Ai/Si, i=1, 2 or 3, i.e., rotation-stop ratio corresponding to the agitating flow, the enhancing flow and the balancing flow respectively.
In this embodiment, a washing machine with rated load capacity of 10 kg is taken as an example:
The first load: 30% of load capacity (3 kg)
The second load: 50% of load capacity (5 kg)
The third load: 70% of load capacity (7 kg)
Rotation-stop ratio of the impeller:
Rotation, including forward rotation and reverse rotation: 0.2 s-3.0 s; stop, including stop after forward rotation and stop after reverse rotation: 0.2 s-2.0 s. Rotation time and stop time of the said two ranges can combine to the rotation-stop ratio of the impeller corresponding to each water flow.
At first, use the agitating flow for washing, completely wet the clothing and realize even overturn and washing. Rotation-stop ratios of the impeller corresponding to different load capacities are shown as follows:
The first load: the optimal rotation-stop ratio is 0.4/0.8 s
The second load: the optimal rotation-stop ratio is 0.5/0.5 s
The third load: the optimal rotation-stop ratio is 0.7/0.7 s
The impeller corresponding to the agitating flow performs alternating forward and reverse rotation as per the said rotation-stop ratios. i.e., the rotation-stop ratio of impeller corresponding to the first load gear is: rotate forward for 0.4 s, stop for 0.8 s, rotate reversely for 0.4 s, stop for 0.8 s, rotate forward again for 0.4 s, stop for 0.8 s, rotate reversely for 0.4 s and stop for 0.8 s. Repeat the said cycle actions for 1 min and 12 s (see FIG. 6 ); in a similar way, the impeller corresponding to the second load gear and the third load gear shares the same rotation method while the rotation-stop ratios and rotation time are different. The rotation-stop ratio of the impeller corresponding to the second load gear is 0.5/0.5 s, with action time of 3 min and 10 s. The rotation-stop ratio of the impeller corresponding to the third load gear is 0.7/0,7 s, with action time of 2 min and 13 s (see FIG. 7 ).
After a certain time period of washing by using the agitating flow, use the enhancing flow for washing and open the clothing, so as to realize up-down overturn of the clothing in the wash tub and achieve adequate washing. At this moment, rotation-stop ratios of the impeller corresponding to the enhancing flow for the different load capacities are shown as follows:
The first load: the optimal rotation-stop ratio is 0.4/0.4 s
The second load: the optimal rotation-stop ratio is 1.2/1.0 s
The third load: the optimal rotation-stop ratio is 2.5/1.2 s
During washing with the enhancing flow, the overturning effect is not obvious due to less load and small friction on the loading cloth on the first load. The rotation-stop ratio of the impeller corresponding to the enhancing flow is that it rotates forward for 0.4 s and then stops for 0.4 s, and again rotates forward for 0.4 s and then stops for 0.4 s. After forward rotation in such a circular manner for 4 s, it will rotate reversely for 0.4 s and then stop for 0.4 s, and again run in such a circular manner for 4 s (Refer to FIG. 6 ). For the gears of the second load and third load, the impeller performs forward and reverse rotation as per corresponding rotation-stop ratio. Namely, the rotation-stop ratio of the impeller corresponding to the enhancing flow at the gear of the second load is that the impeller rotates forward for 1.2 s and stops for 1.0 s, and then rotates reversely for 1.2 s and stops for 1.0 s; and again rotates forward for 1.2 s and stops for 1.0 s, and then rotates reversely for 1.2 s and stops for 1.0 s, repeating said circular actions for 25 s. Similarly, the rotation-stop ratio of the impeller corresponding to enhancing flow at the gear of the third load is that the impeller rotates forward for 2.5 s and then stops for 1.2 s, and then rotates reversely for 2.5 s and then stops for 1.2 s; and again rotates forward for 2.5 s and then stops for 1.2 s, and then rotates reversely for 2.5 s and then stops for 1.2 s, repeating said actions for 45 s (referring to FIG. 7 ).
The balancing flow will maintain the circulation path for load evenly overturning. With different load capacities, the rotation-stop ratios of the impeller corresponding to balancing flow are shown as in the below:
The first load: the optimal rotation-stop ratio is 0.3/0.4 s
The second load: the optimal rotation-stop ratio is 0.5/0.5 s
The third load: the optimal rotation-stop ratio is 0.5/0.5 s
In this embodiment, when the load is the small, namely the first load, the rotation-stop ratio of the impeller corresponding to balancing flow and that corresponding to agitating flow are different, but their action time is the same and all is 1 min and 12 s. For the second load, the rotation-stop ratio of the impeller corresponding to the balancing flow is the same with that corresponding to agitating flow and their action time is the same too, all is 3 min and 10 s, For the third load, the rotation-stop ratio of the impeller corresponding to balancing flow and that corresponding to agitating flow are different, but their action time is the same, all is 2 min and 13 s.
After washing with balancing flow, the agitating flow, enhancing flow and balancing flow will proceed. Said processes will be repeated circularly till finishing washing. Or the agitating flow, the enhancing flow and the balancing flow are applied once for each, and the action time of each flow is prolonged correspondingly.
Embodiment 5
Take the fully-automatic washing machine, the rated load capacity of which is 12 kg, as an example:
The first load: 30% of load capacity (3.6 kg)
The second load: 70% of load capacity (8.4 kg)
The third load: 100% of load capacity (12 kg)
Water level on condition that the loading cloth is completely drenched:
The water level in the wash tub is 100 mm below the loading cloth.
Rotation-stop ratio of the impeller:
Rotation (including forward rotation and reverse rotation): 0.5-3.0 s; stop (including stop after forward rotation and stop after reverse rotation): 0.1-2.5 s. Rotation time and stop time of the said two ranges can combine to the rotation-stop ratio of the impeller corresponding to each water flow.
At first, use the agitating flow for washing, completely wet the cloth and realize even overturn and washing. Rotation-stop ratios of the impeller corresponding to different load capacities are shown as follows:
The first load: the optimal rotation-stop ratio is 0.5/1.0 s
The second load: the optimal rotation-stop ratio is 0.7/0.7 s
The third load: the optimal rotation-stop ratio is 0.8/0.8 s
The forward and reverse rotation mode of the impeller corresponding to the agitating flow are the same with those in Embodiment 1, but rotation-stop ratios and rotation durations are different.
The rotation-stop ratios of the impeller corresponding to the enhancing flow for different load capacities are shown as follows:
The first load: the optimal rotation-stop ratio is 0.5/0.5 s
The second load: the optimal rotation-stop ratio is 1.5/1.2 s
The third load: the optimal rotation-stop ratio is 2.8/1.6 s
The rotation-stop ratio corresponding to the enhancing flow at first load is that the impeller rotates forward for 0.5 s and then stops for 0.5 s, and again rotates forward for 0.5 s and then stops for 0.5 s. After the set time for circular forward rotation, it rotates reversely for 0.5 s and then stops for 0.5 s, and again repeats such reverse rotation for a set duration. The forward and reverse rotation modes of the impeller at other loads are the same with those in Embodiment 1, but the rotation-stop ratios and rotation durations are different.
The rotation-stop ratios of the impeller corresponding to the balancing flow for different load capacities are shown as follows:
The first load: the optimal rotation-stop ratio is 0.5/1.0 s
The second load: the optimal rotation-stop ratio is 0.7/0.7 s
The third load: the optimal rotation-stop ratio is 0.8/0.8 s
The rotation-stop ratio of the impeller corresponding to the balancing flow and that corresponding to the agitating flow are the same. In this embodiment, the washing is finished via applying agitating flow, enhancing flow and balancing flow each for once.
The foregoing is only in the case of washing machines with rated load capacities of 10 kg and 12 kg. But it is also applicable to washing machines with different rated load capacities, for example, 6 kg, 8 kg, etc. However, though the foregoing data is not the best for washing machines with other rated load capacities, corresponding adjustment or application of the data can also realize the overturning modes during washing.
In Embodiments 4 and 5, the rotation-stop ratio of the impeller corresponding to balancing flow and that corresponding to agitating flow for different load capacities are the same or different, the nature of which generate two types or three types of water flows. In the invention, not only two or three types of water flows are disclosed, but the rotation-stop ratio is divided into four or five types, etc. in a more detailed manner on the basis of the three types of water flows, so as to realize the fourth, fifth and more water flows. Such division requires more accurate control to the motor, that is, different rotation-stop ratios will be adopted in different set duration during washing; and during rinsing, and the water flows adopted can be the same as that during washing.
Embodiment 6
As for washing machine in the invention, in the drainage stage at the end of rinsing, simultaneously the drive motor rotates and stops intermittently for dewatering. There are two stages for rotation speeds and rotation-stop modes of the motor for dewatering: during dewatering, the washing machine will use the method of the alternation of no drainage and drainage. At the end of dewatering, the wash tub stops from rotating, and drainage begins, rotation speed of the motor will increase stage by stage. This embodiment is adopted a implementation mode in the drainage stage during rinsing and during dewatering for the washing machine with rated load capacity of 10 kg (referring to FIG. 8 ). Details are shown as follows:
Running
mode of the
Rotation
Procedure
Action
motor
Duration
speed
Drainage
Simultaneous
Rotate for
30 s
100 rpm
stage during
drainage
1 s and
rinsing
and spinning
stop for 3 s
Rotate for
30 s
300 rpm
3 s and
stop for 3 s
Dewatering
Dewatering with no
Rotate for
30 s
300 rpm
drainage
3 s and
stop for 3 s
Dewatering and
Rotate
2 min
560 rpm
drainage
continuously
Dewatering with no
1 min
560 rpm
drainage
Dewatering and
3 min
850 rpm
drainage
Dewatering with no
3 min
850 rpm
drainage
Inertial dewatering
1 min
and
15 s
Brake startup and
10 s
drainage
The table only discloses a running action and parameters in this embodiment. As for washing machines with different rated load capacities, the said running modes, durations and rotation speeds of the motor are different. Preferably, if the same model of washing machine has different load capacities, the said parameters are different.
Washing method in the invention largely reduces the water consumption. About 30% water can be saved for each washing. i.e., wash buffer with the same concentration needs less detergent. Hence, Water saving and detergent saving (relatively) can be achieved simultaneously. Pollution caused by drainage can be eased.
Of course, the invention is not limited to the said embodiments. As for technical schemes which are obvious to a person skilled in the art, in case of not separating from the spirit or scope of the invention, any modification or change to the invention is subject to the scope of Claims of the invention and corresponding substitution.
|
A washing machine contains a wash tub, an impeller and a motor. Clothing is put into the tub and the load is detected. Water is added until the water level is below or equal to the load height. To begin washing, the impeller drives the clothing to overturn, resulting in generating three types of water flows: agitating flow, enhancing flow and balancing flow. At first, the agitating flow breaks the balance of the load to disperse clothing, then the enhancing flow overturns clothing for washing. Finally, the balancing flow maintains the circulation path for the load balance overturning. Single sequential control or repeatedly alternating cycle control of the three types of water flows can be adopted for washing. The invention can save water, improve washing efficiency and avoid intertwining of clothing, characterized by full-range, thorough, repeated and efficient washing.
| 3
|
BACKGROUND OF THE INVENTION
The present invention relates to a car order selecting system for a railway train in which data series-connected transmitting devices are provided on the various cars.
Heretofore, the arrangement of railway cars having series-connected data transmitting devices has been fixed. A data transmitting device serving as the central station is installed on the front car and data transmitting devices serving as terminal station are installed on the following cars. Accordingly, the positional order of the data transmitting devices on the cars is physically fixedly determined, and therefore the data transmitting device serving as the central station carries out transmission control according to station numbers and the positional order of the data transmitting devices, which have been registered in advance in accordance with a polling selection transmission procedure.
FIG. 1 is a connection diagram of a railway car order selecting device of a type described, for instance, in "Collection of Railway Cybernetics Utilization Domestic Symposium Papers", vol. 19, pp. 496. As shown in FIG. 1, data transmitting devices 104a, 104b and 104c, corresponding to the first, second and third railway cars, are provided on railway cars 101, 102 and 103, respectively. These devices 104a, 104b and 104c are connected through transmitting lines 105. The train is fixedly formed by three cars, the first through third carriages.
The operation of the car order selecting device will be described. The data transmitting device on one (the front carriage 101 or 103) of the three cars 101 through 103 operate as the central station, and the remaining data transmitting devices serve as terminal stations. It is assumed that the first car 101 is the front car. In this case, the data transmitting device 104a is the central station. The central station 104a polls the terminal stations 104b and 104c successively to collect data from the terminal stations. The data thus collected is edited and displayed on a display unit 106a. The data thus displayed is transmitted to the terminal station through the transmitting lines 105 so as to be displayed on the display unit 106c. The terminal stations 104b and 104c have car number selecting switches (not shown) to determine their own station numbers (such as 2 and 3). Each terminal station transmits (automatic data) to the central station 104a only when requested to answer with its station number specified. However, since the cars are in the fixed formation, they must be arranged in the order of numbers.
As is apparent from the above description, the conventional car order selecting system is of the semifixed type in which the station numbers of the data transmitting devices are determined by operating selecting switches corresponding to the car numbers. Therefore, when trains are combined together, a plurality of data transmitting devices have the same station number, as a result of which it becomes difficult to transmit data between the data transmitting devices, and it is impossible to accurately detect the positions of the various cars in the train.
In a variable formation type train of more than two cars in which the front-to-rear direction of a car can be changed whenever it is connected, the central station on the front car cannot detect the numbers of terminal stations provided on the following cars or the station numbers and the positional order of the terminal stations. Therefore, the central station cannot communicate with the terminal stations, and cannot display data such as the name of equipment which is out of order and the position of the car having the equipment. Furthermore, in the case where it is required to provide some indication to the operator in response to the data of the data transmitting devices, even if it were possible to communicate with the data transmitting device, it would be impossible to communicate to the operator the correct data because the positional order of the data transmitting device is unknown.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to eliminate the above-described difficulties.
In accordance with the above object, in a variable formation type train, the central station is provided on the front car, and the registration order of the terminal station numbers of the following cars is accurately registered in the central station, whereby the data of the data transmitting devices can be correctly and quickly transmitted to the central station and displayed thereat.
More specifically, a car order selecting device of the invention comprises: extension lines which are connected into one line to apply a supply voltage to an adjacent data transmitting device; and logic circuits for selectively connecting the extension lines so that the station numbers of the terminal station data transmitting devices on the following cars are registered in the central station data transmitting device at the front car, whereby the positional order of the cars is determined.
In the car order selecting system of the invention, when the front car is selected, the data transmitting device on the front car functions as the central station, and a supply voltage is supplied successively to the data transmitting devices on the following cars through the extension lines having the logic circuits. Therefore, the data from the data transmitting devices on the following cars is correctly and quickly inputted to the central station data transmitting device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a connection diagram showing a conventional carriage order selecting system;
FIG. 2 is a connecting diagram of a preferred embodiment of the invention;
FIGS. 3(A) to 3(H) are diagrams for explaining the operation of the car order selecting device shown in FIG. 2; and
FIGS. 4 and 5 are connection diagrams showing other embodiments of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A preferred embodiment of the invention will be described with reference to FIG. 2. FIG. 2 shows a train composed of three cars; however, it should be noted that the arrangements and functions described below are applicable to the case also where more than three cars form a train.
In FIG. 2, reference numeral 1 designates the first car, which is the front car in the train; 2 and 3, the second and third cars, which are the following cars; and 4a, 4b and 4c, data transmitting devices installed on the cars 1, 2 and 3, respectively, the devices being used to transmit data from the respective cars to one another through data transmitting lines 5, which are connected to the data transmitting devices 4a, 4b and 4c. It is assumed that the train runs in the direction of the arrow (to the left in FIG. 2), and the data transmitting device 4a on the first 1 serves as the central station while the data transmitting devices 4b and 4c on the following cars 2 and 3 serve as terminal stations.
Further in FIG. 2, reference numeral 6 designates extension lines provided for each data transmitting device, the lines 6 being connected to the data transmitting devices on the immediately front and rear cars, respectively, and are used to connect a power source 7 to each car; 7, the power sources provided on the cars 1 through 3, respectively, each power source being used to selectively apply signals to the data transmitting devices on the front and rear cars from the transmitting devices on the front and rear cars from the transmitting device on a given car; 8a, 8b and 8c, selecting relays, namely, head control relays which transmit input signals to the data transmitting devices 4a, 4b and 4c to select the front car so that the data transmitting device on the front car thus selected becomes the central station; and 9a, 9b and 9c, and 10a, 10b and 10c, control relay coils and control relay contacts which form respective control relays. Each control relay is used to supply, when the data processing operation in the central station (data transmitting device) 4a is accomplished or the data processing operation (registration of a predetermined station number with respect to the central station and a predetermined car number, etc.) in the terminal stations (data transmitting devices) 4b and 4c is accomplished, a start output signal to the terminal station on the next car to cause the latter to start data communication with the central station 4a.
Further in FIG. 2, 11a, 11b and 11c, and 12a, 12b and 12c designate signal receiving relays receiving the start output signal when the supply voltage 7 is applied through the control relay contacts 10a, 10b and 10c. The signal receiving relays together with the control relays 9a through 9c and 10a through 10c form logic circuits for connecting the extension line 6 selectively to the data transmitting devices 4a, 4b and 4c. Monitoring display units 40a, 40b and 40c are connected to the data transmitting devices 4a, 4b and 4c, respectively.
The operation of the car order selecting device thus constructed will be described with reference to FIGS. 2 and 3. When the car 1 is selected as the front car, the selecting relays 8a is turned on (FIG. 3, (A)). Upon detection of this operation, the data transmitting device 4a turns on the control relay 9a and 10a (FIG. 3, (B)) to start the data transmitting device on the front or rear car, i.e., the data transmitting device 5b on the rear car 2 in this case. As a result, the signal receiving relay 11b is turned on by the power source 7 (FIG. 3, (C)), whereupon data can be transmitted between the data transmitting device 4b and the central station data transmitting device 4a. The data transmitting device 4b, as indicated by a signal X in waveform (D) of FIG. 3, registers the number of the car 2 and the position of the car 2 from the front car in the data transmitting device 4a through the transmitting lines 5, Of course, the car number has been inputted in the data transmitting device 4b, and the position of the car is counted with a signal from the data transmitting device 4a.
Next, the data transmitting device 4a informs the data transmitting device 4b of the fact that the data transmitting device 4b has been connected to the data transmitting device 4a and the car number, etc., have been registered (the signal Y in waveform (E) of FIG. 3). The data transmitting device 4b transmits a confirmation signal Z to the central station data transmitting device 4a to end the communication. (The transmission of the confirmation signal Z may be omitted.)
In order to start the data transmitting device 4c on the following car 3, the data transmitting device 4b turns on the control relays 9b and 10b (FIG. 3, (F)), and the signal receiving relay 11c (FIG. 2, (G)). The signal from the signal receiving relay 11 allows data communication between the data transmitting device 4c and the central station data transmitting device 4a. Under this condition, the data transmitting device 4c transmits a transmission signal X' to register the number of the car 3, etc., in the central station data transmitting device 4a (FIG. 3, (H)). Upon reception of the signal X', the central station data transmitting device 4a registers the number of the car 3 and the fact that the position of the car 3 is the third from the front car 1, and transmits a completion signal Y' to the data transmitting device 4c (FIG. 3, (E)). The data transmitting device 4c transmits a confirmation signal Z' to the central station data transmitting device 4a. (The transmission of the confirmation signal Z' may be omitted.) The control relay 9c and 10c of the data transmitting device 4c is operated to determine whether or not there is a car after the car 3. In the case of a train of three cars, the detection of the following car is ended. In the case where it is determined that the car 3 is followed by another car, the number of the car is registered in the same manner. Thus, in the case of a train of more than two cars, merely by selecting the front car 1, the data transmitting devices 4a, 4b and 4c are started successively, and the position of each car is registered. Therefore, the conditions of all the cars can be comprehended through the display unit 40a of the central station data transmitting device 4a.
FIG. 4 shows another embodiment of the invention. In FIG. 4, elements corresponding functionally to those already described with reference to FIG. 2 are designated by the same reference numerals or characters. Further in FIG. 4, 13a, 13b and 13c designate signal receiving relays corresponding to the signal receiving relays 11a, 11b and 11c, and 12a, 12b and 12c. Diode circuits 14a, 14b and 14c are connected between the power sources 7 of the cars and the signal receiving relays 13a, 13b and 13c, respectively. Each diode circuit is a parallel circuit of two series circuits of diodes, the forward direction being from the power source 7 towards the signal receiving relay (13). The connecting points of these diodes are connected to the extension lines 6.
The operation of the second embodiment shown in FIG. 4 is completely the same as that of the first embodiment shown in FIG. 2. For instance, in the case where the car 1 is the front car and the data transmitting device 4a serves as the central station, the control relay contact 10a is closed. Therefore, the power source 7 is connected through the control relay contact 10a and the diode circuits 14a and 14b to the signal receiving relay 13b to close the latter, as a result of which data can be transmitted between the data transmitting device 4b and the central station 4a. When, after communication, the control relay contact 10b of the data transmitting device 4b is closed, similarly, the power source 7 is connected through the diode circuits 14b and 14c to the signal receiving relay 13c to close the latter 13c so that data can be transmitted between the data transmitting device 4c and the central station 4a. In starting the data transmitting devices of the following cars successively, similar to the case of FIG. 1, the power sources 7 are connected to the data transmitting device of the instant car and the data transmitting device of the front carriage; however, no problem is caused because both the data transmitting devices have been started already. However, control may be effected by the central station so that the start signal is applied selectively to the data transmitting devices.
FIG. 5 shows a third embodiment of the invention in which selecting relays 8a, 8b and 8c (head control relays) are employed as power supplying relay contacts. When the front car 1 is selected, the selecting relay 8a is closed. As a result, the power source 7 is connected to the extension line 6, and the power is applied through the signal receiving relay 11a to the data transmitting device 4a so that the latter operates as the central station. When the control relay contact 10a is closed, the extension line for the adjacent, following car is connected. Therefore, the data transmitting device 4b is started through the signal receiving relay 11b. Continuing this way, the data transmitting devices are started successively. Therefore, power is supplied from the front car 1 through the extension lines 6 to all other cars.
In FIGS. 2, 4 and 5, the leftmost car is the front car of the train. In the case where the rightmost car is the front car, the data transmitting devices of the cars are successively started beginning from the rightmost one in the same manner, and the identifying numbers of the cars are registered in the central station data transmitting device 4c in this case. In any case, the front car is at the end of the train. Therefore, even if a plurality of cars output signals through the extension lines 6 at the same time, the data transmitting devices are successively started beginning from the one on the front car; that is, the data transmitting devices are started in the order of connection of the cars.
The aforementioned signal receiving relays 11a, 11b and 11c, and 12a, 12b and 12c, and the above-described signal receiving relays 13a, 13b and 13c, may be incorporated in the digital circuits (not shown) of the data transmitting devices.
As described above, according to the invention, the data transmitting devices on the following cars are started through extension lines which are connected into one line and include logic circuits. Therefore, the inventive car order selecting system can be readily constructed at a low cost. Accordingly, the data transmitting devices in a train of more than two cars can be successively started without interference, and the positional order of the cars can be correctly detected.
|
A railway car order selecting system in which data representing the positional order of the various cars of a train and other data is accurately communicated to a central station regardless of the particular arrangement of the cars. A selecting relay applies an input signal to one of plural data transmitting devices, one being located on each car, to select a front car of the train. Extension lines connected into a single line connect the data transmitting devices to one another and are used for selecting the car order. Logic circuits are provided for the extension lines to supply, in response to an output signal from the respective data transmitting devices, a supply voltage to the following data transmitting device. Selection of the front car in this manner results in starting the data transmitting devices on the following cars successively and registering the positional order of the following cars in the data transmitting device at the front car.
| 1
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national phase patent application of PCT/DE02/02538, which was filed Jul. 11, 2002, and claims priority to and the benefit thereof and of German patent application no. 10133029.4, which was filed in Germany on Jul. 11, 2001, the disclosures of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to a method and a device for predicting movement trajectories of a vehicle to prevent a collision or reduce the severity of the crash, in which for predicting the movement trajectories, only those trajectories are considered for which, because of a combination of steering intervention and braking intervention, the forces occurring at the wheels of the vehicle are, e.g., as great as the force transferable at a maximum from the wheel to the road. Particularly for systems which provide an automatic braking and/or steering intervention for avoiding a collision with another vehicle, an automatic braking and/or steering intervention is carried out as a function of the pre-calculated movement trajectories.
BACKGROUND INFORMATION
In recent years, adaptive cruise controllers have increasingly come on the market which expand the conventional control of a vehicle-speed controller to the effect that the distance and relative velocity of the preceding vehicle are detected by a radar or lidar system, and this data is utilized for the speed control and/or distance control of one's own vehicle.
Such a system is described in the paper “Adaptive Cruise Control System—Aspects and Development Trends” by Winner, Witte et al., SAE paper 96 10 10, International Congress and Exposition, Detroit, Feb. 26-29, 1996.
In the publication “A Trajectory-Based Approach for the Lateral Control of Vehicle Following Systems” by Gehrig and Stein, presented at the IEEE International Conference on Intelligent Vehicles, 1998, an algorithm is described, which, from the measured data of a radar or lidar sensor, creates a movement trajectory of the preceding vehicle, and controls one's own vehicle according to it. Particularly for movements in which both vehicles are driving into or out of a curve, special demands are made on such a trajectory algorithm. An algorithm of this type for determining movement trajectories is presented by way of example in the aforesaid document.
In the book “Fahrwerktechnik: Fahrverhalten” by Zomotor, from Vogel Book Publishing, Würzburg, first edition 1987, in chapter 2, “Forces on the Vehicle”, the theoretical fundamentals are explained which are necessary for understanding the transfer of force between tire and roadway.
SUMMARY
When pre-calculating all possible movement trajectories of a preceding vehicle or of one's own vehicle, great demand for computing power may be made on the prediction system for pre-calculating the further movement. This may be because a great number of possible movements of the vehicle may be taken into account. Particularly in dangerous situations, in which a strong deceleration or a sharp steering movement may be expected, this large number of possible movements may increase even further. Since in this case, a real-time processing of the movement trajectories may be desired, it may be necessary to use a powerful computer system.
In this context, it may be provided in calculating the movement trajectories, which in the case of an imminent collision may result from steering operations, braking operations or combined steering and braking operations, to be able to calculate them in advance. To minimize the computing expenditure, it may be provided that only those trajectories be pre-calculated for which, because of a combination of steering intervention and braking intervention, the force occurring at the wheels of the vehicle is in the range of the maximum force transferable from the wheel to the road. It may be assumed that, in response to driving through one of these trajectories, the imminent collision with an object may be prevented, or, in the event that a collision may not be avoidable, it may at least be possible to reduce the severity of the crash. To be understood by crash severity is, in this case, the extent of damage from the collision, which may be dependent on the impact energy, but also, for example, on the constitution of the object. Thus, for example, given equal impact energy, the crash severity for a collision with a concrete wall may be greater than for a collision with a preceding vehicle.
This method for pre-calculating movement trajectories may be used on one's own vehicle that is equipped with a radar, lidar or video system, but also on other vehicles detected by the surroundings sensor system.
It may be provided that the surroundings sensor system is composed of a radar sensor, a lidar sensor, a video sensor, etc., or a combination thereof. If a vehicle is equipped with more than one surroundings sensor, it may be possible to ensure a more reliable and higher-resolution detection.
Moreover, it may be provided that the maximum force transferable from the wheel to the road may be corrected as a function of an instantaneous situation. In particular, this maximum transferable force may change due to wetness or snow on the roadway. To ascertain the instantaneous roadway coefficient of friction, which co-determines the maximum force transferable from the wheel to the road, the signals from an anti-lock device and/or an electronic stability program may be utilized. Moreover, it is also possible that signals from further surroundings sensors, such as a rain sensor or a poor-weather detection, may be utilized by the radar, lidar or video sensor system for determining the instantaneous wheel-slip value.
In addition, it may be provided that the predicted movement trajectories may be used for the automatic control of the deceleration devices and/or for the automatic control of the vehicle steering devices, in order to avoid an imminent collision with a preceding vehicle or object.
The method according to the present invention may be implemented in the form of a control element provided for a control unit of an adaptive distance and/or speed control of a motor vehicle. In this context, the control element has stored on it a program that may be executable on a computing element, e.g., on a microprocessor, an ASIC, etc., and may be suitable for carrying out the method of the present invention. Thus, in this case, the present invention may be realized by a program stored on the control element, so that this control element provided with the program may constitute an example embodiment of the present invention in the same manner as the method, for whose execution the program may be suitable. An electrical storage medium, e.g., a read-only memory, may be used as control element.
Further features, uses and aspects of the present invention are described in the following description of exemplary embodiments of the present invention which are illustrated in the drawings. In this context, all of the described or represented features, alone or in any combination, form the subject matter of the present invention, regardless of their combination, as well as regardless of their formulation and representation in the following description and drawings, respectively.
In the following description, exemplary embodiments of the present invention are explained with reference to the Drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of the forces which may occur at a maximum on a wheel without it losing its road adhesion.
FIG. 2 illustrates a traffic situation in which the method of the present invention may be used.
FIG. 3 illustrates a braking force/time diagram of the trajectories illustrated in FIG. 2 .
FIG. 4 illustrates the evasion paths of the various trajectories illustrated in FIG. 2 .
DETAILED DESCRIPTION
FIG. 1 illustrates a construction in which forces 3 , 4 , 7 occurring at a wheel 1 are indicated. This construction is referred to by the name Kamm circle. The plan view illustrates a wheel 1 through which a dot-dash line 5 is drawn in the longitudinal direction, and a dot-dash line 6 is drawn in the transverse direction. The forces which occur between a wheel and the roadway may be divided into the longitudinal direction, thus parallel to dot-dash line 5 , and the transverse direction, thus parallel to dot-dash line 6 . The additionally occurring vertical force, resulting due to the weight of the vehicle, is not indicated. A force arrow 3 , representing the longitudinal forces acting on the tire, is illustrated in parallel to line 5 . These longitudinal forces are generally deceleration and acceleration forces which influence the vehicle in the straight-ahead direction. Moreover, a force arrow 4 is marked in which acts parallel to transverse line 6 . These lateral forces, represented by this force arrow 4 , develop due to steering movements of the vehicle, and cause the vehicle to change direction. A force arrow 7 is also illustrated which represents the diagonal of a rectangle that is constructed on the two force arrows 3 and 4 . This force arrow 7 represents the resulting force of both individual forces 3 , 4 in the longitudinal and transverse directions. Thus, force arrow 7 represents a position or radius vector with origin in the point of intersection of lines 5 and 6 , the length and direction of which are determined by the amounts of the individual components longitudinal force 3 and transverse force 4 . If one plots in this construction all points at which the resultant force of the longitudinal and lateral forces is the same amount as the product of the maximum coefficient of friction between roadway and tire μmax and vertical force Fn acting on the wheel, then one obtains a circle the center point of which corresponds to the point of intersection of lines 5 and 6 . If force 7 resulting from longitudinal force 3 and transverse force 4 is greater according to the amount than the product μmax*Fn, then the end of the position vector of the resulting force is outside of constructed circle 2 . In this case, the wheel has already lost its adhesion to the roadway. If one would like to move a vehicle such that the adhesion of the wheels to the roadway is present at any time, then it may be necessary that the adhesion of the wheels to the roadway is present at any time. Thus, it may be necessary to assure that resultant force 7 from longitudinal force 3 and transverse force 4 is smaller according to the amount at each point of time than circle 2 constructed due to the coefficient of friction and the vertical force.
FIG. 2 illustrates a possible traffic situation. One sees a road 8 upon which two vehicles 9 , 10 are moving. The movements of vehicles 9 , 10 are indicated by velocity arrows v 1 , v 2 . Vehicle 9 following preceding vehicle 10 is equipped with a device according to the present invention for carrying out the method according to the present invention. If velocity v 1 of vehicle 9 is very much greater than velocity v 2 of vehicle 10 , then in this case there may be a risk of collision, since distance 15 between the two vehicles may not be sufficient to avoid this collision by a maximum possible deceleration of vehicle 9 . If in this case an automatically triggered emergency braking were used, then a trajectory as represented by single-dotted arrow 13 may result for the further vehicle movement. In this case, it may be possible that distance 15 between the two vehicles 9 and 10 may not be sufficient to come to a standstill in time. In the event of such a full-brake application without steering movement, longitudinal force 3 may assume a maximum value μmax*Fn. Lateral force 4 may be equal to zero.
Another possibility for avoiding a collision in the traffic situation described may be a pure evasion maneuver. In this case, one may not carry out a braking intervention, but rather may provide as sharp a steering angle as possible. Such a procedure is represented by double-dotted movement trajectories 11 and 12 . In this case, one may have a longitudinal force 3 equal to zero and a maximum transverse force 4 in the construction of Kamm circle 2 . During this maneuver, it may easily happen that, due to too sharp a steering angle, the maximum possible lateral force may be exceeded and the vehicle may go into a spin. A combined braking and steering intervention, as is represented by triple-dotted movement trajectory 14 , may be provided in the traffic situation illustrated. To clarify the combined braking and steering intervention, reference is made to FIG. 3 . In FIG. 3 , a braking force/time diagram is illustrated in which the time is plotted on abscissa 16 , and the braking force is plotted on ordinate 17 . For the case of a full brake application as is represented in FIG. 2 by single-dotted movement trajectory 13 , a braking force/time diagram may result as is represented by single-dotted line 18 . In the case of the emergency braking, this may be a horizontal line which may correspond to a maximum possible, constant braking-force value. The second alternative from FIG. 2 , an evasion maneuver, as is represented by double-dotted movement trajectories 11 and 12 , may correspond to double-dotted curve 19 in the braking force/time diagram illustrated in FIG. 3 . In this case, the braking force over the time constant may amount to the value zero, since there may be no deceleration of the vehicle. The combined braking and steering maneuver, e.g., carried out by the vehicle, according to triple-dotted movement trajectory 14 is represented in the braking force/time diagram illustrated in FIG. 3 as a triple-dotted curve. In this case, there may be a very sharp deceleration at first, which may mean the braking force at small times has a high value. In the further course, curve 20 falls off, since the intensity of the deceleration is reduced in order to go over to a steering intervention. Through this combination of braking and steering, in a first phase in which braking force is high, velocity v 1 of vehicle 9 is sharply reduced, in order to then carry out a steering maneuver in a second phase with only weak deceleration force, to avoid a collision with vehicle 10 .
FIG. 4 illustrates a further diagram in which lateral evasion path y is plotted against longitudinal path x. In one partial area of this y-x diagram, a hatched area 26 is illustrated which represents the obstacle. This area 26 represents the region which the evasion trajectory may not touch, in order to prevent a collision. In the case of a full brake application according to movement trajectory 13 from FIG. 2 , a single-dotted curve 23 , which indicates the spatial movement of the vehicle, results in this y-x diagram. Since in this case no steering maneuver takes place, this single-dotted line 23 is on the x axis. Because of small distance 15 between both vehicles 9 and 10 , as of point 27 , line 23 touches hatched area 26 which represents the obstacle. As of this point of time, there is a collision of vehicle 9 with the object, vehicle 10 in the case illustrated.
The pure steering maneuver as is illustrated in FIG. 2 by double-dotted movement trajectories 11 and 12 is represented in the y-x diagram of FIG. 4 as a double-dotted line 24 . Value y increases continually as a function of path x, which includes the cornering of vehicle 9 . As of value 27 , line 24 also touches hatched area 26 which represents the obstacle. A collision of both vehicles 9 and 10 may occur in this case, as well.
The combined braking/steering maneuver according to triple-dotted movement trajectory 14 is illustrated in the y-x diagram of FIG. 4 as a triple-dotted line 25 . The initially weak steering movement, but strong braking deceleration, causes curve 25 to run very flat at the beginning, but as it continues it increases very sharply in the direction of greater y-values, since the braking deceleration is reduced and the steering intervention is intensified. Due to a strongly reduced initial velocity, it is possible to later carry out a sharper steering movement than is represented by line 24 . In this case, it is possible to prevent the collision of the two vehicles.
The method of the present invention may calculate all possible movement trajectories which are between the two extreme trajectories illustrated, namely, on one hand, a pure full brake application without steering intervention 13 , and on the other hand, a maximum possible steering movement without braking intervention 11 or 12 . However, all the calculated trajectories may have in common that the forces affecting the wheels correspond, e.g., to the forces arranged on the Kamm circle.
In this context, a great number of possible movement trajectories may be possible. The trajectories which, within their course, have points at which the force resulting from the longitudinal and lateral components becomes considerably greater or considerably smaller than is permitted by the Kamm circle illustrated in FIG. 1 remain unconsidered. The computing expenditure for trajectory estimation may thereby be reduced considerably. In these cases, the considered trajectory may lead to a loss of wheel adhesion on the road. Accordingly, those movement trajectories may prove to be actually useful and executable which, viewed over their entire further course, only just have a sufficient frictional grip of the wheels on the roadway at each point of time.
The frictional grip of the wheel on the roadway is variable due to changes in the weather conditions or the outside temperature. To take these changes of the coefficient of friction μmax into account, the radius of Kamm circle 2 is constantly updated. This is accomplished, for example, by taking into account the outside temperature, by taking into account the weather conditions, in that a signal from a rain sensor is supplied, and in that interventions of an anti-lock device or an electronic stability program are evaluated, and changes in the coefficient of friction are passed on to the automatic emergency braking system.
|
In a method and a device for predicting movement trajectories of a vehicle to prevent or reduce the consequences of an imminent collision, in which for predicting the movement trajectories, only those trajectories are considered for which, because of a combination of steering intervention and braking intervention, the forces occurring at the wheels of the vehicle are within the range corresponding to the maximum force transferable from the wheel to the road. Particularly for systems which provide an automatic braking and/or steering intervention for avoiding a collision or reducing the severity of a crash with another object, an automatic braking and/or steering intervention is carried out as a function of the pre-calculated movement trajectories.
| 1
|
TECHNICAL FIELD
This invention relates to the field of transportation, and particularly to apparatus for electrically interconnecting the towing and towed components of an articulated land vehicle, such as a car and a house; horse; or boat-trailer drawn thereby.
BACKGROUND OF THE INVENTION
All automotive vehicles are now equipped with electric lights at their rear ends, including left turn and right turn lights and a tail light which also functions as a stop light. When it is desired to draw a trailer behind a vehicle, the trailer masks the signal lights of the towing vehicle, and so the lights must be duplicated at the rear of the trailer, and electrical connections must be made to the lighting circuits of the car, to operate the trailer lights, as well.
Standard male and female multi-conductor connectors have been developed for this purpose. There has, however, been no standard system agreed on for connecting the conductors of a car or those of a trailer to particular contacts in the standard connectors. Accordingly, the owner of a car having an electrical socket for connection to a first trailer cannot count on being able to connect that socket to the plug of some other trailer.
SUMMARY OF THE INVENTION
The present invention comprises a circuit interchange by means of which the plug of any trailer may be connected to the socket of any car. This is accomplished by arranging male and female connector elements in a matrix of mutually orthogonal rows, and interconnecting the elements so that effective order is different in different rows.
Various advantages and features of novelty which characterize the invention are pointed out with particularity in the claims annexed hereto and forming a part hereof. However, for a better understanding of the invention, its advantages, and objects obtained by its use, reference should be had to the drawing which forms a further part hereof, and to the accompanying descriptive matter, in which there are illustrated and described certain preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawing, in which like reference numerals indicate corresponding parts throughout the several views,
FIG. 1 is a perspective view of an articulated land vehicle where the invention is to be used;
FIG. 2 gives the details of the circuitry for a towing vehicle and a towed vehicle, to illustrate the problems solved by the invention;
FIGS. 3, 4, and 5 give details of a first embodiment of a circuit interchange according to the invention;
FIG. 6 is a view like FIG. 3 showing a second embodiment of the invention;
FIG. 7 shows how a portion of the interchange may be made a permanent part of a towing vehicle; and
FIG. 8 shows a convenient accessory.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows an articulated land vehicle to comprise a towing vehicle 20 and a towed vehicle 21. While a private car is shown towing a utility trailer in this Figure, it will be realized that other towing vehicles, such as vans or trucks, can be used with the invention, while drawing other towed vehicles, such as house-trailers, boat-trailers, or horse-trailers.
FIG. 2 shows the towing vehicle 20 including a right turn light 22 energized through a conductor 23, a left turn light 24 energized through a conductor 25, and a tail and stop light 26 energized through a conductor 27. The circuits to these lights are completed in the towing vehicle by ground connections, one terminal of the car battery being conventionally grounded.
Towing vehicle 20 is shown with a standard trailer connection socket 30 having female connector elements 31, 32, and 33, connected by conductors 34, 35, and 36, respectively, to conductors 23, 25, and 27, and a male connector element 37 grounded by a conductor 38.
Towed vehicle 21 is shown to have a right turn light 40, a left turn light 41, and a tail and stop light 42, having first terminals grounded. A standard trailer connection plug 43 is shown to have male connector elements 44, 45, and 46 connected by conductors 47, 50, and 51 with lights 40, 41, and 42, respectively, and a female connector element 52 grounded by a conductor 53.
The connector elements of plug 43 are physically arranged to inter-engage with the connector elements of socket 30. It will be evident, however, that if this is done directly the trailer lights will not be properly coordinated with the lights of the towing vehicle, right turn light 40 of the towed vehicle being energized at the same time as left turn light 24 of the towed vehicle, for example. The ground connection will be properly made, because this is a standard connection throughout the industry. A circuit interchange 54, according to the invention, is provided to enable proper correlation between the lights of the vehicles, and includes a plug end 55 to engage vehicle socket 30 and a socket end 56 to receive trailer plug 43.
FIG. 4 shows that interchange 54 may be constructed in modular form, plug end 55 and socket end 56 being integrated or encapsulated into a unitary structure. FIG. 5 shows that the plug and socket ends of interchange 54 may be physically separate, the connector elements being interconnected by a cable 57. In either case, socket end 56 comprises a body of insulating material in which are disposed a matrix of male and female connection elements arranged in orthogonal rows comprising three female elements and one male element each. FIG. 3 shows a top row to include female elements 60, 61, 62 and male element 63, a second row to include female elements 64, 65, 66 and male element 67, a third row to include female elements 70, 71, and 72 and male element 73, and a fourth row to include male elements 74, 75, and 76. Considered as vertical rows, a left hand row comprises female elements 60, 64, 70 and male element 74, a second row comprises female elements 61, 65, 71 and male element 75, a third row comprises female elements 62, 66, 72 and male element 76, and a right hand row comprises male elements 63, 67, and 73. The spacings between the connector elements in the vertical and horizontal rows is in accord with the spacing of the contacts of standard socket 30. The physical dimensions of socket end 56 are also in accord with the structure of a standard plug 43, female elements 60, 61, 62, 64, 65, 66, 70, 71, and 72 being on a raised boss 77 and male connector elements 63, 67, 73, and 74, 75, and 76 being on ledges 80 and 81 below boss 77. A pedestal 82 at the same level as boss 77 prevents the attempted mating of a plug with the bottom row or the right hand row of connector elements.
As a part of socket end 56, female connector elements 60, 65, and 72 are inter-connected, as are connector elements 64, 71, and 62 and connector elements 70, 61, and 66. Male elements 63, 67, 73, 76, 75, and 74 are all interconnected.
Plug portion 55 comprises a single row of connector elements, male elements 83, 84, and 85 being at a principal level 86 and female element 87 being at a raised level 90. Conductors 91, 92, 93, and 94 interconnect female connector elements 83 and 60, 84 and 64, 85 and 70, and male connector elements 87 and 74. These conductors may be integral in the embodiment of the invention shown in FIG. 6. In the embodiment of FIG. 5 these conductors comprise cable 57.
If plug portion 55 is connected to towing vehicle socket 30, female connector elements 60, 65, and 72 will be connected to right turn light 22, female connector elements 64, 71, and 62 will be connected to tail light 26, female connector elements 70, 61, and 66 will be connected to left turn light 24, and elements 74, 75, 76, 73, 67, and 63 will be grounded. Using the letters R, T, L, and G to stand for the right turn, tail, left turn, and ground circuits, and reading the rows toward the ground connectors in each case, every possible permutation of the three circuits can be found, the horizontal rows from top to bottom reading RLTG, TRLG, and LTRG, and the vertical rows from left to right reading RTLG, LRTG, and TLRG.
Inspection of FIG. 2 shows that trailer plug 43 reads TLRG. To properly connect the trailer lights to the towing vehicle lights through the interchange, it is therefore only necessary to insert plug 43 into socket 56 in the right hand vertical row of contacts. Other trailer plugs having different wiring arrangements can readily be accepted by using the proper horizontal or vertical row of contacts in socket end 56. It is perfectly safe to do this by a trial and error method, plug 43 being inserted into socket end 56 in various positions at random and shifted from one to another until the trailer lights agree with those of the towing vehicle in every respect.
Attention is now directed to FIG. 6, which shows a modified embodiment of the socket end of interchange 54. This contains the nine female connector elements on the common boss, as before, and the associated six male connector elements at first ends of the rows on ledges 80 and 81. However, in this embodiment, six further male connector elements 101-106 are provided, at the ends of the rows opposite to the first male connector elements, further ledges 107 and 108 and further pedestals 110, 111, and 112 being provided.
This arrangement gives a measure of redundancy to the interchange, as each sequence is now available in two different positions of plug 43. The plug can be inserted into any row in either of two opposite orientations, giving double the number of plug positions, and hence doubling the occurrence of each combination. Thus, RLTG is available either at the top horizontal row using ground contact 63, or at the right hand vertical row using ground contact 106. Mechanical failure or damage to any one contact element does not require replacement of the entire interchange under these circumstances.
It will be evident that availability of an interchange according to the invention enables the proper connection of any trailer plug to any vehicle socket.
FIG. 7 shows that if desired a socket portion 113 of the interchange may be substituted for the usual vehicle socket, and connected to the vehicle wiring through a cable 114, thus, avoiding the need for a separate complete interchange.
As an added convenience it is possible to modify plug 55 of FIG. 5, as shown in FIG. 8, by encapsulating therein three light emitting diodes 120, 121, and 122 and three resistors 123, 124, and 125. Each diode is connected in series with a resistor, the resistors are all connected to female connector element 87, and the diodes are connected to male connector elements 83, 84, and 85, respectively. Any defect in the vehicle wiring to socket 30 can be detected by lack of operation of a light emitting diode. As a further convenience the boss 77, shown in FIG. 3, can be provided with embossed numbers 1 to 6 opposite the six rows of female elements. The numbers provide the user with plug position references.
From the foregoing it will be evident that the invention comprises a circuit interchange for use in connecting the lights of a towing vehicle to those of a towed vehicle, so that a functionally correct interconnection can be made regardless of the particular wiring arrangement of the vehicles, plugs, and sockets.
Numerous advantages and characteristics of the invention have been set forth in the foregoing description, together with details of the structure and function of the invention, and the novel features thereof are pointed out in the appended claims. The disclosure, however, is illustrative only, and changes may be made in detail, especially in matters of shape, size, and arrangement of parts, within the principle of the invention, to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
|
A circuit interchange for interconnecting towing and towed components of an articulated land vehicle, including a socket having an array of male and female connector elements so positioned and interconnected that by proper orientation of a trailer plug in the socket the trailer lights can be properly coordinated with the towing vehicle lights regardless of the wiring systems to the plug and socket. The interchange may be modular or in jumper form, or may be in part permanently substituted for the socket of the towing vehicle.
| 7
|
FIELD OF THE INVENTION
[0001] The invention relates to a guiding system for an intermittent aerobic exercise system and method. Particularly, the invention provides a device guiding an intermittent aerobic exercise system in intervals of moderate or strong intensity.
BACKGROUND OF THE INVENTION
[0002] Aerobic metabolism refers to a method of producing energy in a body by a process requiring oxygen. Whenever the available amount of oxygen-based energy fails to meet the demand, an anaerobic state occurs where energy is produced by a process that does not require oxygen, but may result in an oxygen debt.
[0003] Aerobic exercise is physical exercise of moderate to high intensity over a long period of time, which mainly uses the energy generated from aerobic metabolism and consumes fat and glycogen in the body. Aerobic exercise can improve heart and lung capacity, and it has also been widely used for weight loss because it can burn fat. Aerobic exercise includes, for example, jogging, cycling, boating, skiing, skating, jumping rope, swimming, walking, rhythmic gymnastics, climbing and so on. The general definition of aerobic exercise such as jogging is exercise maintaining the same heart rate (HR) intensity for more than 15 minutes. The continuous moderate endurance (CME) refers to the heart rate maintained at the same heartbeat intensity for 15 minutes or maintained at moderate intensity (50 to 70% of the maximum heart rate). Besides high intensity interval training (HIIT) including intervals of warm up and high intensity (75% to 100% of the maximum heart rate) is a precise workout regimen for health. There is a need in how to guide users to conduct aerobic exercise during exercise without producing too much oxygen debt. In sports and exercise testing, the Borg Rating of Perceived Exertion (RPE) Scale measures perceived exertion. There is grossly ranking of 6 to 7 easy 8 to 9 very light 10 to 11 light 12 to 13 somewhat hard 14 to 15 hard 16 to 17 very hard 18 to 19 extremely hard 20 maximal exertion. The score of 6 to 20 is to follow the general HR of a “healthy” adult by multiple by 10. While the two parameters are not consistent during exercise, physical problem may be concerned during exercise. Double-checking of the two parameters during exertion workout is crucial for health and safety.
[0004] U.S. Pat. No. 7,828,697 relates to a portable personal training device including an operable geographic location determining component to determine the location of the device, where a housing having a first portion and a second portion coupled to the first portion is at an angle, and a strap operable to secure the housing to a user's wrist such that the first portion is operable to be positioned on top around the wrist and the second portion is operable to be positioned offset from the top of the wrist. Such configuration facilitates both the wearing and the operation of the device. U.S. Pat. No. 7,789,802 provides a physical training device using GPS data to assist a user in reaching their performance goals and completing training sessions by tracking their performance, by communicating progress including progress relative to user-defined goals, by communicating navigation directions and waypoints, and by storing and analyzing training session statistics. U.S. Pat. No. 8,033,959 further provides a portable fitness monitoring system that includes: a portable fitness monitoring device; a sensor that communicates with the portable fitness monitoring device to sense the performance parameters during physical activity conducted by the user and communicates the performance parameter data to the dedicated portable fitness monitoring device; a music device directly coupled to the portable fitness monitoring device; and an audio output device directly coupled to the portable fitness monitoring device, wherein music is transmitted from the portable music device to the audio output device through the portable fitness monitoring device.
[0005] US20110151420A1 provides a convenient device (such as a mobile phone) providing a user interface for a system that generates personalized exercise programs and guides users through the exercises in a generated program. US20110077130A1 provides an exercise assistance device that includes: a first acquisition unit which acquires plural pieces of exercise scene information representing a scene when an exercise motion is performed and plural pieces of motion information representing the exercise motions, the plural pieces of exercise scene information being associated with the plural pieces of motion information; a second acquisition unit which acquires plural pieces of exercise order information which describes an order to perform the exercise motions corresponding to the exercise scene information; a first selection unit which selects one of the pieces of exercise order information acquired by the second acquisition unit; a decision unit which decides, from plural pieces of motion information, the motion information corresponding to the exercise scene information included in the exercise order information selected by the first selection unit; and a generation unit which generates a display signal to display the motion information decided by the decision unit on a display unit. Taiwan Patent Laid-open NOs 403668 and 403669 detect body fat rate prior to exercise and determine a target body fat rate; an exercise program should be decided to determine what load level, what frequency of exercise, and what continuous time for the exercise so that the load of exercise meets the program. Although the above prior art teaches guiding aerobic exercise system, it can only reach the effect of common aerobic exercise and cannot guide user to perform aerobic exercise that can improve metabolism.
[0006] Current exercise programs have not been subjected to precise evaluation, so whether the exercise can improve metabolism and aging cannot be ascertained. Therefore, there is a need to develop an aerobic exercise system that can improve metabolism and is beneficial to health.
SUMMARY OF THE INVENTION
[0007] If a high intensity maximum heart rate (75% to 100%) is used as a target interval during exercise, it is effective in resisting metabolic diseases; however, the exercise cannot be continuously performed over a long period of time. Moreover, it needs a graded elevation and a recovery interval with a lower intensity maximum heart rate (40% to 70%) between two high intensity intervals. The graded intervals having high and low intensities for fixed times refer to aerobic interval training or high intensity interval training, which have better efficacy in reducing blood pressure and blood sugar, strengthening the heart and burning fat than aerobic exercise of continuous moderate endurance. Accordingly, the invention provides a system and method that guides a user to perform an intermittent aerobic exercise in moderate or strong intensity interval(s) preferably with a warm-up period for gradually elevating HR intensity to a target zone, and the inventor surprisingly found that the user performing the exercise guided by the system and method of the invention can improve metabolism and thus attain better health.
BRIEF DESCRIPTION OF THE DRAWING
[0008] FIG. 1 shows a block diagram illustrating elements of the intermittent aerobic exercise system as one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0009] In one aspect, the invention provides an intermittent aerobic exercise system, comprising:
(a) a heart rate sensor unit for detecting a heart rate reference of a user; (b) a memory unit for saving one or plural target heart rate reference intervals, said one interval comprising a target heart rate reference and a time period of maintaining the target heart rate reference; (c) a process unit connecting the heart rate sensor unit and a guiding unit, said process unit receiving the heart rate reference detected by the heart rate sensor unit and sending a signal of directing to the target heart rate reference interval according to the target heart rate reference interval saved in the memory unit; and (d) a guiding unit connecting the process unit, receiving the signal from the process unit and providing a direction signal to guide the user to adjust exercise intensity following the target heart rate reference interval.
[0014] In another aspect, the invention provides a method for guiding an intermittent aerobic exercise, comprising the following steps:
(a) providing a heart rate sensor unit for detecting a heart rate reference of a user; (b) setting one or plural target heart rate reference intervals, said one interval comprising a target heart rate reference and a time period of maintaining the target heart rate; (c) receiving the heart rate reference detected by the heart rate sensor unit to a process unit and sending a signal of directing to the target heart rate reference interval according to the target heart rate reference interval saved in the memory unit; and (d) receiving and displaying the signal from the process unit to guide the user to adjust exercise intensity following the target heart rate reference interval.
[0019] In one embodiment, the heart rate sensor unit of the guiding aerobic exercise system of the invention is used to detect the heart rate reference of the user. The heart rate reference can be detected based on pulse, heart rate or heart intensity. The pulse is the impulse of artery and the impulse is caused by cardiac impulse. Under normal condition, the pulse equals to heart beats, so pulse or heart rate is the frequency of heart's blood output per minute.
[0020] The heart rate (HR) intensity refers to exercise intensity calculated from heart rate. Various equations or formulae for determining the HR intensity can be used in the invention. In one example, HR intensity equals to HRmax multiplied by (220−age), which can be calculated based on the following equation: (220−age)x %.
[0021] In the above equation, HRmax is the maximum heart rate that of an individual under safe exercise pressure and depends to age. Other calculations of predicted maximum heart rate based on age are provided by Hirofumi Tanake et al. ( J of Am College of Cardiology 2001: 153-6).
[0022] In one embodiment, the heart rate sensor unit is an internal or external rhythm.
[0023] In one embodiment, the memory unit of the aerobic exercise system of the invention is used for saving one or plural target heart rate reference intervals, said interval comprising a target heart rate reference and a time period of maintaining the target heart rate. The target heart rate reference interval includes any length of time period of maintaining the target heart rate reference and a target heart rate reference with any heart rate intensity. In one embodiment, the arrangement of the plural target heart rate reference intervals can be gradually increased or decreased according to heart rate intensity or repeated with identical heart rate intensity. In one embodiment, the target heart rate reference interval in the memory unit can be originally set in the system or artificially set by the user. Since the health effects generated by exercise can be accumulated; therefore, the system and method of the invention can improve metabolism and aging. The invention can use various combinations of exercise intensity and time period that can achieve intermittent aerobic exercise to set target heart rate reference intervals.
[0024] In one embodiment, the target heart rate reference intervals are set based on heart rate intensity. Preferably, the target heart rate reference interval is preceded by a warm-up period. Preferably, a target heart rate reference interval of the invention includes an aerobic exercise with a target heart rate reference of about 70% to about 100% of maximum heart rate for a time period of at least several minutes, preferably following a heart rate recovery interval guiding of a heart rate intensity with about 40% to about 70% of maximum heart rate. Preferably, after the above intermittent aerobic exercise, another interval includes heart rate intensity with about 70% to about 100% of maximum heart rate for a time period of several minutes, following a heart rate recovery interval guiding of a heart rate intensity with about 40% to about 70% of maximum heart rate. Preferably, the target heart rate reference interval further includes a warm-up period and a target heart rate reference with a heart rate for a time period is set for the warm-up period. As such, several intervals can be repeated (preferably, 2 to 20 times). Elevation of the heart rate reference (i.e., heart rare intensity) is guided in graded steps for user to adapt every level. Preferably, the target heart rate reference interval includes in sequence, a section with a target heart rate reference of about 70% of maximum heart rate for a time period of about 8 to about 12 minutes (preferably about 10 minutes), four sections with a target heart rate reference of about 90% of maximum heart rate for a time period of about 2 to about 6 minutes (preferably about 4 minutes) and an intermission between two sections with a target heart rate reference of about 70% of maximum heart rate for a time period of about 1.5 to about 5 minutes (preferably about 3 minutes), and a recovery section with a time period of about 3 to about 8 minutes (preferably about 5 minutes). In one embodiment, the target heart rate reference intervals include the following intervals: a target heart rate reference of about 70% of maximum heart rate for a time period of about 10 minutes, a target heart rate reference of about 90% of maximum heart rate for a time period of about 4 minutes, a target heart rate reference of about 70% of maximum heart rate for a time period of about 3 minutes, a target heart rate reference of about 90% of maximum heart rate for a time period of about 4 minutes, a target heart rate reference of about 70% of maximum heart rate for a time period of about 3 minutes, a target heart rate reference of about 90% of maximum heart rate for a time period of about 4 minutes, a target heart rate reference of about 70% of maximum heart rate for a time period of about 3 minutes, a target heart rate reference of about 90% of maximum heart rate for a time period of about 7 minutes and a target heart rate reference of about 70% of maximum heart rate for a time period of about 5 minutes. Preferably, the initiating target heart rate reference interval further includes a warm-up period. Preferably, after a target heart rate reference interval, a heart rate recovery interval guiding of a heart rate intensity with about 40% to about 70% of maximum heart rate can be followed.
[0025] In another embodiment, the target heart rate reference intervals are set based on peak oxygen uptake. The “peak oxygen uptake” refers to the maximum rate of oxygen consumption (VO2peak) as measured during an exercise. Preferably, the target heart rate reference interval includes in sequence, a section with 70% VO2peak for about 1.5 to 6 minutes (preferably about 3 minutes) and a section with ≦40% VO2peak for about 1.5 to 6 minutes (preferably about 3 minutes). Preferably, the above interval can be repeated three to seven times (preferably five times).
[0026] In one embodiment, the system of the invention further comprises an interface of converting a perceived exertion of a user rated by Borg scale to a target heart rate reference. Alternatively, the heart rate sensor unit can be replaced by an interface of converting a perceived exertion of a user rated by Borg scale to a target heart rate reference. The consistency of the heart rate reference detected by the heart rate sensor unit and that converted from Borg scale are continuously checked during exercise. If the heart rate reference detected by the heart rate sensor unit is inconsistent with that converted from Borg scale, it represents that the user may has physical problem. Borg scale measures perceived exertion according to the use's feeling in heartbeat, respiration, sweating and muscle fatigue (“Perceived exertion as an indicator of somatic stress”. Scandinavian journal of rehabilitation medicine 2 (2): 92-98; Borg scale for measuring perceived exertion (Borg (1998) Human kinetics, Champaign, Ill.; Nybo (2003) Med Sci Sports Exerc, 35, 589-594). The scale ranges from 6 to 20, where 6 means no exertion at all, 7 and 8 mean extremely light, 9 and 10 mean very light, 11 and 12 mean light, 13 and 14 mean somewhat hard, 15 and 16 mean hard/heavy, 17 and 18 mean very hard, 19 means extremely hard and 20 means maximal exertion. The heart rate can be obtained by multiplying Borg scale by 10.
[0027] The process unit of the intermittent aerobic exercise system of the invention connects the heart rate sensor unit and a guiding unit and it receives the heart rate reference detected from the heart rate sensor unit and sends a signal of directing to the target heart rate reference interval according to the target heart rate reference interval saved in the memory unit so that the user can adjust exercise intensity following the target heart rate reference interval. Elevation of the heart rate intensity is guided in graded steps for user to adapt every level of the target intensity. In another embodiment, the process unit can transmit a signal to a server through internet or global positioning system (GPS), receives a signal in order to save heart rate reference of the user and change target heart rate reference interval in the memory unit to employ the process unit to provide instant information guiding the user to adjust exercise intensity.
[0028] The guiding unit of the connecting the process unit to receive the signal from the process unit and providing a direction signal to guide the user to adjust exercise intensity following the target heart rate reference interval. In one embodiment, the guiding unit guides the exercise intensity by stepped increased or decreased.
[0029] In another embodiment, the guiding unit is a display showed by light, color, voice, vibration, icon or words to guide the user to adjust exercise intensity. Preferably, the guiding unit is a light-emitting diode guiding a user to adjust exercise intensity by light. Preferably, the guiding unit is a vibrating motor guiding a user to adjust exercise intensity by vibration. Preferably, the guiding unit is an amplifier guiding a user to adjust exercise intensity by voice. Preferably, the guiding unit is a visual display guiding a user to adjust exercise intensity by color; more preferably, the numbers and types of color levels of the visual display can be designed according to the objective and necessity of the manufactures. For example, the color levels can be shown with fixed colors and/or blinking colors and the numbers of the color levels may range from 1 to 20 color levels, 1 to 10 color levels, 1 to 7 color levels, or 1 to 5 color levels. For example, 5 color levels in combination with a fixed and/or a blinking color can be used for display. For example, the color levels range from blue to red, so that from the lowest to the highest sequence are blue (B) 151 , green (G) 152 , yellow (Y) 153 , orange (O) 154 and red (R) 155 and the blinking color of the color level is denoted with the symbol “*.”
[0030] In one embodiment, the guiding unit connects to an exercise device for adjusting velocity of the exercise device to guide the user to adjust exercise intensity so that the user follows the target heart rate reference interval. Preferably, the exercise device is a treadmill or ergometer; the guiding unit connects to the treadmill to automatically adjust race velocity to guide a user to adjust exercise intensity following the target heart rate reference interval.
[0031] In one embodiment, the guiding unit sends a signal (such as beat or musical rhythm) to guide a user to adjust exercise motion. After heart rate intensity follows the target heart rate reference intensity, if the heart rate intensity of the user is lower (or higher) than the target heart rate reference intensity, the process unit can further send a signal to the guiding unit so that the guiding unit sends a further instruction signal to guide the user to enlarge or reduce motion to achieve the target heart rate reference. For examiner, the motion of step, leg list and/or hand waving can be enlarged.
[0032] Now with reference to the embodiment as illustrated in the accompanying drawings of the present invention to the present invention will be described in detail. One embodiment“, an example embodiment”, etc. refer to directions, an embodiment may include a particular feature, structure, or characteristic of the described, but each of the embodiments may not necessarily include the particular feature, structure, or characteristic. In addition, these phrases may not necessarily represent the same embodiment. Further, when a combination of the described embodiments a particular feature, structure, or characteristic is that a particular feature, structure, or characteristic lines in the knowledge of the skilled person skilled in the connection with other embodiments to affect this feature, structure, or characteristic, regardless of whether clear description.
[0033] Referring to FIG. 1 as one embodiment, the guiding aerobic exercise system 1 includes a heart rate sensor unit 11 , a memory unit 12 , a process unit 13 and a guiding unit 14 . The heart rate sensor unit 11 detects pulse, heart rate or heart rate intensity of a user. The memory unit 12 saves one or plural target heart rate reference interval; for example, the interval includes in sequence, a section with 70% of maximum heart rate for 10 minutes, four sections with 90% of maximum heart rate for 4 minutes and an intermission between two sections with 70% of maximum heart rate for 3 minutes, and a recovery section for 5 minutes. The heart rate sensor unit 11 transmits heart rate reference to the process unit 13 and the process unit 3 connects the heart rate sensor unit 11 and the memory unit 12 . After the process unit 13 receives the heart rate reference from the heart rate sensor unit 11 , it sends a signal to the guiding unit 14 according to the saved target heart rate reference interval so that the guiding unit 14 provides a signal to the user to adjust exercise intensity following the target heart rate reference interval.
|
The present invention provides a guiding aerobic exercise system and method for guiding a user to perform intermittent aerobic interval exercise with moderate or high intensity. The invention surprisingly demonstrates that following the guidance of the system and method of the invention, the user can improve metabolic conditions to attain a healthier body.
| 0
|
BACKGROUND OF THE INVENTION
This invention relates to a folding roof for an automobile.
A known folding roof has a front hood bar, slidably guided at both sides of the roof opening on lateral guide rails and movable by a drive device, a fixed, rear hood bar and a foldable hood extending between the hood bars, which foldable hood is tightened by the front hood bar on closure, the front hood bar, when the roof is closed, being pressed with its front edge sealed onto the fixed automobile roof.
In folding roofs of this type, it is of great importance that the front hood bar, when the roof is closed, shall hold the hood tightened and, in the last phase of its movement, shall be pressed sealingly and firmly with its front edge onto the forward, fixed roof surface.
In a known folding roof of this type (DE 37 22 434 A1), on either side of the forward hood bar, opening/closing mechanisms are provided which, in conjunction with the drive device acting thereon, are intended to assure the tightening and pressing-on. For this purpose vertically disposed guide plates, displaceable on the lateral guide rails, are provided on the opening/closing mechanisms, in the straight, oblique guide slits of which guide plates guide pins engage, these pins being mounted on driven slide blocks, also displaceable on the lateral guide rails.
By the lateral arrangement of the opening/closing mechanisms, fairly remote from the front edge of the front hood bar, the front edge is not subjected to a pressure sufficient for all requirements, especially not in its central region. Since the inclined guide slits in the vertically disposed guide plates are only comparatively short, only a small guide slit travel distance is available for the tightening and closing of the known folding roof, so that considerable application of force is necessary in tightening and closing. Furthermore, the vertically mounted plates of the opening/closing mechanisms increase the overall height of the folding roof construction.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a folding roof for automobiles which, with comparatively small application of force, shall facilitate a tensioning and closing movement of the front hood bar, but achieves a high application pressure of this front edge against the fixed roof surface and which is of low overall height.
According to the present invention, there is provided a folding roof for an automobile for the optional closure or partial exposure of a roof opening formed in a fixed vehicle roof, comprising a front hood bar, slidably guided at both sides of the roof opening on lateral guide rails and movable by a drive device, a fixed, rear hood bar and a foldable hood extending between the hood bars, which foldable hood is tightened by the front hood bar on closure, the front hood bar, when the roof is closed, being pressed with its front edge sealed onto the fixed automobile roof, wherein the lateral guide rails are adjoined at the front by curved transitions, which are continued parallel to the front edge of the roof opening and are provided with an upwardly open guide channel, continuous at least partly also along the lateral guide rails, in which guide channel, at each side, an upwardly projecting entraining element is slidably guided and the entraining elements are synchronously movable by drive cables, the entraining elements are each force-transmittingly connected with the front hood bar by a control plate guided slidably in the transverse direction on the front hood bar, the upper ends of the entraining elements each engaging longitudinally slidably but axially immovably into a control slit formed in each control plate, which slit, starting from a section, parallel to the front edge of the roof opening, continues into a rearwardly curved section, of which the radius of curvature is larger than that of the guide channel in the curved transitions, the control slits are arranged upwardly ascending in their sections, parallel to the front edge of the roof opening, starting from the curved sections, and the control plates bear slidably with their outer ends against wall surfaces of the guide rails corresponding to the curved transitions.
By the curved form of the guide channels, continuing to the forward edge of the roof opening and parallel to it there, in conjunction with the curved control slits in the substantially horizontally orientated control plates, large tightening and closure forces, increasing still further as the movement proceeds, can be achieved in the tightening and closing movement with a relatively low drive force, and with a correspondingly slowing-down movement control of the front hood bar. The application of the force acts increasingly towards the central region of the front edge of the front hood bar, and in the vicinity of this front edge, so that a reliable seal of the front edge is achieved. The application pressure is created by the ascending portions of the control slits provided in the control plates. By the substantially horizontally guided control plates, a favourably low overall height of the folding roof construction is maintained.
The use lateral guide rails having forward, curved transitions facilitates the construction of a single-piece guide frame, which in its forward region, parallel to the front edge of the roof opening, permits the fitting of a drive device engaging with the drive cables.
If the guide frame is a rigid frame, closed on all sides, then the folding roof can be constructed as a fully preassembled unit. This is particularly advantageous because folding roofs of this type are usually manufactured outside the automobile factory and this construction makes possible complete functional testing of the folding roof construction before it is installed into an automobile roof.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the invention and to show how the same may be carried into effect, reference will now be made, by way of example, to the accompanying drawings, in which:
FIG. 1 is a plan view of a folding roof, constructed as a single installation unit, in a closed position of its functional parts and with a hood itself largely cut away,
FIG. 2 is a partial, sectional view taken along the line II--II in FIG. 1,
FIG. 3 is a partial, sectional view taken along the line III--III in FIG. 1,
FIG. 4 is a partial plan on the left, front corner of the folding roof construction, with most of a front hood bar not shown due to the horizontal orientation of the section, the components being in the closed position,
FIG. 5 is a plan view corresponding to FIG. 4, but in an intermediate position of the functional parts, and
FIG. 6 is a plan view corresponding to FIGS. 4 and 5, but in the position of the functional parts when the front hood bar is completely lifted off and ready for sliding.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference is first made to FIGS. 1 to 3, of which FIG. 2 shows a cross-section through the arrangement of the front hood bar and the front edge of the roof opening, while FIG. 3 shows a cross-section through a lateral guide rail. In FIG. 3 and also in FIGS. 4 to 6, only the left side of the roof construction is shown in each. The right side is the same but to opposite hand.
The fixed automobile roof 1 is shown in FIGS. 2 and 3 only as a cut-away and sectioned, curved metal plate, in which is disposed the roof opening into which the folding roof is installed. On either side of the roof opening there are lateral guide rails 2, 3 respectively, which are combined together by curved transitions 4, 5 respectively and a front portion 6, connecting the curved transitions 4, 5 together, into a single-piece guide frame 7, having a uniform cross-section throughout. The guide frame 7 is provided with two mutually facing, continuous guide channels 8 for drive cables 9. The drive cables 9 are guided in the guide channels 8 in tension-stiff and compression-stiff manner and engage, in the example shown, in a pinion 10 shown in FIG. 1, which can be rotated by means of a hand crank 11 of a drive device 12, mounted on the front section 6. Rotation of the hand crank 11 and thus of the pinion 10 produce displacements in opposite directions of the flexible drive cables 9, constructed like toothed racks, which in turn cause movements of the folding roof in a manner to be described. An electric motor could, of course, be provided for the crank drive.
The guide frame 7, with its outwardly directed flange 13, fits over the fixed automobile roof 1 and bears against it through an elastic sealing profile 14 placed between. The fixing of the guide frame 7 to the automobile roof 1 is provided by a fixing frame 15, which bears on the one hand against the lower face of the automobile roof 1 and on the other hand against the lower face of the guide frame 7, with which it is connected by screws 16. The guide frame 7, fixing frame 15 and screws 16 are covered off from the interior of the vehicle by a cladding profile 17.
The folding roof possesses, furthermore, a movable front hood bar 18, a fixed rear hood bar 19, which connects the free ends of the lateral guide rails 2, 3 of the guide frame 7 rigidly together to a stiff frame, closed on all sides, and a foldable hood 20, extending between the hood bars 18, 19. In FIG. 1, the forward hood bar 18 is partly cut away, to illustrate the functional parts situated beneath. In addition, two transverse bars 21, supporting the hood 20, are shown in this example distributed over the length of the folding roof, the ends of these bars being displaceably guided in the lateral guide rails 2 and 3. On the front hood bar 18 and on the two transverse bars 21, elastic folding supports 22 are fitted, which during the opening displacement of the hood 20 cause the forming of upwardly directed folds of the hood.
The lateral guide rails 2, 3, the curved transitions 4, 5 and the front portion 6 of the guide frame 7 have a continuous, upwardly open guide channel 25, in which on each side a vertically, upwardly projecting entraining element 26 is slidably guided. The entraining elements 26 each have a sliding foot 27, which is slidably guided by lateral projections in undercut, lateral grooves of the guide channel 25, as FIG. 2 illustrates. The entraining elements 26, therefore, cannot be pulled out upwards from the guide channel 25. Moreover, the entraining elements 26 are each force-transmittingly connected by a web 28 to one of the drive cables 9. When the drive device 12 is actuated, the entraining elements 26 are displaced synchronously and in opposite directions in the guide channel.
On the front hood bar 18, in the region of each front roof corner, there are two mutually facing, downwardly orientated ribs 29 and 30, extending parallel to the front portion 6 of the guide frame 7. In these ribs 29 and 30 there are mutually facing grooves 31, 32 respectively, in which a control plate 33, 34 respectively is displaceably guided in the transverse direction on each side of the roof. With their outer ends, these control plates 33 and 34 are slidingly supported against the wall faces 35 of the guide frame 7, of which the curvature is adapted to the curved transitions 4, 5 respectively and the curvatures of the portions of the guide channel 25 situated therein.
In the control plates 33 and 34 there are control slits 36, 37 respectively, which each continue, starting from a section 38 parallel to the front portion 6 of the guide frame 7 and to the front edge of the roof opening, into a backwardly curved section 39. The radii of curvature of the curved sections 39 are larger than those of the guide channel 25 in the curved transitions 4 and 5 of the guide frame 7. The control slits 36, 37, approximately in their sections 38 parallel to the front portion 6 of the guide frame 7 or front edge of the roof opening, are disposed upwardly ascending starting from the curved sections 39, as can be seen from FIGS. 2 and 3. For this purpose, the control plates 33 and 34 are provided with upwardly orientated, ramp-like indentations 40, in which the sections 38 of the control slits 36, 37 run. The arrangement is such that the sections 38 of the control slits 36, 37 are in alignment with the portion of the guide channel 25 situated beneath them when the roof is closed, as FIG. 4 shows. The curved sections 39, in contrast, because of the described differences in radii of curvature, do not register with the portions of the guide channel 25 in the curved transitions 4, 5 of the guide frame 7.
At the free end of each of the entraining elements 26 there is a guide flange 41, from which there projects upwards a guide pin 42, which passes through the control slit 36, 37 respectively and on which a washer 43 is fitted on with sufficient axial clearance, being secured by a snap ring or the like. The front hood bar 18 can therefore not be lifted upwards off the entraining elements 26.
When the folding roof is wholly or partly opened, the entraining elements 26 are situated within the lateral guide rails 2, 3, the control plates 33, 34 on the front hood bar 18 being displaced as far as possible outwards, as shown in FIG. 6 at the example of the left control plate 33. The guide pin 42 of entraining element 26 is here in the abutment position against the outer end of the control slit 36. It will be seen that, on account of this abutment between the guide pins and the end faces of the control slits 36, 37, with a further opening displacement the entraining elements 26 entrain the control plates 33, 34 and with them the front hood bar 19 and also the hood 20 fixed thereto, backwards out of the position shown in FIG. 6.
If the opened folding roof is to be closed, then the entraining elements 26 move the front hood bar 18 forwards in the relative position of the functional parts shown in FIG. 6, until the entraining elements 26 run into the curved transitions 4, 5 of the guide frame 7. With a uniform displacement velocity of the entraining elements 26 within the now curved guide channels 25, the displacement velocity of the front hood bar 18 in the direction of travel becomes increasingly less, until the displacement is completed when the entraining elements 26 enter the section of the guide channel 25 situated in the front portion 6 of the guide frame 7. During their displacement in the curved portions of the guide channel 25, the guide pins 42 of the entraining elements 26 simultaneously slide within the curved sections 39 of the control slits 36, 37, the control plates 33 and 34, now entrained further forwards, bearing with their ends against the correspondingly curved wall surfaces 35 in sliding manner. Consequently, the control plates 33, 34 are displaced transversely inwards, in a movement along the front hood bar 18 superimposed upon their forward movement.
FIG. 5 shows an intermediate position of the functional parts during the closure movement of the folding roof. If the described movement sequence is continued, then the entraining elements 26, at the end of their curved travel in the curved transitions 4, 5, enter from both sides into the straight section of the guide channel 25 in the front portion 6 of the guide frame 7. Approximately simultaneously, the guide pins 42 of the entraining elements 26 leave the curved sections 39 of the control slits 36, 37 and enter the sections 38, parallel to the front member 6. At this instant, the forward displacement of the front hood bar 18 is completed. Just before entry into the sections 38, the guide pins 42 have already run into the upwardly ascending sections of the control slits 36, 37, with the result that the front hood bar 18 is increasingly displaced downwards. This means that, as the actuation of the drive in the same rotational direction is continued, the front hood bar 18 is no longer displaced forwards, but downwards, the guide pins 42 moving in the sections 38 of the control slits 36, 37 until they have reached the inner ends of the control slits, which is illustrated by the example of the left, front folding roof corner in FIG. 4. In this position, the front hood bar 18 has already been displaced fully downwards into the sealed position according to FIGS. 2 and 3. The control plates 33, 34 have now been displaced transversely into their inner limiting position.
On the basis of the construction described, the front hood bar 18, in the opening and closing displacements, with a constant rotational speed of the hand crank is displaced linearly at a constant speed in the direction of travel, so long as the entraining elements 26 are moving in the lateral guide rails 2, 3. With the entry of the entraining elements into the curved transitions 4, 5 during the closure displacement of the front hood bar 18, the velocity of displacement of the hood bar 18 in the direction of travel becomes, however, progressively smaller, until, on entry of the entraining elements 26 into the front member 6 of the guide frame 7, the value zero is reached. With continuing actuation of the hand crank at constant rotational speed in the same direction, the hood bar 18 is moved with considerable closure force downwards until it bears sealingly against the fixed automobile roof 1, without the actuation force to be applied to the hand crank being thereby notably increased. Since the entraining elements 26 or their guide pins 42 have already reached the ascending portions of the control slits 36, 37 before the forward displacement of the front hood bar 18 is completely finished, in this last phase of the closure operation a superposition of movements occurs, i.e. with a still slowly forward moving hood bar 18, this bar is simultaneously displaced downwards.
If the folding roof is now opened out of its closure position illustrated in FIGS. 1 to 4, the described movement sequence takes place in the reverse direction.
As FIGS. 1 and 2 show, the front hood bar 18 is held by the two entraining elements 26, which have moved inwards during the closure operation, in its central region and near its front edge in its pressed-on, closure position, with the result that the folding roof is securely and sealingly closed.
|
In a folding roof for an automobile, a front hood bar is moved by entraining elements driven by cables, which entraining elements can travel in curved transitions of lateral guide rails and simultaneously in curved control slits of control plates, slidable transversely on the front hood bar. The control slits run partly ascending towards the closure position, in order to create a downward displacement of the front hood bar as the roof is closed and an upward displacement of the hood bar as the roof is opened. The closing of the roof takes place with a continually decreasing speed of movement and continually increasing closure force, without any noticeable feedback effect upon the actuating force to be applied.
| 8
|
FIELD OF THE INVENTION
The present invention relates to the field of attaching one or more accessories to an appliance, where the accessories are intended to be used in close physical proximity or functional collaboration with the appliance. In particular, the invention pertains to attaching one or more accessories to an electronic display device such as a computer monitor.
BACKGROUND OF THE INVENTION
A variety of appliances are currently in use which can be used with improved functionality or convenience in conjunction with one or more accessories in business, home, and other applications. In many applications the accessories are best used when tightly coupled to the appliance. For example, various computers are often coupled with attendant accessories for a variety of applications. This is particularly true for modern multi-media computers, but often is seen in simply adding accessories to a traditional business or home computer. Other appliances which might be used in collaboration with tightly coupled accessories may include, for example, a television in conjunction with accessory speakers, a video input device such as a camera, e.g. for video conferencing, and perhaps a telephone.
In many applications, a computer may be used in conjunction with a variety of accessories. For example, referring to FIG. 1, a user might have a computer 20 and monitor 21, usually a keyboard 18 and pointing device such as mouse 19, plus one or more of a microphone 2, a video camera 13, a video conferencing camera 11, a camcorder 4, and a headset 15 integrating an earphone 15A and voice pickup 15B, a telephone 6, a modem 17, and external speakers 22. In current applications, each accessory comes with an independent mounting or positioning solution. For the most part, each accessory is intended for placement on a horizontal surface, such as a desktop or shelf. Speakers and telephones and larger video pickup devices are usually in this category. Some accessories, such as microphones and small video input devices, are designed to rest on top of a computer monitor.
In some instances, an accessory may be provided with a mounting solution to allow attaching the accessory directly to a vertical or horizontal surface such as an edge of a computer monitor. For example, certain accessories are packaged with a patch of hook-and-loop fabric, each side backed with adhesive, so that the accessory can be removably secured to a computer monitor, or other desired mounting location.
Each of the presently available mounting solutions suffer from a variety of disadvantages. For one, there is no universal or integrated solution, so each accessory vendor provides a different solution. As mentioned above, many accessories must be stabilized on a horizontal surface. In most installations, this uses valuable desk space. An ancillary difficulty of positioning accessories on a desktop is that the height may be inappropriate for optimal functioning of the accessory. For example, in some instances, speakers are best placed some distance above a desktop. For another example, most video input devices should be placed at approximately the level of a user's head, some significant distance above a desktop.
Mounting accessories on the top of a monitor also suffers from a variety of disadvantages. For example, most monitors include a substantial curved area and so lack large horizontal surfaces, so there is a limited space for positioning any accessory on a flat surface. Next, in most applications, a monitor will be tipped at some angle. In many instances, the angle of the monitor is changed from time to time. This is particularly true in a situation where different users share the same appliance. Such instances include a school or home or most any public access area, such as a library or information kiosk. These factors limit the available horizontal, or approximately horizontal, surface space but add the complication that the surface is not stable. If various accessories are balanced on such a surface, it may be quite difficult to keep them in position during any adjustment.
The issue of coordinating accessories with an appliance such as a computer display will become more acute as use of accessories becomes more commonplace. It is now common to provide speakerphone capabilities with a computer. This requires both speakers and a microphone, which beneficially are incorporated into or mounted close to a computer. However, often it is useful to be able to hold a private conversation. To this end, it would be helpful to have a telephone handset integrated with the computer as an alternative mode for telephonic communication. Video communication and conferencing is still in its infancy but within a short time a large number of computer users will use a video input device such as a small camera for routine communication and collaboration. For certain applications, a user may prefer to use a camcorder or other relatively heavy accessory in conjunction with the computer display.
Some computer vendors offer detachable connection solutions, but these address only some of the concerns described above. For example, the Hewlett-Packard Pavilion monitor and certain monitors available from Packard Bell provide for detachable speakers to the sides of a monitor. These solutions, however, provide only for the attachment of a single accessory, and at a single, predetermined position.
The issues described above may become increasingly relevant to other types of appliances, such as televisions. Common accessories for a television include a video cassette recorder (VCR), computer game player (and attendant joysticks, game pads, etc.), remote controls, auxiliary speakers, set top box and cable or other interface boxes. Some, but not all, of these accessories might be suitable for close integration with a television, while others may be useful only in general proximity to but not necessarily integrated with the television.
The present invention provides a mounting system that can be used with a variety of appliances and accessories to overcome these difficulties.
SUMMARY OF THE INVENTION
The present invention provides a plurality of mounting connections in close proximity to the appliance, and one or more appliances with a compatible, mating, mounting connection. In a preferred form, the mounting connections are integrated with the appliance and may take the form of a series of holes, or perhaps projections. In a particularly preferred form, the mounting connections are a series of holes arranged vertically and positioned in a recess such as a channel designed into the appliance so that the mounting connections are not a prominent aspect of the visual impact of the appliance, yet are readily available for securing an accessory. The channel can include at some point a wedge shape such as a chamfer. If corresponding accessories are designed with a corresponding shape, this can provide desirable distribution of forces as the accessory is fitted to or used with the appliance.
If the mounting connections are arranged symmetrically, accessories can be mounted on the right or left side at any of several heights allowed by the mounting connections. For example, one user might mount a telephone accessory on the right side of a computer, while another user might mount such a telephone on the left side of their own computer. In general, an accessory can be mounted on either side and perform appropriately. The height options are beneficial for mounting a variety of accessories, particularly a video camera. A video conferencing camera is preferably mounted at the user's eye level. The typical mounting position of a camera above the monitor results in an image looking down on the user which for most instances is rather unflattering to the user.
It is an object of this invention to provide a flexible mounting solution so that an accessory can be closely coupled to an appliance.
It is a further object of this invention to integrate the mounting solution with other design elements in order to maximize utility of the mounting but minimize any negative visual impact of the mounting solution.
It is a further object of this invention to allow positioning an accessory at a preferred one of several available optional positions in conjunction with the appliance.
It is a further object of this invention to allow positioning an accessory at a height appropriate for the function of that accessory for a particular user.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a computer monitor and several related accessories positioned using prior art solutions.
FIG. 2 illustrates a flexible mounting solution illustrating securing an accessory video camera to a monitor in accordance with the teachings of this invention.
FIG. 3 illustrates a preferred embodiment of the present invention.
FIGS. 4A and 4B illustrate in detail the mounting mechanism of the embodiment of FIG. 3.
FIG. 5 illustrates a detailed view of the mounting mechanism for a video camera accessory.
FIG. 6 illustrates a detailed view of the mounting mechanism for a generic, heavy accessory.
FIG. 7 illustrates an accessory with a hinge to move between a position for storage and a position for use.
FIG. 8 illustrates an accessory for supporting another device.
FIG. 9 illustrates an alternate support for mounting accessories.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a mounting mechanism on or near an appliance of interest and a compatible mounting mechanism on one or more accessories. The thrust of the invention is to allow positioning one or more appliances at a selected one of several possible positions in close proximity to the appliance. In one preferred embodiment, accessories are mounted to the appliance. In another preferred embodiment, accessories are mounted to a stand which is useful in connection with the appliance. The selection of materials and specific mounting mechanisms can be adapted to the nature of the specific accessories, including weight, size, potential number to be included in a single integrated group, and other factors well understood by one skilled in the art.
Referring to FIG. 2, one possible solution includes a series of holes within a groove where the groove is secured to the appliance and corresponding hooks on an accessory, enabling the accessory to be positioned at any one of a number of positions 1, 1'. Referring to FIG. 3, these principles can allow mounting of a variety of accessories to a selected appliance, including, for example, video camera 31, telephone handset support 32 and telephone handset 33, and document holder 34.
In one preferred embodiment, each side grove is fitted with a series of holes. Each hole is designed to fit in the normal width of a standard groove, which may, for example be about 1.3 mm wide. The standardized hole pattern and dimensions provides manufacturability advantages. For example, the holes can be molded partially in each of two mating elements such as a monitor housing and a front bezel. The exact point of meeting can be selected according to design criteria using methods well known in the art. These might include considerations of the material properties of plastic or other material forming each component of the groove. Selection of tooling is also important in that a mold tends to be designed to release a molded part along a principal axis. If the grooves and or holes can be included in the mold without interfering with this principal axis of release, then these features can be easily included in the product.
One skilled in the art will recognize that a variety of designs are possible for a mounting mechanism. For example, the appliance might have a series of holes, preferably in some sort of regular pattern. Alternatively, an appliance could be fitted with a series of pegs or knobs.
In a preferred embodiment, the mounting mechanism includes a series of slots secured to or integrated with the appliance. Providing a groove or slot provides some engineering advantages, as well as some aesthetic advantages. Incorporating a wedge along with the groove provides additional benefits.
For example, in a computer monitor, a channel can be provided along the right and left sides of the monitor at an appropriate position. Referring to FIGS. 4A and 4B, groove 10 is provided between front bezel 12 and main housing 14 of a computer monitor 16. The groove might be formed in just one of the main housing 14 or front bezel 12, or part in each but, for example, including material from each to meet at the midpoint or some other section of the groove, or perhaps by portions of each overlapping in the groove section, providing, for example, additional rigidity. Depending on a specific design, it may be desirable to include a backing plate, perhaps of metal, behind the groove to provide some desired material properties, including perhaps strength or rigidity.
A series of slots 20 are disposed in evenly spaced fashion along the primary axis of groove 10. As hook 41 is inserted into slot 20, segment 42 is fitted into channel 44. Accessory wedge portion 45 moves into position against channel wedge portion 46. Hook 41 engages slot 20 so as to pull the accessory into the groove. In a preferred embodiment, hook 41 includes elements to secure the hook into place against the appliance. Gravity can pull the appliance down relative to the appliance, further securing the fit of the accessory to the appliance.
The wedge feature provides two advantages. First, during insertion of an accessory, the wedge provides a guide directing the hook into the channel, since the opening of the wedge is wider than the final channel dimension. Second, once the accessory is inserted, the wedge provides support and resistance against bending around the hook, shown by arrow 49, in an axis parallel to the channel but approximately flush with the edge of main housing 14 and/or front bezel 12. A wedge provides more material in the accessory itself to allow better distribution of forces within the accessory when compared with a straight, non-wedged accessory. If there is little or no wedge, there is correspondingly less material to resist bending stress around the axis of rotation, which could promote a failure or breakage at that point.
The angle and depth of the wedge portion need not be identical necessarily for all compatible appliances and devices. It is preferable that the angle be consistent among a series of compatible devices, but the depth of the wedge need not be identical. For example, an appliance may be designed with a wedge of a certain depth while a second appliance, or perhaps a stand as described below, may have a wedge of greater depth. As long as an accessory can fit in a compatible channel of the greatest depth, it will also fit in a correspondingly shallower channel or groove. One skilled in the art will understand a variety of dimensional selections that are encompassed in the teachings of the invention.
Accessory 53 may be connected directly to accessory wedge portion 45 so as to maintain the accessory in a fixed relationship with hook 41 and therefore with the appliance. In one preferred embodiment, accessory 53 is connected to hook 41 in a way to permit some flexibility in this connection. For example, accessory wedge portion 45 may be connected to hook pivot 51 which is coupled to accessory pivot 52 through shaft 54 and head 55. Shaft 54 and head 55 are secured to accessory pivot 52, for example by molding from a single piece of plastic, and rotate within chamber 57 in hook pivot 51. As another example, the pivot connection could be a ball and socket type connection to allow additional degrees of freedom. A locking mechanism may or may not be included, as desired.
An accessory might be mounted using a single hook, but two or more hooks provide additional support. In addition, providing at least two hooks sharply limits the possibility of rotating around a hook along an axis perpendicular to the channel, illustrated by arrow 47 where the axis of rotation is perpendicular to the plane of the drawing in this view.
Referring to FIG. 5, each hook 50 is attached through extension 52 to video camera 59. Each hook 50 is sized to fit into a corresponding slot 20 when inserted along an axis approximately orthogonal to the main axis of groove 10, then secured in position by moving hook 50 down relative to slot 20. This takes advantage of gravity to keep the accessory (video camera 59) securely attached to the appliance (monitor 16). If extension 52 provides some sort of rotational freedom, each hook 50 can be rotated by 180° and video camera 59 can be mounted on the right or left side of the appliance.
Referring to FIG. 6, another useful accessory provides a standard camera mount, similar to those found on a tripod or monopod. One preferred embodiment of accessory bracket 61 is reinforced to spread weight over three holes, but a similar accessory bracket could be designed using only two holes or with different reinforcing for selected applications to support a variety of loads. The connection to the accessory may be selectively or completely flexible, as in a typical camera tripod with mechanisms for selectively choosing various rotational positions. Such an accessory bracket is useful for mounting an arbitrary device such as a camera, camcorder, and the like.
Referring to FIG. 7, another useful accessory includes one or more hinges to allow rotation between positions. The illustrated device is a document holder that can be rotated at hinges 72 between working position 71 and stored position 71'. One skilled in the art will appreciate that a wide variety of accessories with many degrees of freedom can be designed to work with the present invention.
Referring to FIG. 8, another useful accessory is holder 81 for a companion accessory, here headset 15 with earphones 15A and microphone 15B. A variety of useful support accessories can be designed by one skilled in the art. Referring also to FIG. 9, other useful accessories might include a simple board 96 for attaching sticky notes, a holder for an input device such as a mouse or remote control unit, a picture frame, a vase 97, or any number of other creative accessories.
The teachings of this invention can be useful even if the appliance does not itself include a stable, relatively vertical portion by using an accessory stand. Referring to FIG. 9, portable computer 91 is not designed to support the weight of any of these accessories, and the screen portion 92 may assume a variety of angles, many of which would be inappropriate for mounting an accessory. Stand 93 incorporates one or more channels 94 as described above to provide a means of securing one or more accessories as described above. Computer 91 can be coupled to accessories in a variety of ways including a docking station or infrared transceiver link 95, which may be wired in turn to appropriate accessories.
One skilled in the art understands how to modify the specific shape, sizing, and spacing of slots or hooks as needed for specific applications. One skilled in the art also understands that fitting an accessory with more hooks increases the area over which to distribute any loading. In addition, using more than one hook to secure an accessory provides some positional benefits, including effectively eliminating rotation of the accessory around an axis orthogonal to the groove.
A general description of the device and method of using the present invention as well as a preferred embodiment of the present invention has been set forth above. One skilled in the art will recognize and be able to practice many changes in many aspects of the device and method described above, including variations which fall within the teachings of this invention. The spirit and scope of the invention should be limited only as set forth in the claims which follow.
|
An integrated mounting solution provides a plurality of mounting connections in close proximity to the appliance, and one or more appliances with a compatible, mating mounting connection. In a preferred form, the mounting connections are integrated with the appliance and may take the form of a series of hole, or perhaps projections. In a particularly preferred form, the mounting connections are a series of holes arranged vertically and positioned in a recess designed into the appliance so that the mounting connections are not a prominent aspect of the visual impact of the appliance, yet are readily available for securing an accessory.
| 8
|
BACKGROUND OF THE INVENTION
The present invention relates to padlocks and particularly to pad locks having a U-shaped shackle partially separable from a lock body.
Padlocks having a U-shaped shackle extending from an openable tabular shaped lock body are known and described in, for example, U.S. Pat. Nos. 5,377,511; 5,363,678; 4,938,039; 4,998,422; and 5,174,136. Such padlocks provide a lock body having two cylindrical cavities through a top side, both in communication with a retainer cavity which holds two lock balls and a rotatable retainer. The shackle legs include inwardly directed cavities which by engagement with the locking balls prevent the upward movement of the shackle. The retainer cavity is open to a third cylindrical cavity penetrating longitudinally from a bottom side. This third cavity holds a lock cylinder assembly. The lock cylinder assembly receives a key from a bottom side through a keyway. When rotated by a correct key, the cylinder causes the rotation of an actuator which rotates the retainer to retract the balls. This allows the shackle to be retracted upwardly to open a lock. One leg of the shackle includes a 360° recess to allow rotation of the shackle around one locking ball, which also prevents removal of the shackle from the lock body.
Known padlocks of the above described configuration typically use a steel brass or aluminum lock body. This provides a rugged and secure lock to prevent forced removal. However, there are applications were other considerations predominate to maximum security, such as lightweightness, convenience, low cost, and corrosive resistance.
Also known are security seals or safety lock out devices which are used for locking a closure, and if broken, indicate that an unauthorized access has occurred. These devices can be used to lock out panel doors, or switches or controls or other parts of machinery. These devices can also prevent the inadvertent or unintentional access by requiring an intentional breakage to gain access. Such security devices are disclosed for example in U.S. Pat. Nos. 5,427,423 and 5,314,219. These devices typically are low cost devices which are used one time and are destructively removed, i.e., they are not key operated for removal. U.S. Pat. No. 4,502,305 describes a security device which is key operated but which uses a flexible J-shaped plastic shackle which lacks a degree of structural toughness of the aforementioned U-shaped metallic shackle.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a lightweight padlock. It is an object of the invention to provide a padlock which can be produced at low cost but retains effectiveness for its particular application. It is an object of the invention to provide a padlock which can be used more effectively in a corrosive environment.
It is an object of the invention to provide a padlock which can be used as a safety lock out device and which can be key operated for removal. It is an object of the invention to provide a safety lock out device which has an electrically non-conductive lock body. It is an object of the invention to provide a safety lock out device which can be repeatedly used. It is an object of the invention to provide a safety lock out device which is structurally resistive to removal by unauthorized personnel.
It is an object of the invention to provide a padlock for use in controlled environments such as penitentiaries or institutions which provides a medium degree of security for personal item security, such as gym lockers, but which are also lightweight so as to reduce a potential use as a projectile weapon by inmates or patients. It is an object of the invention to provide a low cost manufactured lock for reduced security applications, where security against massive-force tampering, such as by sledgehammer or lock cutters, or other tools, is not a great concern, or where the items secured are not extremely valuable such as for school gym lockers, school lockers, supply cabinets, etc.
The objects of the invention are achieved by a padlock composed of a plastic lock body which retains a locking ball to retain a U-shaped shackle. The lock body is effectively manufactured by injection molding two body half shells which are non-removably welded together to complete the enclosed lock body. The plastic lock body is electrically non-conductive for additional safety as a lock out device. The plastic lock body is resistive to corrosion as compared to aluminum or steel. The locking balls and shackle can be metallic, such as steel, to increase tampering security over an all plastic safety lock-out device which can be severed easily at a plastic shackle. The lock provides the U-shaped shackle is openable by key activation and rotatable on the lock body for opening.
The lock provides a greatly reduced lock weight over typical steel lock bodies and a softness increase and cost advantage over aluminum lock bodies. The lock is suitable for use as a security device in a controlled environment such as penitentiaries or mental health institutions because its lightweightness reduces its destructive potential as a projectile weapon. The plastic lock body is made significantly hollow with reinforcing ribs for structural strength and integrity.
The lock body is advantageous composed of fiberglass reinforced plastic such as polypropylene or nylon 6/6 with glass fibers at 30-50%. Advantageously polypropylene with 40% long glass fibers can be used. The addition of a chemical coupling agent improves physical properties over standard glass reinforced compounds. This material has resistance to chemicals, thermal aging and has a low moisture absorption.
The inventive plastic lock body is thus advantageous for a low cost medium security padlock and also as a safety lock-out device which requires minimal security since the purpose is to provide lock-out protection for machinery. The material cost is less than a comparable metal lock body and scrap is minimal since the body is injection molded.
The plastic composite provides improved resistance to chemical attack as well as improved resistance to galvanic corrosion. The part geometry of the lock body allows all components to be placed in position during assembly before the lock body is welded together, rear shell to front shell. This creates a unit which cannot be altered without damaging the assembled lock.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of a padlock of the present invention partially assembled;
FIG. 2 is a rear perspective view of a front half shell of a lock body of the embodiment of FIG. 1;
FIG. 3 is a front perspective view of a back half shell of the lock body of the embodiment of FIG. 1;
FIG. 4 is a rear view of the lock body half shell shown in FIG. 2;
FIG. 5 is a front view of the lock body half shell shown in FIG. 3;
FIG. 6 is a top view of the assembled lock body half shells with a top plate removed for clarity; and
FIG. 7 is a bottom view of the assembled lock body half shells.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates in elevational view a padlock 10 of the present invention partially assembled. The lock 10 includes a lock body 14 (showing one half shell portion) containing a lock cylinder 18 engageable to a retainer assembly 20. When the correct key is inserted and turned inside the cylinder 18, a tail piece 24 is turned, which turns a rotator bolt 26. A cylinder "bible" 28 which holds the spring pins which define the correct key extends laterally from the cylinder 18. The bible 28 is tabular shaped and is clamped in place to prevent rotation of the cylinder 18. A U-shaped shackle 30 is held in a first bore 32 and a second bore 34 of the lock body 14, by locking balls 38, 40 held within the body.
The balls 38, 40 are held in recesses 42, 44 formed on inside surfaces of the shackle 30. When the bolt 26 is turned, the balls 38, 40 can move away from the shackle to allow upward movement of the shackle. A short leg 46 of the shackle can be completely removed from the lock body 14. A long leg 48 can only move upward until a circumferential groove 50 receives the locking ball 38 and the long leg 48 is retained in the body 14 thereby. The shackle 30 can rotate about the vertical axis of the long leg 48 as the ball 38 moves around the groove 50.
Details of locking cylinder and retainer assemblies can be derived from U.S. Pat. Nos. 5,377,511; 5,363,678; 4,938,039; 4,998,422; and 5,174,136, herein incorporated by reference.
FIGS. 2-7 illustrates the lock body of the present invention. The lock body 14 is composed of a reinforced plastic such as a composite plastic with embedded glass fibers. Advantageously, a polypropylene with 40% long glass fibers is used. Also, a nylon 6/6 with 30% short glass fibers or 50% long glass fibers can be used as well.
The lock body 14 of the present invention is injection molded in two half shells, front and back and the two half shells are ultrasonically welded together after the mechanical parts are installed, such as retainer assembly 20, cylinder 18, locking balls 38, 40, and shackle 30.
As illustrated in FIG. 2, a front half shell 60 of the lock body 14 provides a top plate 62 having a first hole 64 for receiving the shackle short leg 46, and a second hole 65 for receiving the shackle long leg 48. The top plate 62 connects at opposite sides to a first side plate 66 and a second side plate 68. The side plates are connected by a bottom plate 70. First and second inner side plates 71, 72 are recessed forwardly of the side plates 66, 68. Between inner side plate 71 and first side plate 66 is a vertical slot 73. Between inner side plate 72 and second side plate 68 is a vertical slot 74. The top plate 62 and bottom plate 70 overhang the side plates 66, 68, extending rearwardly. The side plates 66, 68 are connected at the top and bottom plates with triangular gusset plates 76, 78, 80, 82. A front wall 84 connects the top, bottom and sides of the shell 60.
Formed with a bottom plate 70 is a floor plate 86 having a tongue 88 and groove 90. The floor plate 86 is recessed from a rear edge 92 of the bottom plate 70.
The top plate 62 has formed on its underside a ceiling plate 96 which has a tongue 98 and groove 100, similar to the tongue 88 and groove 90 of the floor plate 86.
Beneath the first hole 64 is a short half-cylinder cavity 104; and beneath the second hole 65 is formed a long half-cylinder cavity 106. These cavities receive the shackle legs 46, 48 respectively. A plurality of ribs 110, 112, 114 are arranged horizontally and spaced apart between the second inner side plate 72 and the long half cylinder cavity 106. These ribs serve to strengthen the lock body against external forces such as a crushing force, and also guide the cylinder 18 within the lock body 14. Semicircular cut outs 110a, 112a, 114a guide a circular key housing 18a of the cylinder, while tabs 110b, 112b, 114b retain the key cylinder "bible" 28 or pin housing, against rotation by coacting with an opposite half shell of the body 14. A top rib 118 connects the cavities 104, 106 and includes a semicircular recess 118a for additionally guiding the cylinder.
An "8" shaped keyhole 120 is formed through the floor plate 86 and bottom plate 70 to allow insertion of a key to operate the cylinder 18. The first and second holes 64, 65 also pass through both the top plate 62 and ceiling plate 96.
FIG. 3 illustrates a rear half shell 126 of the body 14. A top ridge 128 provides a forwardly facing tongue 130 and groove 132. The ridge 128 connects to a first side plate 134 and a second side plate 136. The first side plate 134 has triangular recesses 138, 140. A first inner side plate 142 extends forwardly of the first side plate 134. The second side plate 136 also has triangular recesses 146, 148 and a second inner side plate 150 extending forwardly thereof. A rear wall 152 connects the top, bottom, and sides of the shell 126. Extending from a top ledge 156 is a long semi-cylindrical recess 158 and a short semi-cylindrical recess 160.
Three horizontal ribs 162, 164, 166 extend between the long semi-cylindrical recess 158 to the first inner side plate 142. A top rib 170 connects the two cavities 158, 160. Semi-circular recesses 170a, 162a, 164a, 166a guide the cylinder 18 when installed. Adjacent the semi-circular recesses 162a, 164a, 166a are angled edges 162b, 164b, 166b. The angled edges and the tabs 110b, 112b, 114b clamp the cylinder bible therebetween to prevent rotation of the cylinder 18 with respect to the body 14. Between the first and second inner side plates 142, 158, at a bottom thereof, is a bottom ridge 176 having a tongue 178 and groove 180.
As illustrated in FIG. 4, the front half 60 includes a semi-cylindrical cavity 190 which houses the rotatable bolt 26 of the retainer assembly 20. Side cavities 192, 194 hold the locking balls 38, 40 and are open between the semi-cylindrical cavity 190 and the short and long cavities 104, 106. The slots 73, 74 are shown between the inner and outer side plates. Further voids 196 are formed to reduce molding thicknesses to accommodate shrinking defects and reduces weight.
As illustrated in FIG. 5, the rear half body shell 126 includes a semi-cylindrical recess 200 for housing the rotatable bolt 26, and side recesses 202, 204 open therewith and with the short and long cavities 160, 158. The side recesses hold the locking balls 38, 40.
FIGS. 6 and 7 illustrate the front and rear shells 60, 126 connected together. When the front half shell 60 is mated with the rear half shell 126, the tongues 130, 178 interfit into the grooves 100, 90 respectively as the top plate 62 and bottom plate 70 overlie the ridges 128, 176. The gusset plates 76, 78, 80, 82 interfit into the triangular recesses 138, 140, 146, 148 as the inner plate 142, 150 insert into the slots 73, 74 and abut the side plates 71, 72, forming tongue-in-groove joints. The ribs 170, 162, 164, 166 and complementary ribs 118, 110, 112, 114 meet to form circular guides. The tabs 110b, 112b, 114b and edges 162b, 164b, 166b clamp the cylinder bible in place within the lock body 14. The front and rear half shells 60, 126 are provided with recesses 200 on the outside of the lock body 14 as shown in FIGS. 6 and 7. The recesses 206 are formed on the outside of the front and rear walls 84, 152. The recesses 206 provide a convenient location for adhering labels to the plastic lock.
The two piece body 14 is then ultrasonically welded at its tongue-in-groove joints to form an integral assembly. Alternatively, other methods of joining the two half shells can be used such as adhesively securing.
The thus formed lock is fracture resistant and tough, with reinforcing against crushing and cracking. It is efficiently and cost effectively assembled. It is electrically non-conductive through its body. It provides a secure U-shaped shackle arrangement for locking. The shackle can be steel for resistance to cutting, as can the other mechanical components such as the cylinder, locking balls, and retainer assembly, all held by the plastic lock body.
Although the present invention has been described with reference to a specific embodiment, those of skill in the art will recognize that changes may be made thereto without departing from the scope and spirit of the invention as set forth in the appended claims.
|
A padlock having a U-shaped rigid shackle, a pair of locking balls, a rotatable retainer, and a lock cylinder held into a two piece composite plastic lock body. The two piece lock body can be ultrasonically welded together to capture the mechanical parts inside. The shackle can be metal such as steel, as can be the other mechanical parts. A lightweight, inexpensive yet reliable medium security lock is thus provided. The lock can be used as a safety lock out device or it can be used as a padlock for medium security applications.
| 4
|
BACKGROUND OF THE INVENTION
In numerous applications it is necessary to impregnate or coat linear materials such as fibers, strands or textile ribbons, particularly mineral fibers such as glass fibers, with a liquid, for example, an elastomeric emulsion.
Generally, it is necessary that this deposit be regularly distributed on these linear materials which may be done by drying these materials. It is known, in order to carry out this drying operation, to submit the impregnated or coated linear materials to the effects of rollers or pneumatic apparatus.
These drying methods display various inconveniences which this invention proposes to eliminate particularly by doing away with the irregularity of the deposit and the formation of elastic agglomerates adhering to the walls bordering the components used for scooping up excess coating or impregnant.
SUMMARY AND OBJECTS OF THE INVENTION
According to the invention, the impregnated or coated linear materials are dried in at least one calibrated space while they are laterally moved assuring a sweeping of the aforesaid space.
The calibrated spacing controls the percentage of weight of the matter placed on the materials and controls the lateral movement assuring the complete sweeping of the aforesaid space and thus assuring the self-cleaning of this space. The self-cleaning is particularly important where the physical or chemical creation of the dispersed matter is rapid (for example, drying and coagulation of the emulsions).
According to another characteristic of the invention the sweeping motion of the linear materials is begun upstream of the calibrated space.
Another characteristic of the invention consists of:
directing the impregnated linear materials towards at least one pair of rigid components forming a calibrated space between themselves;
introducing the materials into this calibrated space in a direction transverse to these elements;
drying the excess matter while the materials are passing into the aforesaid space; and
submitting these materials to a lateral movement which assures the sweeping of the calibrated space.
The lateral sweeping movement of the materials can be a to and fro alternating movement.
According to a particularly advantageous characteristic of the invention the displacement of the linear materials is carried out in the same plane upstream and downstream of the calibrated space, the drying carried out essentially by calendering.
According to one variation, the plane in which the linear materials are moved upstream of the calibrated space is separate from tne plane in which they move downstream, the drying being carried out simultaneously by calendering and by pressure on a component bordering the calibrated space.
According to another characteristic of the invention the linear materials are submitted to a drying comprising a succession of compressions and decompressions facilitating the separation of the excess of the impregnation material. For drying one strand the quantity of matter retained depends particularly on the linear density of the matter, on its form upon its passage into a calibrated space and on the number of calibrated spaces passed through. For a weak strand it may be advantageous to provide close compression zones, the sweeping movement being maintained.
These successive compressions and decompressions take place according to the invention in the interior of a series of calibrated spaces.
According to one method of use the linear materials are led toward the interior of this series of calibrated spaces, and pass through the intervals separating the pairs of elements responsible for the drying, these intervals, such as grooves, causing a decompression after each compression.
An object of the invention likewise is an apparatus for the embodiment of the method defined hereabove.
This apparatus comprises:
two parts each having at least one rigid element, the element of one part being in such a position in relation to the corresponding element on the other part that these two elements are separated by a calibrated space and cooperate in the drying of the matter deposited on the linear materials;
means acting on the corresponding elements in order to control the calibrated space;
means for controlling the lateral movement of the linear materials in order to sweep the calibrated space; and
tightening means maintaining the two parts of the apparatus and control means for the drying interval.
According to one particularly advantageous characteristic of the invention, the rigid elements forming a calibrated space between themselves are comprised of a ceramic material with a weak friction coefficient and, particularly, ceramic known on the market as TITAL sintered titanium oxide, reference T 8 , state B, manufactured by the CERATEX Company).
According to another characteristic of the invention, these rigid elements are fixed onto plates maintained on a frame, this placement permitting voluntary selection of the form, number and spacing of the rigid elements.
Other characteristics and advantages of the invention will become apparent from the description which follows and which relates to forms of embodiment given as means of unlimited examples.
DESCRIPTION OF THE DRAWINGS
In this description, the attached drawings are referred to, in which:
FIG. 1 is a cross-sectional view of the apparatus;
FIG. 2 is a longitudinal sectional view along line II--II of FIG. 1;
FIG. 3 is a sectional view showing the sweeping movement of the linear material in the calibrated space;
FIG. 4 is a plan view showing an apparatus conveying this sweeping movement to the material;
FIGS. 5, 6 and 6a are detailed views relating to the direction of the material before and after its passage into the calibrated space;
FIG. 7 is an enlarged view of a variation of the embodiment;
FIG. 8 is a view in perspective of a system for deactivating the apparatus in case the sweeping and the means assuring this sweeping are halted;
FIGS. 9, 10 and 11, are end, elevated, and plan views respectively of the support plates for the rigid elements bordering a succession of calibrated spaces.
DETAILED DESCRIPTION OF THE INVENTION
In the form of embodiment illustrated in FIGS. 1 and 2 the apparatus comprises a body 1 having substantially the shape of a "U" split on the sides. On the bottom of this body, along the axis of the split, the element 2 is situated forming the lower lip of the interval comprising the calibrated space.
The upper lip of this interval is itself comprised of the element 3 which is fixed to a parallelepidic block 4 introduced into the crevice of the body 1. Two screws 5 penetrate the block 4 permitting control of the interval between the lips 2 and 3 and consequently the calibrated space. This control is maintained by one screw 6 pressing on the block 4 and screwing into a piece 7 on which the body 1 rests.
The space between the lips 2 and 3 controlled by means of a thickness gauge, controls the weight percentage of matter deposited on the linear material.
The pieces 2 and 3 are of ceramic such as TITAL and have a half-circular shape, the diameter of which is 6 mm in the example under consideration; their contact with the linear material is brought about by the two face to face generating lines of the said pieces, which implicates that the material moves in the same plane upstream and downstream of the pieces 2 and 3. Practically no abrasion of the material takes place; the intensity of the drying is independent of the tension of the said material.
In order to prevent the formation of deposits of matter from the sides of the material in the calibrated space, which would lead to an uncontrolled modification of the percentage of matter applied to the said material, an alternating sweeping movement is transmitted to the material in the calibrated space. This movement assures the self-cleaning of this space and, in addition, permits the use of linear materials having surface irregularities.
The sweeping movement can be obtained with any appropriate means such as, for example, as illustrated diarammatically in FIG. 4, a pulley 10 engaged by the material and movable betweeen two end positions 10a and 10b, this pulley having an axis of rotation which is inclined with respect to its plane of rotation. The sweeping movement can be likewise acquired with the help of a fork engaged by a cam device.
As illustrated in FIG. 5 the movement of the linear material 9 can be in one plane upstream and downstream of the calibrated space. The percentage of matter retained by the material is effected essentially by calendering and depends only on the calibrated space. It is independent of the material tension.
FIGS. 6 and 6a illustrate arrangements according to which the plane in which the material is moving upstream of the calibrated space is separate from the plane in which it is moving downstream. The percentage of matter retained by the material thus depends on the calibrated space as well as on the tension of the material. The drying takes place in this case by calendering and by pressure on the piece 2 in the case in FIG. 6 and on the pieces 2 and 3 in the case in FIG. 6a.
FIG. 7 shows a form of embodiment of the apparatus according to which the elements 2 and 3 forming the lips of the calibrated space are comprised of ceramic, cylindrical barrels, particularly of TITAL, fixed into grooves 11 provided respectively in the body 1 and the block 4.
In the embodiment illustrated in FIG. 8 the apparatus responsible for controlling the sweeping comprises a fork 23 through which the linear material 9 passes. This fork is mounted by a rod 24 to a piece 25 itself mounted to a rod 26, screws 27 and 28 allowing control of the position of the fork.
The rod 26, which assures the alternating movement of the fork according to the arrows f', is fixed to a plate 29 mounted off center on the plate 30 activated into a rotating movement by the motor 31.
According to this same FIG. 8 the body 1 is fixed to a frame 1a and the block 4 is itself mounted to a rod 12 terminated by a head 12a engaged by a slot 32 provided in the block 4. The other end of the rod 12 is fixed by a screw 14 into a socket 15 mounted on the electromagnet 16 fixed to a frame 19. A spring 17 is provided between the body of this electromagnet and a ring 18 fixed to the rod 12.
On a cross-piece 20, fixed to the frame 1a, is mounted a vibration detector downstream of the calibrated space, crossed by the linear material 9. This detector is connected by a servocontrol apparatus to the electromagnet 16. When the sweeping movement of the calibrated space stops, that is when the linear material passes through the center of the detector without moving as shown by arrows f, the servo-control apparatus regulates the electromagnet 16 which pulls on the rod 12 while thus disengaging the element 3 borne by the block 4 from the element 2, itself borne by the body 1. When a defect immobilizes the strand in the calibrated space, the vibration detector causes the opening of this space until the defect passes.
In the form of embodiment illustrated in FIGS. 9 to 11, a succession of separate calibrated spaces are provided so that the impregnated or coated linear materials are submitted to a succession of compressions and decompressions facilitating the elimination of excess matter.
In this form of embodiment, the apparatus contains a frame 41 holding two opposite plates 42. These plates display grooves 43 in which are attached ceramic, cylindrical small bars 44, particularly of TITAL. An inset piece, such as a thickness gauge, is provided between the two plates in order to maintain their spacing at a desired value corresponding to the calibrated space 45.
This arrangement allows for modification of the diameter, number and spacing of the small bars.
Between each pair of bars 44 a decompression interval 48 is located.
The example hereafter, given as a nonlimited example, illustrates the invention.
EXAMPLE
The drying of an assembly of glass fibers composed of five ES 9 68Z 25 strands, impregnated with an elastomeric mixture with the help of an apparatus identical to that described hereabove with reference to FIG. 1, the calibration gauge having a thickness of 20/100 millimeter and the speed of passage of the material being 100 meters per minute.
The impregnation mixture used, with a viscosity of 20 centipoises, was comprised as follows:
______________________________________Solution 1 In Weight______________________________________water 432.6resorcinol 36.6470 g/L of sodium hydroxide ina water solution 2.230% formaldehyde solution 66.6______________________________________
The solution was permitted to set for four hours 30 minutes at 20° C. under agitation, then the following was added:
______________________________________470 g/L sodium hydroxide in a water 4.8solutionSolution 2water 250.0S BR latex 40% (Firestone 251) 342.0UGITEXVP 60% latex 768.0ammonia 28% 52.6______________________________________
Solution 1 was poured into solution 2 under agitation.
The percentage of matter deposited on the assembly, after drying with repeated compression and expansion by exposure at a temperature of 120° C. for 0.8 seconds is 20%±0.5% with relation to the total weight of the material and the deposit.
|
Impregnated or coated linear material, for example, coated glass fibers, are dried in one or more calibrated spaces which control the percentage of impregnate or coating. A sweeping device moves the material laterally assuring complete sweeping and hence self-cleaning of the calibrated spaces.
| 3
|
This is a Continuation-in-Part of prior U.S. application Ser. No. 640,525 Filing Date: Jan. 11, 1991, now U.S. Pat. No. 5,231,980 which in turn is a continuation of application Ser. No. 162,450 Filing Date Mar. 1, 1988 now abandoned.
FIELD OF THE INVENTION
This invention relates to the recovery of halogenated hydrocarbons from a gas stream and recovery thereof for reuse.
BACKGROUND OF THE INVENTION
Halogenated hydrocarbon compounds include the family of compounds of bromo-, fluoro- and/or chloroethers, fluorinated alkyl ethers, chlorofluorocarbons and chlorofluoro ethers and their derivatives. This family of compounds are typically used as solvents, refrigerants, anesthetic gases, aerosol propellants, blowing agents and the like. Many of these compounds are widely used and normally discharged into the atmosphere. However, if these compounds could be recovered and re-used there would be a considerable cost saving and reduction in environmental pollution. In view of the possible effects of released anesthetic gases, attempts have already been made to recover such gases.
An example of anesthetic gas removal, is with regard to patient exhalent to ensure that the environment in the operating theatre does not contain anesthetic gases which can have a long term effect on the professionals conducting the operation. Commonly, anesthetic gases are removed from patient exhalent by use of various types of disposable absorbers, such as that disclosed in U.S. Pat. Nos. 3,867,936 and 3,941,573. In the United States patent to Kelley, U.S. Pat. No. 3,867,936, an absorber unit is in the shape of a hollow drum filled with activated carbon to absorb anesthetic gases exhaled by the patient. When the weight of the absorber unit increases to a predetermined value, the unit is replaced with a fresh one. In Chapel, U.S. Pat. No. 3,941,573, a molecular sieve is used in combination with the activated carbon in a disposable cartridge. The cartridge is included in the patient anesthetic administration breathing system to absorb on both the activated carbon and the molecular sieve materials the exhaled anesthetic gases.
It is common to dispose of the absorber units used to absorb anesthetic gases. However, in view of the rising costs of the anesthetic gases, attempts are being made to recover them. For example, in U.S. Pat. No. 3,592,191, a system is provided for recovering exhausted anesthetic gases from patient exhalent by removing water vapor from the collected gases by their condensation thereof or with a hygroscopic material. This treated gas then has the anesthetic agent extracted therefrom by a cryogenic process in which the vapors of the anesthetic gases are condensed to liquid phase, or by removal on an absorbent material which is processed later to remove the anesthetic agents. The collected anesthetic liquids are then reintroduced directly into the anesthetic system. Such approach has little if any facility to control bacterial contamination and recycle of harmful microorganisms to the patient.
Another approach in the recapture of anesthetic gases is disclosed in Czechoslovakian patent 185,876. An absorbent material is used to absorb halogenous inhalant anesthetics from the patient exhalent. When the adsorbent material is saturated, it is removed in an appropriate container and placed in a regeneration system. A purging gas, such as steam, is used to remove the anesthetic agents from the adsorbent material. The purged gas is then collected with water removed therefrom and the separated anesthetic agents are subjected to fractionation to separate out the individual anesthetic agents from the supply of anesthetic gases from various operating theatres.
The use of molecular sieves to adsorb gaseous components is exemplified in U.S. Pat. No. 3,729,902. Carbon dioxide is adsorbed on a molecular sieve which is regenerated with heated steam to remove the carbon dioxide from the adsorbent material. Another example of the use of molecular sieves to adsorb organic materials is disclosed in Canadian patent 1,195,258. In this instance, a hydrophobic molecular sieve is used to adsorb organic species from a gas stream containing moisture. The hydrophobic molecular sieve selectively adsorbs the organic molecular species into the adsorbent material, while preventing the collection of water vapor from the gas stream on the adsorbing material. The temperature and pressure at which the system is operated is such to prevent capillary condensation of the water in the gas stream onto the adsorbing material. By removing the adsorbing material from the system, the adsorbing material is essentially free of water yet has absorbed thereon the desired organic molecular species. The organic molecular species are then recovered from the adsorbent material by purging.
Particularly desirable types of anesthetic gases are commonly sold under the trade marks ETHRANE and FORANE, as disclosed in U.S. Pat. Nos. 3,469,011; 3,527,813; 3,535,388; and 3,535,425. These types of anesthetic gases are particularly expensive; hence an effective method of recovering them from patient exhalent for reuse would be economically advantageous.
SUMMARY OF THE INVENTION
According to an aspect of the invention, a process for the recovery of halogenated hydrocarbons from a gas stream is provided. The process comprises passing the gas stream through a bed of hydrophobic molecular sieve adsorbents having pore diameters large enough to permit molecules of the halogenated hydrocarbon to pass therethrough and be adsorbed in the large internal cavities of the crystal framework, whereby the halogenated hydrocarbons are removed from the gas stream. The gas stream is passed through the bed of adsorbent material at least until just prior to breakthrough of an essentially saturated halogenated hydrocarbon absorption front. The adsorbent material containing the adsorbed phase is regenerated by exposing it to an inert purging gas stream whereby the halogenated hydrocarbons are desorbed into the purging gas stream. The halogenated hydrocarbons are removed from the purging gas stream and are purified to a purity suitable for reuse.
According to another aspect of the invention, a canister is provided for use in adsorbing halogenated hydrocarbons from a gas stream passed through the canister. The canister has a peripheral side wall, a first end wall with an inlet port and a second end wall with an outlet port. A first fine mesh screen is spaced from the first end wall and closes off the first canister end. A second fine mesh screen is spaced from the second end wall and closes off the second canister end. Hydrophobic molecular sieve granular adsorbents are packed in the canister between the first and second screens. The sieve adsorbents have pore diameters large enough to permit molecules of the halogenated hydrocarbons to pass therethrough and be adsorbed in the large internal cavities of the crystal framework, whereby the halogenated hydrocarbons are removed from the gas stream. The first and second screens have a mesh sizing to retain the granular material in the canister. A means is provided for resiliently urging one of the first or second screens towards the other to compress such granular material between the screens.
According to another aspect of the invention, an anesthetic machine is provided having an inlet port of the canister connected to an exhaust port of the machine thereby passing patient exhalent from the anesthetic machine to the canister to absorb anesthetic gases.
According to another aspect of the invention, an apparatus is provided for regenerating the canister of adsorbent as connected to an anesthetic machine comprising means for connecting an incoming line of nitrogen gas to the inlet. A means is provided to heat the canister and optionally the nitrogen gas in the incoming line to a temperature in the range of 30° C. to 150° C. Means is provided for connecting an outgoing line to the canister outlet and for measuring temperature of nitrogen gas enriched with the desorbed anesthetic in the outgoing line. Regeneration is ceased shortly after the temperature of the nitrogen gas in the outgoing line is at a level of the temperature of the nitrogen gas in the incoming line.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are shown in the drawings wherein:
FIG. 1 is a schematic of an anesthetic machine with canister connected thereto for removing anesthetics from the patient exhalent;
FIG. 2 is a section through the canister of FIG. 1;
FIG. 3 is a schematic of the apparatus used to regenerate the adsorbent material in the canister of FIG. 2;
FIG. 4 is a schematic of the multi-stage fractional distillation system for separating components of the anesthetic absorbed by the canister coupled to the anesthetic machine.
FIG. 5 is a plot of the inlet and outlet concentrations versus time for an airstream saturated with isoflurane passed into a canister of adsorbent material.
FIG. 6 is a plot of the net amounts of isoflurane evaporated, exhausted and retained in the canister versus time.
FIG. 7 is a plot of the concentration versus time of concentration of isoflurane in the purging gas stream exiting from the recovery system and;
FIG. 8 is a plot versus time of the net volume of isoflurane lost in the regenerative gas stream exiting the recovery system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, a system is provided which can recover a variety of halogenated hydrocarbons and purify the recovered compounds. Typical halogenated hydrocarbons include bromo-, chloro- and/or fluoroethers, fluorinated alkyl ethers, chlorofluorohydrocarbons, chlorofluoroethers and their derivatives. Anesthetic gases are well known types of halogenated hydrocarbons which include isoflurane, enflurane, halthane, and methoxyflurane. Other well known halogenated hydrocarbons include the variety of Freons (trade mark) such as trichlorofluromethane, and dichlorodifluoromethane. This family of halogenated hydrocarbon compounds which include, for example, an alkyl group or ether group substituted with one or more of chloro, fluoro and bromo groups are readily absorbed on the high silica zeolite adsorbent and can be readily desorbed from the adsorbent. A preferred aspect of the invention is described with respect to the recovery of various anesthetic gases. It is appreciated that the principles of the invention which are demonstrated by the following embodiments are equally applicable to the recovery of other types of halogenated hydrocarbons.
A variety of organic based anesthetics are used in patient surgery. Common forms of anesthetics are those sold under the trade marks ETHRANE and FORANE by (ANAQUEST of Quebec, Canada). The respective chemical formulae for these anesthetics are as follows: 1,1,2-trifluoro-2-chloroethyl difluoromethyl ether and 1-chloro-2,2,2-trifluoroethyl difluoromethyl ether. Other types of anesthetics are, for example, Halothane (trade mark) of the formula bromochlorotrifluoroethane and Penthrane (trade mark) of the formula 2,2-dichloro-1,1-difluoroethyl methyl ether which are readily available from various suppliers, such as, Hoechst, Ayerst, Abbott, etc.
By way of an anesthetic machine, these anesthetics either singularly or in combination are delivered to the patient in combination with oxygen, nitrous oxide and/or air. As the patient breathes the gas stream containing the anesthetic, a desired degree of unconsciousness is achieved and monitored by an anesthetist. Not all of the anesthetic inhaled by the patient is absorbed into the blood system. In fact, very little of the anesthetic is absorbed. During procedures, the gas flow rate to the patient may be in the range of 0.5 to 7 liters per minute, where the concentration by volume of the anesthetic may be in the range of 0.3% to 2.5%. Normally, the patient exhalent is not recycled via the anesthetic machine. Instead, it is exhausted to the atmosphere by way of appropriate ducting. It is very important to ensure that the patient exhalent is not exhausted into the operating theatre, because the presence of the anesthetics can have a long term effect on the people in the operating room. It is appreciated that the use of the term patient is in a general sense. It is understood that anesthesia is practiced on a variety of mammals not only including humans but also animals such as horses, cattle and other forms of livestock, domestic pets and the like.
As shown in FIG. 1, the patient represented at 10 is connected to a mask 12 having a gas line 14 communicating therewith. The desired mixture of anesthetic gas is delivered in line 14 to the patient 10. The patient exhalent is delivered in line 16 to the anesthetic machine 18. The anesthetic machine 18, which is supplied with oxygen, a source of anesthetic and air in lines 20, 22 and 24, is operated to introduce the desired mixture in line 14. The patient exhalent in line 16 is discharged via line 26. Normally line 26 leads to external ducting for exhausting the anesthetics to atmosphere. In accordance with this invention, a canister 28 having an inlet 30 and an outlet 32 is interposed in line 26 at a position sufficiently downstream of the machine so as to have no or minimal effect on its operation. The patient exhalent in line 26, therefore, flows through the canister 28 before exhausting to atmosphere at 34. The canister 28 is charged with a hydrophobic molecular sieve granular material of silicalite which adsorbs from the patient exhalent stream the organic gaseous anesthetic. Hence, the stream discharge at 34 is free of the anesthetic gases.
An anesthetic sensor 36 may be provided in the exhaust line 38 to sense the presence of anesthetics exiting from the canister 28. It is appreciated that the adsorption front of the adsorbed anesthetics, in the bed of adsorbent travels along the bed towards the canister outlet. Such adsorption front will usually have a curved profile across the canister as it approaches the outlet. The curved profile normally assumes an elongated "S" shape. The sensor will sense when any portion of that front has broken through the adsorbent into the outlet. Replacement of the canister is normally required at this time though the bed of adsorbent is not entirely saturated with organic anesthetic. The sensor 36 may be connected via signal line 40 to the anesthetic machine 18. The anesthetic machine may be equipped with a light and/or audible alarm 42 which is actuated when the sensor 36 senses anesthetic gases in line 38. This indicates to the anesthetist that the canister 28 should be replaced so that continued recovery of anesthetics is achieved. It is appreciated that a bypass 44 controlled by valve 46 may be provided to route the patient exhalent past the canister 28 during replacement thereof. In this instance, a valve 48 is provided in line 26 to shut off the supply to canister 28 during replacement of the canister.
The canister may be charged with any of a variety of adsorbents. However, according to an aspect of this invention, the molecular sieve adsorbent utilized has an adsorptive preference for the less polar organic materials with respect to water, i.e., be hydrophobic. In the case of zeolitic molecular sieves, as a general rule the more siliceous the zeolite, the stronger the preference for non-polar adsorbate species. Such preference is usually observable when the framework molar SiO 2 /Al 2 O 3 ratio is at least 12, and is clearly evident in those zeolite species having SiO 2 /Al 2 O 3 ratios of greater than 50. A wide variety of zeolites can now be directly synthesized to have SiO 2 /Al 2 O 3 ratios greater than 50, and still others Which cannot at present be directly synthesized at these high ratios can be subjected to dealumination techniques which result in organophilic zeolite products. High temperature steaming procedures involving zeolite Y which result in hydrophobic product forms are reported by P. K. Maher et al., "Molecular Sieve Zeolites", Advan. Chem. Ser., 101, American Chemical Society, Washington, D.C., 1971, p. 266. A more recently reported procedure applicable to zeolitic species generally involves dealumination and the substitution of silicon into the dealuminated lattice site. This process is disclosed in U.S. Pat. No. 4,503,023 issued Mar. 5, 1985 to Skeels et al. Many of the synthetic zeolites prepared using organic templating agents are readily prepared in a highly siliceous form--some even from reaction mixtures which have no intentionally added aluminum. These zeolites are markedly organophilic and include ZSM-5 (U.S. Pat. No. 3,702,886); ZSM-11 (U.S. Pat. No. 3,709,979); ZSM-12 (U.S. Pat. No. 3,832,449) and ZSM-35 (U.S. Pat. No. 4,016,245) to name only a few. It has been found that the silica polymorphs known as silicalite, F-silicalite and TEA-silicalite are particularly suitable for use in the present invention and are thus preferred, though not, strictly speaking, zeolites, because of a lack of ion-exchange capacity, these molecular sieve materials are included within the terms zeolite or zeolitic molecular sieve as used herein. These materials are disclosed in U.S. Pat. No. 4,061,724; U.S. Pat. No. 4,073,865 and U.S. Pat. No. 4,104,294, respectively.
As shown in FIG. 2, the canister 28, which may be cylindrical in shape, has a side wall 50 with a first end 52 having an inlet 30. A second end 54 has the outlet 32. It is appreciated that the canister 28 may be disassembled by having releasable fasteners 56 about the perimeter of the side wall 28 to clip respectively the first and second end walls 52 and 54 to the side wall 50. Within the canister 28, the hydrophobic molecular sieve granular material of silicalite 58 is contained. At the second end of the canister, a fine mesh screen 60 is positioned to close off the second end defined by flange 62. The fine mesh screen 60 conforms to the interior shape of the canister side wall 50 which, in this instance, is circular and abuts the flange 62. A coiled spring 64, as spaced between the wall 54 and the fine mesh screen 60, holds the screen in place against the flange 62. With the other end 52 and the fine mesh screen 66 removed, the silicalite material 58 may be charged into the canister 28. Once the silicalite material has achieved a level indicated by arrow 68, the screen 66 is placed in the canister. A spring 70 is positioned between the wall 52 and the screen 66. When the clips 56 are clamped in position, the spring pushes the fine mesh screen 66 against the silicalite material 58 to compress and hold the silicalite material in place in the canister 28. This ensures that the silicalite material remains relatively fixed in the canister during use.
The patient exhalent in line 26 from the anesthetic machine 18 of FIG. 1 is naturally moist. This has presented significant problems in the past in attempting to recover organic anesthetics from the moist patient exhalent. It has been discovered that the use of a hydrophobic molecular sieve granular material of silicalite overcomes those problems. The silicalite material has a pore diameter which permits the material to selectively adsorb and remove the organic gaseous anesthetic from the humid patient exhalent and which minimizes coadsorption of water molecules in the patient exhalent. The benefits in using silicalite adsorbents is that there is no bacterial growth on the adsorbents which can become a problem because of the presence of bacteria in the patient exhalent. The adsorbent is non-flammable in the presence of oxygen. This is a significant drawback with organic forms of adsorbents since for certain concentrations of oxygen, the organic adsorbents are at least flammable if not explosive. The silicalite adsorbent is inert so that minimal if any decomposition of the anesthetic agent is induced whereas with organic adsorbents, such as activated carbon, hydrochloric acid can be produced in the presence of iron by way of decomposition of the halogenated anesthetics. The inert silicalite adsorbents are readily re-sterilized using ozone, steam, peroxide or other disinfectants without in any way affecting the adsorptive reuse characteristics of the adsorbent. The silicalite adsorbents are found to be microwave transparent. Therefore, regeneration can be accomplished using microwave heating.
A preferred form of silicalite is that manufactured and sold by Union Carbide under the trade mark "S-115 Silicalite". The chemical properties of S-115 Silicalite are as follows:
Chemical properties (greater than) 99% SiO 2 (less than) 1% aluminum oxide.
The Silicalite has the following physical properties:
______________________________________Free apertureZig-zag channels 5.4 AStraight channels 5.75 × 5.15 APore volume 0.19 cc/gmPore size approx. 6 angstroms in diameterCrystal density 1.76 gm/ccLargest molecule adsorbed BenzeneForm Powder, Bonded Bead or Pellet______________________________________
By use of a silicalite material having those properties, it has been discovered that the organic anesthetics are adsorbed by the silicalite while other components of the patient exhalent, including moisture, pass through. Hence, a minimum of moisture is retained in the canister. Supplemental heating of the canister 28, as shown in FIG. 1, may be provided by control 72 for heater 74. The purpose of the heat is to ensure that the canister 28, during use on the anesthetic machine, remains at a temperature which prevents the moisture in the patient exhalent condensing on the silicalite material in the canister and also on the canister surfaces.
Once it has been determined that the silicalite material in the canister is saturated with adsorbed organic anesthetic, or that the adsorption front has broken through to the outlet, the canister has to be replaced in the manner discussed. To regenerate the silicalite material in the canister 28 and to recover the anesthetic components for reuse, a silicalite regeneration system 76 is shown in FIG. 3. The system permits interposing canister 28 in lines 78 and 80 by couplings 82 and 84 which connect to the inlet and outlet 30 and 32 of the canister 28. The canister may be optionally heated within a conventional oven 85. An inert purging gas is passed through the silicalite material of the canister 28 to desorb the organic anesthetics from the silicalite granular material. In accordance with a preferred aspect of this invention, nitrogen gas or air is used as the purging gas. To enhance the desorption of the adsorbed organic anesthetics, the silicalite material is preferably heated to a temperature range of 30° C. to 150° C. It is appreciated that with other types of halogenated hydrocarbons, different temperature ranges may be necessary to effect desorption of the compounds.
In order to heat the silicalite material within the canister to this temperature the oven 85 having heating coils 87 surrounded by insulating material 89 is controlled on the basis of prior experimentation in a manner to ensure that the silicalite is in this temperature range for passing of the purging gas through the canister. It is understood that in view of the transparency of the silicalite adsorbent to microwaves, then a microwave oven may be substituted for the conventional oven 85.
The silicalite material in canister 28 during regeneration may either be heated by direct application of heat to the canister or by heating the nitrogen gas or air purging stream. In accordance with the embodiment shown in FIG. 3, the nitrogen gas from the source 86 may also be heated in heater 88 to a desired temperature in the range of 30° to 150° C. The purging gas passes through the silicalite material of the canister 28 where the fine mesh screen, as shown in FIG. 2, serve to retain the silicalite material in the canister. Hence any desired flow rate of purging gas may be used. The purging gas exits the canister 28 through line 80 and passes through a temperature sensor 90. Temperature sensor 90 provides an indication of the temperature of the purging gas in line 80. When the temperature of the purging gas in the exit line achieves a temperature nearing that of the temperature in the entrance lines 78, it has been determined that the silicalite material is at a temperature approximating the inlet temperature and that most of the organic anesthetic is desorbed. The system is then run for a desired period of time beyond that point to complete desorption. That aspect of the process may be automated and a temperature sensor 92 may be included in the inlet side to measure the temperature of the incoming stream. By way of suitable microprocessor, the signals from temperature sensors 90 and 92 may be fed to a control system 94 which compares the temperatures and actuates a signal 96 to indicate that canister regeneration is complete. It is appreciated, that regeneration of the silicalite adsorbent may take place at lower temperatures outside of the preferred range. For example, regeneration of absorbent can be achieved at temperatures as low as 25° C. where the time for regeneration is thereby extended.
It is appreciated that in the alternative, silicalite adsorbent carrying anesthetic compounds may be removed from the canister and placed with adsorbent removed from other canisters. The collected adsorbent may then be regenerated in a separate vessel in a manner as discussed with respect to a single canister.
The purging gas continues in line 80 through condenser 98. The purpose of the condenser is to remove, in liquid form, the organic anesthetics from the purging gas. Liquid nitrogen at a cryogenic temperature is fed through the condenser 98 via its inlet 100 and exit 102. This provides sufficiently cool temperatures in the line 104 of the condenser to cause the organic anesthetics to condense and permits collection in vessel 106 of liquid form anesthetics 108. To assist in the condensing of the organic anesthetics, a partial vacuum is drawn in line 104 by vacuum pump 110 connected to line 104 via line 112. The condensed liquid 108 then consists primarily of the organic anesthetics. In the course of one day, several operations may be conducted involving the same anesthetic machine 18. It may require many operations to saturate the canister 28 with anesthetics from the patient exhalent. During the different operations, it is appreciated that different anesthetics may be used. For example, Forane (trade mark) or Ethrane (trade mark) may be used separately or in combination with or without Halothane (trade mark). When the canister is saturated, two or more gases may be present inside. Hence, liquid 108 will correspondingly consist of a mixture of anesthetic components.
Regardless of the composition of the liquid 108, it is important to purify it before reuse. In accordance with standard practice, anesthetics must have a high purity level normally in excess of 90% providing remaining impurities are non-toxic. To achieve that purity, the liquid 108 is subjected to fractional distillation. A preferred system is shown in FIG. 4 consisting of a multi-stage fractional distillation comprising three columns 114, 116 and 118. The liquid 108 is fed to column 114 via line 120. Sufficient heat is applied to the bottom of column 114 to cause the liquid 108 to boil and provide a vapor take-off in line 122. The vapor 122 is fed to column 116 where heat is applied to cause boiling of the vapor 122 as it condenses in column 116. The bottoms of columns 116 are removed via line 124 for recycle with new product into column 114. The vapors removed from column 116 via line 126 are fed to column 118. The vapors in line 126 condense in column 118 and with heat supplied thereto, cause boiling resulting in a take-off of two fractions, one in vapor phase in line 128 and secondly in liquid phase in line 130. Assuming that two anesthetics are in the liquid 108, the system of FIG. 4 separates them to provide desired purities in the lines 128 and 130. For example, with Forane and Ethrane, there is a difference in boiling points of approximately 8° C. which is sufficient to provide separation of the Ethrane from the Forane.
Bacteria is present in the patient exhalent. It has been found, however, that a bacteria in the patient exhalent is not adsorbed on the silicalite material to any appreciable extent. Hence, the anesthetic produced by fractional distillation and particularly as provided in lines 128 and 130 is not contaminated and is ready for reuse. In accordance with this invention, an inexpensive process and apparatus is provided for what in essence is the manufacture of anesthetic gases from mixtures which are normally discharged to the atmosphere. Significant economic advantages are realized.
Without limiting the scope of the appended claims, the following examples exemplify preferred aspects of the inventive process.
EXAMPLE 1
A canister of the type shown in FIG. 2 was subjected to a known flow rate of air with a known concentration of the anesthetic isoflurane while monitoring the inlet and outlet concentration of isoflurane in the canister outlet until saturation of the adsorbent in the canister was detected by breakthrough of the adsorption front. The apparatus was set up to generate a constant concentration of isoflurane in the air stream. The source of air was from a cylinder of "Zero" grade air a portion of the air metered through a flow meter was passed through two midget impingers each containing 15 ml of the anesthetic isoflurane. A third impinger prevented droplets of the isoflurane from being carried over and into the air stream. The isoflurane saturated air was then mixed with the zero air. The total flowrate was measured with a second flow meter. A dry gas meter was installed at the canister outlet to provide confirmation of the flow rate indicated by the upstream flow meter. The outlets and inlets were sampled periodically throughout the tests by way of a Miran (trade mark) 1A infrared analyzer. This instrument is a variable wavelength, variable pathlink analyzer capable of measuring isoflurane to concentrations well below 1 ppm. The instrument was calibrated before use to provide accurate readouts of the inlet and outlet concentrations of the canister.
FIG. 5 is a plot of the inlet and outlet concentrations versus time at the canister. The inlet concentration was about 0.77% by volume for most of the program and the average flow rate was approximately 5.2 meters per minute. Breakthrough started to occur after about 30 minutes. The canister appeared to be fully saturated after about 100 minutes. At that point the outlet value for isoflurane concentration was only slightly less than the inlet value. The inlet value dropped because most of the isoflurane had been evaporated. There were 8 ml of isoflurane remaining in the impingers at the end program.
FIG. 6 is a plot of the net amounts of isoflurane evaporated, exhausted and retained versus time as calculated from the measured flow of isoflurane concentrations. The figure shows that about 19.5 ml were evaporated and about 12.7 ml were expected to have been adsorbed by the adsorbent in the canister at the end of the test run.
The canister of adsorbent was regenerated by use of an apparatus of the type shown in FIG. 3. The canister was heated in an oven to a temperature of approximately 140° C. The nitrogen gas passed through the canister was at a flow rate of approximately 1.3 liters per minute during regeneration. During such regeneration the nitrogen gas emerging from the coal trap was monitored for isoflurane.
FIG. 7 is a plot of the concentration versus time for the monitored isoflurane concentration in the emerging nitrogen gas stream.
FIG. 8 is a plot of the net volume of isoflurane lost versus time based on a flow rate of the 1.3 liters per minute of the regeneration gas.
The volume of isoflurane recovered from the flow trap was 11 ml. The amount expected was 12.7 ml.-1.5 ml.=11.2 mls. No water was recovered as expected since dry air was used. Furthermore, the adsorbent is principally hydrophobic. The results of the tests are therefore summarized in the following Table 1.
TABLE 1______________________________________Laboratory Test Results - Summary______________________________________Average inlet concentration 0.76%Amount of Isoflurane in impinger 30.0 mlsAmount remaining 8.0 mlsCalculated isoflurane entering canister 19.5 mlsIsoflurane exhausted 6.7 mlsAmount of isoflurane expected 12.7 mlsAmount lost during desorption 1.5 mlsNet amount expected from recovery 11.2 mlsActual amount recovered 11.0 mls______________________________________
Approximately 90% of the isoflurane was recovered by thermal desorption using a low purge flow rate for the purging gas. According to this particular set up the canister capacity for isoflurane is approximately 13 mls or 18 grams of the isoflurane. The volume of adsorptive material in the canister was approximately 185 grams of the SR-115 high silica zeolite adsorbent material.
EXAMPLE 2
The procedure of Example 1 was repeated with a view to establishing what the effect of the presence of water vapour in the gas stream had on the adsorption of the anesthetic gases. An impinger, containing water, was used to add moisture to the gas stream carrying the anesthetic gases. The average absolute humidity of 2.2% v/v was established. The inlet concentration of isoflurane was 0.84% by volume and the average flowrate was 5.2 liters per minute. Breakthrough occurred in approximately 25 minutes and the canister was completely saturated after approximately 78 minutes. Approximately 12.1 mls of isoflurane was adsorbed in the canister which is similar to the amount adsorbed in Example 1 under similar flowrate conditions. Hence the presence of moisture did not appreciably affect the adsorption of isoflurane.
The procedure of Example 1 was followed to desorb the isoflurane from the canister. Similar volume of isoflurane was recovered along with a minimal volume of water. Fractional distillation was used to separate the isoflurane from the water.
EXAMPLE 3
As the canister approaches saturation with adsorbed isoflurane continued passage of the gas stream through the canister has the potential for stripping isoflurane from the canister. The following procedure was established to determine if stripping could occur. A canister with 185 grams of silicalite was saturated with isoflurane. Air was then passed through the canister at a rate of about 6 liters per minute. The air at the exit of the canister was monitored for isoflurane using the Miran (trade mark) analyzer. At the beginning of the passage of the air stream, approximately 1.5 ml of isoflurane was removed from the saturated canister. Thereafter there was a nearly constant but extremely low concentration of isoflurane detected at the exit of the canister. This low concentration could not be accurately measured but was estimated to be at about 0.01 to 0.02% v/v for approximately 0.2 ml of liquid isoflurane per hour. Stripping of isoflurane from saturated or partially saturated canisters is therefore avoided and does not have a significant impact on the net amount of isoflurane that can be recovered from a gas stream.
EXAMPLE 4
Several canisters were used in a "real" situation by coupling the individual canisters to anesthetic machines which were in use at the Toronto General Hospital. Recovery of isoflurane from these canisters by thermal desorption in accordance with the procedure of Example 1 revealed that certain impurities were appearing in the recovered mixture. To determine the extent of impurities the following procedure was followed.
A new canister was loaded with 185 grams silicalite and regenerated at 120 degrees centigrade before use. The clean canister was coupled to a new anesthetic machine which was then put into use. After saturation of the canister it was then subjected to the procedure of Example 1 for recovery of the isoflurane. Recovery was carried out a desorption temperature of 120 degrees centigrade. The impurities identified in the recovered mixture were as follows:
1. 1-1-1-trifluoro-2-chloroethane;
2. bromochloro-1-1-difluoroethylene;
3. ethanal;
4. ethylene oxide;
5. trichlorofluoromethane;
6. dichlorodifluoromethane;
7. isopropyl alcohol;
8. 2-2-2 trifluoroethanol.
The fact that the above impurities appeared as desorbed from the adsorbent indicates that the high silica zeolite, adsorbent is capable of absorbing a variety of halogenated hydrocarbons and in turn desorbing such compounds at suitable desorption temperatures. It is thought that impurity #8 is the result of the degradation of the isoflurane. Impurity #2 is thought to be a breakdown product of halothane, ethanol (acetaldehyde) is possibly present as a patient exhalent, ethylene oxide and isopropyl alcohol are common chemicals used as disinfectants in the hospital. Impurities 5 and 6 are commonly known as Freon 11 (trade mark) and Freon 12 (trade mark). It is believed these compounds were present in the new anesthetic machine as potential filler gases, however, the presence of such gases indicate that these types of halogenated hydrocarbons are adsorbed onto the adsorbent of the canister and can be subsequently desorbed by temperature desorption.
Although the use of this canister has been demonstrated in association with an anesthetic machine, it is appreciated that the canister may be used in other systems to adsorb other types of halogenated hydrocarbons such as those commonly used as solvents, blowing agents, refrigerants, aerosol propellants and the like. Suitable systems may be set up to collect the vapours of these various agents and direct them through canisters which function in the same manner as the canisters specifically exemplified. Canisters can then be subjected to temperature desorption to provide for recovery and subsequent purification of the adsorbed halogenated hydrocarbons.
Although preferred embodiments of the invention have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.
|
A process for the recovery of halogenated hydrocarbons from a gas stream comprises passing the gas stream through a bed of hydrophobic molecular sieve adsorbent, preferably of the high silica zeolite type. Such adsorbent has pore diameters large enough to permit molecules of the halogenated hydrocarbons to pass therethrough and be selectively adsorbed in the large internal cavities of the crystal framework, whereby the halogenated hydrocarbons are removed. The gas is continued to be passed through the bed of adsorbent material until the material is saturated to the extent that breakthrough of the hydrocarbons is determined. The adsorbent material with adsorb phase of halogenated hydrocarbons is removed from the machine and regenerated by exposing the saturated material to an inert purging gas stream under conditions which desorb the halogenated hydrocarbons from the adsorbent material into the purging gas stream. The halogenated hydrocarbons are then removed from the purging gas stream and purified to a purity for reuse of the recovered halogenated hydrocarbons.
| 0
|
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention concerns a novel method and apparatus for placing a medical agent into a vessel of the body, and in particular concerns a novel method for placing embolic coils within an aneurysm of the brain.
[0003] 2. Description of the Prior Art
[0004] The use of embolic coils placed within an aneurysm for treating the aneurysm within the brain is well known. Various devices are known for delivering embolic coils through the patient's vessel to the aneurysm. Typically these embolic coils, which generally take the form of helically wound coils, or random wound coils, are carried by a coil deployment device which serves to introduce the coils into the aneurysm. The coils are then released by the coil deployment device using one of various types of release mechanisms.
[0005] An example of such a coil deployment device is disclosed in U.S. Pat. No. 6,113,622 entitled, “Embolic Coil Hydraulic Deployment System”, issued Sept. 5, 2000 and assigned to the same assignee as the present patent application. The disclosure of this patent is incorporated herein and made a part of this application. It has been found to be difficult to place these coils in the exact desired position because of the relative lack of stability of the deployment device within the vessel during the introduction of the embolic coil to an aneurysm. An example of a delivery system used to stabilize a coil deployment device is disclosed in U.S. patent application Ser. No. 09/878,530, entitled “Delivery System Using Balloon Catheter”, filed Jun. 11, 2001 and assigned to the same assignee as the present patent application. The disclosure in this patent application is incorporated by reference and is made a part of the subject patent application.
[0006] It is, therefore, an object of this invention to provide a method for placing embolic coils in a relatively precise manner by the use of a stabilizing delivery catheter.
[0007] Another object of the present invention is to provide a method for placing embolic coils within an aneurysm of the brain, which system is relatively simple in use for the physician.
[0008] A further object of the present invention is to provide a method for delivering medical agents such as diagnostic or therapeutic agents, and other medical agents by the use of a delivery catheter in a relatively simple, efficient and stable manner.
[0009] A still further object is to provide a delivery catheter which enables the delivery of embolic coils within an aneurysm in a relatively simple, efficient and stable manner.
[0010] Another object of the present invention is to provide a delivery catheter which may be utilized to deliver embolics, diagnostic, and therapeutic agents by way of a delivery lumen.
[0011] A further object of the present invention is to provide a delivery catheter that is relatively simple in construction.
[0012] Other objects of the present invention will become apparent from the following description.
SUMMARY OF THE INVENTION
[0013] In accordance with one aspect of the present invention, there is provided a method for placing an embolic coil into an aneurysm, such as an aneurysm within the brain, by use of a delivery catheter. The delivery catheter includes a first lumen and a second lumen with a side opening which extends positioned generally proximal to the distal end of the catheter. The delivery catheter also includes a puller wire which extends through the first lumen and is fixedly attached to the delivery catheter at a location proximal to the distal end of the catheter. The method comprises the steps of introducing the delivery catheter into the vessel of a patient over a guidewire. The guidewire extends through the second lumen and serves to generally align the side opening with the aneurysm. The method also includes the steps of withdrawing the guidewire, pulling the proximal end of the puller wire to cause the delivery catheter to deflect, or bow, at a location proximal to the side opening to thereby cause the side opening to move in a position adjacent to the aneurysm, introducing an embolic coil deployment device into the delivery catheter through the second lumen and then through the side opening into the aneurysm, delivering an embolic coil into the aneurysm, withdrawing the embolic coil deployment device from the delivery catheter, releasing the proximal end of the puller wire to permit the catheter to straighten, and thereafter withdrawing the delivery catheter from the vessel of the patient.
[0014] In accordance with another aspect of the present invention, there is provided a method for placing a medical agent, which may take the form for example of a diagnostic or therapeutic device, or a liquid embolic material, or an embolic coil, at a preselected position within a vessel of the body. The method utilizes a delivery catheter having a first and second lumen and a side opening in the second lumen proximal the distal end of the catheter. Also the catheter includes a puller wire which extends through the first lumen and is fixedly attached to the delivery catheter at a location proximal to the distal end of the catheter. The method comprises the steps of pre-loading the delivery catheter with a guidewire by placing the guidewire into the second lumen, thereafter introducing the catheter into the vessel of a patient to generally align the side opening of the catheter at a preselected position within the vessel, pulling the proximal end of the puller wire to cause the catheter to deflect, or bow, at the preselected position within the vessel to thereby stabilize the catheter within the vessel, withdrawing the guidewire, introducing a deployment device for carrying the medical agent into the second lumen of the delivery catheter and through the side opening to deliver the medical agent at the preselected position, releasing the proximal end of the puller wire to permit the delivery catheter to become straighten, and thereafter withdrawing the delivery catheter from the vessel of the patient.
[0015] In accordance with other embodiments of the present invention, the method may include delivery of a medical agent which takes the form of a diagnostic or therapeutic agent, an embolic coil, or other medicament.
[0016] In accordance with still another embodiment of the invention, the method includes the use of a hydraulic deployment system for delivering an embolic coil through a delivery catheter to an aneurysm. The hydraulic deployment device includes a positioning catheter having a distal tip for retaining the embolic coil. When the positioning catheter is pressurized with a fluid, the distal tip of the positioning catheter expands outwardly to release the coil at the preselected position within the aneurysm.
[0017] In accordance with another aspect of the present invention there is provided an apparatus for placing an embolic agent into a vessel. The apparatus comprises a delivery catheter having a proximal section, a distal section and an intermediate section which is formed of a relatively flexible polymeric material. The catheter also includes a side opening at a location within the intermediate section, and a puller wire extending through the first lumen and being fixedly attached to the delivery catheter at a location proximal the distal end of the catheter. When the puller wire is pulled proximately the relatively flexible intermediate section deflects to thereby cause the side opening of the catheter to move laterally with respect to the catheter.
[0018] A more detailed explanation of the invention is provided in the following description and claims, and is illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] [0019]FIG. 1 is a partial sectional view of a delivery catheter constructed in accordance with the principles of the present invention;
[0020] [0020]FIG. 2 is a partial sectional view of a vascular occlusive coil deployment system that may be used with the delivery catheter of FIG. 1;
[0021] [0021]FIG. 3 is a side elevational view of the delivery catheter of FIG. 1 in use to delivery an embolic coil to an aneurysm;
[0022] [0022]FIG. 4 is a cross-sectional view of the catheter of FIG. 3, taken along the plane of the line 5 - 5 ′ of FIG. 3;
[0023] [0023]FIG. 5 is a cross-sectional view of the catheter of FIG. 3, taken along the plane of line 5 - 5 ′ of FIG. 3; and,
[0024] [0024]FIGS. 6 through 8 are diagrammatic sequential views of a method of placing embolic coils in accordance with an embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] [0025]FIG. 1 generally illustrates the construction of a preferred embodiment of the delivery catheter of the present invention which generally comprises a dual lumen catheter 10 having a “Y” connector 12 coupled to the proximal end of the catheter. More particularly, the dual lumen catheter includes a first lumen 14 and a second lumen 16 . The second lumen 16 extends from the proximal end of the catheter to the distal end of the catheter and also communicates with a lumen 18 which extends from the distal end to the proximal end of the “Y” connector 12 . As illustrated, a side opening 20 extends from the second lumen 16 through the side wall of the catheter at a position which is slightly proximate the distal tip of the delivery catheter 10 . This side opening, as will be subsequently explained in more detail, serves to permit the introduction of an embolic coil deployment device into an aneurysm for placement of an embolic coil into the aneurysm.
[0026] As further illustrated in FIG. 1, the first lumen 14 extends from the proximal end of the delivery catheter 10 to a position slightly proximal the location on the catheter of the side opening 20 . At that point the first lumen 14 exits the side wall of the catheter. A corresponding first lumen 14 a extends along the same axis as lumen 14 , but extends from the distal end of the catheter and also exits through the side wall of the catheter at a position slightly distal on the catheter of the side opening 20 . In addition, the proximal end of the first lumen 14 communicates with a second passageway in the “Y” connector 12 and extends out of the side port 22 of the “Y” connector 12 . As may be seen, a puller wire 24 extends from the proximal end of the side port 22 of the “Y” connector and through the lumen 14 of the delivery catheter 10 and exits the first lumen 14 and re-enters the corresponding first lumen 14 a . Still further, the puller wire 24 is fixedly attached within the corresponding first lumen 14 a at the distal end of this lumen.
[0027] While the delivery catheter 10 may be constructed of various flexible materials including various polymers, preferably, the catheter 10 is formed in three different sections of materials having different durometers and different polymer compositions. The proximal section of the catheter 23 A, designated as “A” is preferably formed of a nylon material having a durometer of about 75D and extends for a length of about 100 centimeters. The intermediate section 23 B, designated “B”, is preferably formed of a pellethane material having a durometer of about 65D and is generally about 40 centimeters in length, and the distal section 23 C of the catheter, designated “C”, is preferably formed of a pellethane material having a durometer of about 80A and extends for a length of about 10 centimeters. With this construction the catheter is sufficiently flexible to be delivered through the various tortuous vessels of the human brain but at the same time provides sufficient rigidity or “back-up” support for introducing the catheter into and through these vessels. This construction also makes possible the ease of deflection, or bowing, of the intermediate section 23 B.
[0028] [0028]FIG. 2 illustrates a hydraulic occlusive coil deployment device 100 which is comprised of a hydraulic injector, or syringe, 102 , coupled to the proximal end of a positioning catheter 104 . An embolic coil 106 is disposed within the lumen at the distal section 108 of the catheter. The proximal end of the coil 106 is tightly held within the lumen of the distal section 108 of the catheter 104 until the deployment device is activated for release of the coil. As may be seen, the syringe 102 includes a threaded piston 110 which is controlled by the handle 112 for infusing fluid into the interior of the catheter 104 . Also, as illustrated, the catheter 104 includes a winged hub 114 which aids in the insertion of the catheter.
[0029] The embolic coil 106 may take various forms and configurations, and may even take the form of a randomly wound coil. Preferably, the distal section of the coil deployment device 100 is formed of a polymeric material with a relatively low durometer which exhibits the characteristic that, when a fluid pressure of approximately 300 psi is applied to the interior of the catheter, the walls of the distal section 108 expand radially, somewhat similar to the action of a balloon inflating, to thereby release the proximal end of the coil 106 . Reference is made to the above-mentioned U.S. Pat. No. 6,113,622 for a more detailed description of the hydraulic occlusive coil deployment device 100 .
[0030] [0030]FIG. 3 illustrates in detail the delivery catheter 10 which has been inserted into a blood vessel 26 of the brain in order to place an embolic coil 106 into an aneurysm 28 . FIGS. 4 and 5 illustrate cross-sections taken through the delivery catheter 10 at locations indicated by 4 - 4 ′ prime and 5 - 5 ′, respectively, shown in FIG. 3. More particularly, FIG. 4 in conjunction with FIG. 3 illustrates the location 30 where the puller wire 24 exits and re-enters through the side wall of the catheter. Also illustrated in FIG. 4 is an end view of the embolic coil deployment device which extends through the side opening 20 of the catheter 10 . FIG. 5 illustrates a sectional view of the delivery catheter 10 with the first lumen 14 and second lumen 16 which serve to carry the puller wire 24 and the embolic coil deployment device 100 .
[0031] Reference is made to FIGS. 3 and 6 through 8 for an understanding of the operation of the delivery catheter used in conjunction with the embolic coil deployment device 100 . As illustrated in FIG. 6, the delivery catheter is inserted into a vessel, preferably over a guidewire 32 , and is positioned such that the side opening 20 is adjacent to an aneurysm 28 . The guidewire 32 is then removed. Thereafter, the puller wire 24 is pulled proximally, as illustrated in FIG. 7, to thereby cause the delivery catheter 10 to deflect, or bow, in the region where the side opening 20 is located to thereby cause the side opening to essentially mate with the opening of the aneurysm 28 . Once the opening has been positioned at the mouth of the aneurysm 28 , the embolic coil deployment device 100 may then be inserted through the second lumen and then out of the side opening 20 and into the aneurysm 28 . An embolic coil 106 may then be placed into the aneurysm and released from the distal end of the deployment device 100 . The deployment device 100 may then be removed and this process may be repeated until such time as sufficient coils have been placed into the aneurysm. When the aneurysm 28 has been sufficiently filled with embolic coils, the coil deployment device may be removed from the delivery catheter. Thereafter, the puller wire may be released to thereby permit the catheter to straighten within the vessel. Once the catheter has straightened within the vessel, the catheter may be easily withdrawn from the vessel and from the body of the patient.
[0032] As may be appreciated, with the present invention it is possible to stabilize the delivery catheter at a position where the side opening of the delivery catheter is adjacent to the aneurysm. Embolic coils may be delivered through the side opening of the delivery catheter directly into the aneurysm with relatively good precision. With this system it is possible to fill an aneurysm with a plurality of embolic coils in very short order without the loss of coils into the main blood vessel, or other vessels within the body. These and other advantageous of this invention will become more apparent from an understanding of the invention as claimed.
[0033] A novel system and method have been disclosed in which an embolic coil, or coils, may be securely placed within an aneurysm with a delivery catheter which is stabilized. Although an illustrative embodiment of the invention has been shown and described, it is to be understood that various modifications and substitutions may be made by those skilled in the art without departing from the spirit and scope of the present invention. Further, in addition to the delivery of embolic coils, the system may be utilized to deliver other medical agents such as diagnostic or therapeutic agents of various types including liquid embolic materials. Other modifications may be made which would be within the spirit and the scope of the following claims.
|
A method and apparatus for placing a medical agent, such as an embolic coil into a vessel, or aneurysm, by utilizing a stabilizing catheter to retain or support a medical agent deployment device.
| 0
|
TECHNICAL FIELD
[0001] The invention relates to a fastener for a roof installation support, in particular a support for a solar technology plant. It further relates to a roof installation system, in particular for a solar technology system.
PRIOR ART
[0002] Solar technology systems, including photovoltaic systems and solar collectors are installed on house roofs using special roof installation systems which are designed to avoid as much as possible penetrating the roof covering by auxiliary installation means.
[0003] It is important, especially in the case of fiat roofs whose seal is produced by plastic sealing webs (KDB), to avoid a penetration of the roof seal by the support or fastening means of the roof installation system. EP 2 418 438 A2 discloses a support for a roof installation system for photovoltaic systems, which support can be connected by means of flexible fastening strips to a plastic sealing web without penetration thereof, by welding or adhesive fastening.
[0004] A fastener for a roof installation support is known from WO 2012/004542 A2 and comprises a base plate in which pins are introduced, which penetrate the base plate. On the whole, the structure according to WO 2012/004542 A2 is comparatively complex, which is associated with a correspondingly expensive manufacture. A one-piece holder is known from DE 20 2010 005 531 U1, in which a base plate is constructed designed as integral with angular webs. Screw holes which cooperate with corresponding screws are provided for the actual fastening. The angular webs therefore serve merely as a guide, with the actual fastening being accomplished by a screw connection. As a result, this solution is also comparatively complex and is associated with high production and installation cost.
DESCRIPTION OF THE INVENTION
[0005] The object of the invention is to indicate an improved fastener for a roof installation support and a correspondingly improved roof installation system that offer increased strength and reliability and can be economically produced and installed.
[0006] This object is attained by a fastener having the features of Claim 1 and by a roof installation system having the features of Claim 11 . Advantageous further developments of the concept of the invention are the subject matter of the respective dependent claims.
[0007] One concept of the invention consists in constructing the fastener with two sections that are defined differently in terms of function and as regards significant mechanical properties: On the one hand, a baseplate section is provided for attachment to the base, which baseplate section has a sufficiently large surface and a certain flexibility for adapting to a (slightly) uneven base. On the other hand, a (rather) stiff section is provided for securely fixing the profile section of the support that will be fastened. Furthermore, the invention also comprises the concept of constructing this latter section as a profile section which is geometrically constructed for surrounding and positively fixing a profile section of the roof installation support without additional fastening means such as screws or the like. In particular, the fastener has precisely one such surrounding profile section. “Profile section” denotes a longitudinally extended section of a structural component with a given cross section (e.g. with or comprising a C, U, T, L, I cross section). In particular, the material thickness of such profile sections is constant.
[0008] In one embodiment of the invention the baseplate section has a strip-like first partial section from which the profile section rises up, and a second partial section extending from the first partial section to a longitudinal side as a widened area, said second partial section being more flexible than the first partial section. In another embodiment the baseplate section has a third and a fourth partial section extending from the ends of the first partial section to the side opposite the second partial section. Both embodiments serve to make a sufficiently large base surface of the fastener available in an advantageous manner that will ensure, in particular, a support on the base on both sides of the profile support section fixed to the fastener.
[0009] In another embodiment the profile section is U-shaped and the “U” is open toward the base plate section in such a way that the profile section of the roof installation support, which section is surrounded in the installed state, is enclosed between the base plate section and the profile section of the fastener. In this case, the “U” has a free first shank which is spaced by a sufficiently wide slot from the base plate section that the profile section of the roof installation support can be introduced laterally into the profile section of the fastener through the slot by tilting it about an axis parallel to its longitudinal extension.
[0010] It is provided in one embodiment that the second shank of the “U” is connected stiffly, in particular integrally to the base plate section. Furthermore, it is provided in terms of design that stiffening ribs running transversely to the longitudinal extent of the first partial section of the base plate section are formed in the throat between the profile section and the base plate section where the second shank of the “U” is connected to the base plate section. On the whole, a configuration of the fastener that is preferably constructed in such a manner ensures sufficient stiffness and a stable position of the fastened support on the base, while at the same time ensuring sufficient ease of installation and a durable fastening on the base.
[0011] In a manufacturing embodiment, the fastener is manufactured as integral, in particular as in injection-molded part. In this case a unified material construction can be provided, but as an alternative a construction consisting of a first material component for the flexible base plate section and a second material component for the (substantially) stiff profile section can be provided.
[0012] For the most important areas of use currently envisioned, at least the base plate section is manufactured from heat weldable material, in particular PVC or TPO, or adhesive material. This takes into account the fact that plastic sealing webs on which the fastener is to be used typically consist of PVC or TPO (also referred to as FPO), although so-called liquid films are also considered as possible bases.
[0013] One length of the profile section is preferably (on average) at least 3 times, preferably at least 5 times as large as a maximal extension in one direction perpendicular to the longitudinal direction of the profile section. As a result, the fastener can create an especially reliable fastening. Alternatively or additionally, the profile section can have a constant material thickness. As a result, the profile section can be produced in an especially simple manner and can nevertheless ensure a secure connection.
[0014] A material thickness of the profile section is (on average) preferably greater (at least 1.2 times or at least 1.5 times greater) than a material thickness of the baseplate section. Alternatively or additionally, an E modulus of the profile section can (on average) be greater than an E modulus of a material of the baseplate section (at least 1.2 times or at least 1.5 times or at least twice as great). As a result of these measures, an increased stiffness of the profile section relative to the baseplate section can be achieved in a simple manner.
[0015] In a preferred embodiment, a (average) height of the profile section is greater than a (average) width of the profile section (preferably at least 1.5 times greater, further preferably at least 2 times greater and even more preferably at least 3 times greater). The direction of the height is perpendicular to the surface of the baseplate section. The direction of the width is perpendicular to the direction of the height and the longitudinal direction provided by the extension of the profile section. As a result, a longitudinal edge of a roof installation support can be accommodated especially securely in the profile section, wherein the different degrees of stiffness can be utilized synergistically by the base body section and the profile section. On the whole, a reliable fastening can be achieved with simple measures. If the profile section is a U profile section (as described further above), the second shank of the “U” opposite the first shank can be larger than a connecting section between the two shanks, in particular at least 1.5 times, preferably at least 2 times, and even more preferably at least 3 times as large. In the case (as described above) of a U-shaped design of the profile section, the height of the profile section is defined by the second shank opposite the first shank. A width is defined by the connecting section between the two shanks.
[0016] In an embodiment of the proposed roof installation system, the one or the plurality of roof installation supports have a longitudinally extended base body with two longitudinal sides and two end face sides and the fasteners are constructed for attaching at least one longitudinal side of the roof installation system. For commercially available supports which have two profiles on their bottom side for support on the base, two or more, especially four fasteners are provided, in conformity with the system.
[0017] In a preferred embodiment of the roof installation system, said system comprises at least one first and one second (separate from the first) fastener, wherein the first fastener is provided for attaching a first longitudinal edge of the roof installation support and the second fastener is provided for attaching a second longitudinal edge of the roof installation support. In addition, (at least) two first fasteners and (at least) two second fasteners are preferably provided. Therefore, according to a general concept of the present invention, a plurality of (separate) fasteners that are associated with a (respective) roof installation support are provided within a roof installation system. As a result, in combination with the flexible base plate section and the comparatively stiff profile section, even given uneven bases, a reliable fastening of the roof installation support can be synergistically achieved.
[0018] At least one first and one second fastener are preferably provided, wherein the fasteners have a “U-shaped profile section, with the openings of the “U” of the first and of the second fastener facing one another. Such a construction facilitates the fastening of the roof installation support. In particular, use is made of the fact that the separate fasteners can be moved and/or tilted relative to one another (before fastening), so that the longitudinal edges of the roof installation support can be introduced into the profile sections (by tilting). This would not be possible, for example, with fastening sections constructed as fixed relative to one another.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Advantages and uses of the invention also result from the following description of exemplary embodiments and aspects, in part in reference to the figures. In the figures:
[0020] FIG. 1 shows a perspective view of a fastener according to an embodiment of the invention, and
[0021] FIG. 2 shows a perspective view of the roof support of a roof installation system provided with a plurality of fasteners according to FIG. 1 .
WAY OF CARRYING OUT THE INVENTION
[0022] FIG. 1 shows a perspective view of a fastener 1 of a roof carrier for a photovoltaic system, which fastener is manufactured as an integral injection molded part and comprises a substantially level base plate section 3 which has a certain flexibility and a stiff profile section 5 projecting upward from it. The baseplate section has a strip-like first partial section 3 a from the central area of which the profile section 5 rises up, and has a second partial section 3 b extending therefrom to a longitudinal side as widened section. Two other widening partial sections 3 c, 3 d extend from the ends of the first partial section 3 a to the opposite side. Two stiffening ribs 3 e, 3 f are formed in the strip-like first partial section 3 a in the vicinity of its two longitudinal edges and running parallel to the latter.
[0023] The profile section 5 projects upward from the first stiffening rib 3 e and has a narrow “U” shape in its cross section. The “U” is open on one side toward the baseplate section 3 , that a profile section of a roof installation support is adapted to the shape of the fasteners in its geometrical shape, is pushed in and enclosed between the baseplate section and the profile section 3 and can be jointly fixed by the latter. Accordingly, the U-shaped profile 5 has a free first shank 5 a and a second shank 5 b connected to the baseplate section. Stiffening ribs 5 c on the second shank 5 b of the profile section 5 that additionally support the latter vis-à-vis the baseplate section 3 and stiffen the connection between both are not shown in FIG. 2 but can be recognized in FIG. 2 (see below in this regard).
[0024] FIG. 2 shows four fasteners of the type shown in FIG. 1 and described further above, attached to a support 7 of a roof installation system. Support 7 comprises a bottom part consisting of two profile parts 7 a, 7 b and an upper part 7 c opposite the bottom part and inclined at an angle relative thereto, on which upper part photovoltaic modules are held when the support is being used. The precise construction of the support is not important in with the context of the invention, however it should be pointed out that the profile section 5 of the fastener 1 is adapted to the profile parts 7 a, 7 b of the support 7 such that it engages into the latter in the manner shown in FIG. 2 and surrounds a section of the support profile part and exclusively holds it positively (without additional fastening elements) on the baseplate section 3 of the fastener. Since the former is, for its part, welded or (in the case of liquid film) adhesively fastened to the underlying plastic web, the fasteners hold the support reliably on the roof covering.
[0025] Furthermore, it is clear that the widened-out areas 3 c, 3 d not only serve to enlarge the support surface of the fastener on the roof surface but also form a base for the end sections of the support profiles 7 a, 7 b and help prevent possible damage to the roof covering by said end sections. Radii in all corners of the base plate section of the fastener serve the same purpose.
[0026] The implementation of the invention is not limited to the examples and aspects explained above, but rather is possible in a plurality of modifications that are part of the knowledge of a person skilled in the art.
LIST OF REFERENCE NUMERALS
[0000]
1 . Fastener
3 . Base plate section
3 a, 3 b, 3 c, 3 d Partial section of the base plate section
3 e, 3 f Stiffening rib
5 Profile section of the fastener
5 a, 5 b Shanks of the profile section
5 c Stiffening ribs
7 . Roof installation support
7 a, 7 b Profile section of the roof installation support
7 c Upper part
|
A fastener for a roof installation support, in particular for a support of a solar technology system, having an at least sectionally flexible baseplate section and a substantially stiff profile section rising up from the baseplate section, which profile section is constructed to surround and positively fix a profile section of the roof installation support.
| 5
|
[0001] The present invention relates to compounds of formula I or pharmaceutically acceptable salts thereof, that selectively modulate, regulate, and/or inhibit signal transduction mediated by certain native and/or mutant protein kinases implicated in a variety of human and animal diseases such as cell proliferative, metabolic, allergic, and degenerative disorders. More particularly, these compounds are potent and selective native and/or mutant c-kit inhibitors.
BACKGROUND OF THE INVENTION
[0002] Protein Kinases are receptor type or non-receptor type proteins, which transfer the terminal phosphate of ATP to aminoacid residues, such as tyrosine, threonine, serine residues, of proteins, thereby activating or inactivating signal transduction pathways. These proteins are known to be involved in many cellular mechanisms, which in case of disruption, lead to disorders such as abnormal cell proliferation and migration as well as inflammation.
[0003] As of today, there are over 500 known Protein kinases. Included are the well-known Abl, Akt1, Akt2, Akt3, ALK, AlkS, A-Raf, Axl, B-Raf, Brk, Btk, Cdk2, Cdk4, CdkS, Cdk6, CHK1, c-Raf-1, Csk, EGFR, EphA1, EphA2, EphB2, EphB4, Erk2, Fak, Fes, Fer, FGFR1, FGFR2, FGFR3, FGFR4, Flt-3, Fms, Frk, Fyn, Gsk3α, Gsk313, HCK, Her2/Erbb2, Her4/Erbb4, IGF1R, IKK beta, Irak4, Itk, Jak1, Jak2, Jak3, Jnk1, Jnk2, Jnk3, KDR, Kit, Lck, Lyn, MAP2K1, MAP2K2, MAP4K4, MAPKAPK2, Met, Mer, MNK1, MLK1, mTOR, p38, PDGFRα, PDGFRβ, PDPK1, PI3Kα, PI3Kβ, PI3Kγ, PI3Kδ, Pim1, Pim2, Pim3, PKC alpha, PKC beta, PKC theta, Plk1, Pyk2, Ret, ROCK1, ROCK2, RON, Src, Stk6, Syk, TEC, Tie2, TrkA, TrkB, Tyk2, VEGFR1/Flt-1, VEGFR2/Kdr, VEGFR3/Flt-4, Yes, and Zap70.
[0004] Abnormal cellular responses triggered by protein kinase-mediated events produce a variety of diseases. These include autoimmune diseases, inflammatory diseases, neurological and neurodegenerative diseases, cancer, cardiovascular diseases, allergies and asthma, Alzheimer's disease and hormone-related diseases.
[0005] Tyrosine kinases are receptor type or non-receptor type proteins, which transfer the terminal phosphate of ATP to tyrosine residues of proteins thereby activating or inactivating signal transduction pathways. These proteins are known to be involved in many cellular mechanisms, which in case of disruption, lead to disorders such as abnormal cell proliferation and migration as well as inflammation.
[0006] As of today, there are about 58 known receptor tyrosine kinases. Included are the well-known VEGF receptors (Kim et al., Nature 362, pp. 841-844, 1993), PDGF receptors, c-kit, Flt-3 and the FLK family. These receptors can transmit signals to other tyrosine kinases including Src, Raf, Frk, Btk, Csk, Abl, Fes/Fps, Fak, Jak, Ack, etc.
[0007] Among tyrosine kinase receptors, c-kit is of special interest. Indeed, c-kit is a key receptor activating mast cells, which have proved to be directly or indirectly implicated in numerous pathologies for which the Applicant filed WO 03/004007, WO 03/004006, WO 03/003006, WO 03/003004, WO 03/002114, WO 03/002109, WO 03/002108, WO 03/002107, WO 03/002106, WO 03/002105, WO 03/039550, WO 03/035050, WO 03/035049, U.S. 60/359,652, U.S. 60/359,651 and U.S. 60/449,861, WO 04/080462, WO 05/039586, WO 06/135721, WO 07/089,069, WO 07/124,369, WO 08/137,794, WO 08/063,888, WO 08/011,080, WO 09/109,071, WO 10/096,395.
[0008] It was found that mast cells present in tissues of patients are implicated in or contribute to the genesis of diseases such as autoimmune diseases (rheumatoid arthritis, inflammatory bowel diseases (IBD)), allergic diseases, bone loss, cancers such as solid tumors, leukaemia and GIST, tumor angiogenesis, inflammatory diseases, interstitial cystitis, mastocytosis, graft-versus-host diseases, infection diseases, metabolic disorders, fibrosis, diabetes and CNS diseases. In these diseases, it has been shown that mast cells participate in the destruction of tissues by releasing a cocktail of different proteases and mediators such as histamine, neutral proteases, lipid-derived mediators (prostaglandins, thromboxanes and leukotrienes), and various cytokines (IL-1, IL-2, IL-3, IL-4, IL-5, IL-6, IL-8, TNF-α, GM-CSF, MIP-1a, MIP-1b, MIP-2 and IFN-γ).
[0009] The c-kit receptor also can be constitutively activated by mutations leading to abnormal cell proliferation and development of diseases such as mastocytosis (D816V mutation) and various cancers such as GIST (c-kitΔ27, a juxtamembrane deletion).
[0010] Sixty to 70% of patients presenting with AML have blasts which express c-kit, the receptor for stem cell factor (SCF) (Broudy, 1997). SCF promotes growth of hematopoietic progenitors, and act as a survival factor for AML blasts. In some cases (1 to 2%) of AML, a mutation in a conserved residue of the kinase domain (Kit816) resulting in constitutive activation of c-kit has been described (Beghini et al., 2000; Longley et al., 2001). This gain of function mutation (Asp to Val/Tyr substitution) has been identified in mast cell leukemic cell lines and in samples derived from patients with mastocytosis (Longley et al., 1996). Preliminary results show that this mutation is expressed in most cases of systemic mastocytosis ([˜60%], P Dubreuil, AFIRMM, study in progress on about 300 patients).
GOAL OF THE INVENTION
[0011] The main objective underlying the present invention is therefore to find potent and selective compounds capable of inhibiting wild type and/or mutated protein kinase, in particular wild type and/or mutated tyrosine kinase, and more particularly wild type and/or mutated c-kit.
[0012] In connection with the present invention, we have discovered that compounds of formula I are potent and selective inhibitors of certain protein kinases such as wild type and/or mutated c-kit. These compounds are good candidates for treating diseases such as autoimmunes diseases, inflammatory diseases, cancers and mastocytosis.
DESCRIPTION OF THE INVENTION
[0013] Compounds of the present invention were screened for their ability to inhibit a protein kinase and in particular a tyrosine kinase, and more particularly c-Kit and/or mutant c-Kit (especially c-Kit D816V).
[0014] In a first embodiment, the invention is aimed at compounds of formula I, which may represent either free base forms of the substances or pharmaceutically acceptable salts thereof:
[0000]
[0015] Wherein
[0016] A is five or six member heterocycle ring;
[0017] R 1 is hydrogen, halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms, a thioalkyl group or an alkoxy group;
[0018] R 2 is halogen (selected from F, Cl, Br or I), an aryl group, an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably sulfur, oxygen or nitrogen, optionally substituted with an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group, a thioalkyl group or an haloalkoxy group; as well as a —COOR, —NRR′, —NR—CO—R′, —CONRR′, —SO 2 NRR′ or —NR—SO 2 —R′ group wherein R and R′ are each independently selected from hydrogen, aryl group, heteroaryl group, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group;
[0019] R 3 is hydrogen, halogen (selected from F, Cl, Br or I), cyano, an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group; as well as CF 3 , —NRR′, —NR—CO—R′, —CONRR′, —SO 2 NRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably sulfur, oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group;
[0020] Q is O or S;
[0021] W is N or CR 4 ;
[0022] R 4 is hydrogen, cyano, CF 3 , halogen (selected from F, Cl, Br or I), a thioalkyl group, an alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably sulfur, oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group, a solubilising group, an heterocycle, —CO—NRR′, —SO 2 —NRR′, —NRR′, —NR—CO—R′ or —NR—SO 2 R′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0023] X is N or CR 5 ;
[0024] R 5 is hydrogen, cyano, halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms, an alkoxy group, —CO—OR, —CO—NRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably sulfur, oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group.
[0025] In one embodiment, the invention relates to compounds of formula I or pharmaceutically acceptable salts thereof, wherein R 2 is halogen (selected from F, Cl, Br or I), an aryl group, an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably sulfur, oxygen or nitrogen, optionally substituted with an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group, a thioalkyl group or an haloalkoxy group; as well as a —NRR′, —NR—CO—R′, —CONRR′, —SO 2 NRR′ or —NR—SO 2 —R′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group.
[0026] Unless otherwise specified, the below terms used herein are defined as follows.
[0027] As used herein, the term “alkyl” means a saturated straight chain or branched non-cyclic hydrocarbon having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms. Representative saturated straight chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl; while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2-dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4-ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, 3,3-diethylhexyl and the like. Alkyl groups included in compounds of this invention may be optionally substituted with one or more substituents. Alkyl groups included in compounds of this invention may be optionally substituted with a solubilising group.
[0028] As used herein, the term “aryl” means a monocyclic or polycyclic-aromatic radical comprising carbon and hydrogen atoms. Examples of suitable aryl groups include, but are not limited to, phenyl, tolyl, anthracenyl, fluorenyl, indenyl, azulenyl, and naphthyl, as well as benzo-fused carbocyclic moieties such as 5,6,7,8-tetrahydronaphthyl. An aryl group can be unsubstituted or substituted with one or more substituents. Aryl groups included in compounds of this invention may be optionally substituted with a solubilising group.
[0029] As used herein, the term “alkoxy” refers to an alkyl group as defined above which is attached to another moiety by an oxygen atom. Examples of alkoxy groups include methoxy, isopropoxy, ethoxy, tert-butoxy, and the like. Alkoxy groups may be optionally substituted with one or more substituents. Alkoxy groups included in compounds of this invention may be optionally substituted with a solubilising group.
[0030] As used herein, the term “thioalkyl” refers to an alkyl group as defined above which is attached to another moiety by a sulfur atom. Thioalkyl groups may be optionally substituted with one or more substituents. Thioalkyl groups included in compounds of this invention may be optionally substituted with a solubilising group.
[0031] As used herein, the term “heterocycle” refers collectively to heterocycloalkyl groups and heteroaryl groups.
[0032] As used herein, the term “heterocycloalkyl” means a monocyclic or polycyclic group having at least one heteroatom selected from O, N or S, and which has from 2 to 11 carbon atoms, which may be saturated or unsaturated, but is not aromatic. Examples of heterocycloalkyl groups including (but not limited to): piperidinyl, piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, 4-piperidonyl, pyrrolidinyl, hydantoinyl, valerolactamyl, oxiranyl, oxetanyl, tetrahydropyranyl, tetrahydrothiopyranyl, tetrahydropyrindinyl, tetrahydropyrimidinyl, tetrahydrothiopyranyl sulfone, tetrahydrothiopyranyl sulfoxide, morpholinyl, thiomorpholinyl, thiomorpholinyl sulfoxide, thiomorpholinyl sulfone, 1,3-dioxolane, tetrahydrofuranyl, dihydrofuranyl-2-one, tetrahydrothienyl, and tetrahydro-1,1-dioxothienyl. Typically, monocyclic heterocycloalkyl groups have 3 to 7 members. Preferred 3 to 7 membered monocyclic heterocycloalkyl groups are those having 5 or 6 ring atoms. A heteroatom may be substituted with a protecting group known to those of ordinary skill in the art, for example, the hydrogen on a nitrogen may be substituted with a tert-butoxycarbonyl group. Furthermore, heterocycloalkyl groups may be optionally substituted with one or more substituents. In addition, the point of attachment of a heterocyclic ring to another group may be at either a carbon atom or a heteroatom of a heterocyclic ring. Only stable isomers of such substituted heterocyclic groups are contemplated in this definition.
[0033] As used herein, the term “heteroaryl” or like terms means a monocyclic or polycyclic heteroaromatic ring comprising carbon atom ring members and one or more heteroatom ring members (such as, for example, oxygen, sulfur or nitrogen). Typically, a heteroaryl group has from 1 to about 5 heteroatom ring members and from 1 to about 14 carbon atom ring members. Representative heteroaryl groups include pyridyl, 1-oxo-pyridyl, furanyl, benzo[1,3]dioxolyl, benzo[1,4]dioxinyl, thienyl, pyrrolyl, oxazolyl, imidazolyl, thiazolyl, isoxazolyl, quinolinyl, pyrazolyl, isothiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, triazolyl, thiadiazolyl, isoquinolinyl, indazolyl, benzoxazolyl, benzofuryl, indolizinyl, imidazopyridyl, tetrazolyl, benzimidazolyl, benzothiazolyl, benzothiadiazolyl, benzoxadiazolyl, indolyl, tetrahydroindolyl, azaindolyl, imidazopyridyl, quinazolinyl, purinyl, pyrrolo[2,3]pyrimidinyl, pyrazolo[3,4]pyrimidinyl, imidazo[1,2-a]pyridyl, and benzo(b)thienyl. A heteroatom may be substituted with a protecting group known to those of ordinary skill in the art, for example, the hydrogen on nitrogen may be substituted with a tert-butoxycarbonyl group. Heteroaryl groups may be optionally substituted with one or more substituents. In addition, nitrogen or sulfur heteroatom ring members may be oxidized. In one embodiment, the heteroaromatic ring is selected from 5-8 membered monocyclic heteroaryl rings. The point of attachment of a heteroaromatic or heteroaryl ring to another group may be at either a carbon atom or a heteroatom of the heteroaromatic or heteroaryl rings.
[0034] As used herein, the term “haloalkyl” means an alkyl group as defined above in which one or more (including all) the hydrogen radicals are replaced by a halo group, wherein each halo group is independently selected from —F, —Cl, —Br, and —I. The term “halomethyl” means a methyl in which one to three hydrogen radical(s) have been replaced by a halo group. Representative haloalkyl groups include trifluoromethyl, bromomethyl, 1,2-dichloroethyl, 4-iodobutyl, 2-fluoropentyl, and the like. Haloalkyl groups may be optionally substituted with one or more substituents. Haloalkyl groups included in compounds of this invention may be optionally substituted with a solubilising group.
[0035] As used herein, the term “haloalkoxy” means an alkoxy group as defined above in which one or more (including all) the hydrogen radicals are replaced by a halo group, wherein each halo group is independently selected from —F, —Cl, —Br, and —I. Representative haloalkoxy groups include trifluoromethoxy, bromomethoxy, 1,2-dichloroethoxy, 4-iodobutoxy, 2-fluoropentoxy, and the like. Haloalkoxy groups may be optionally substituted with one or more substituents. Haloalkoxy groups included in compounds of this invention may be optionally substituted with a solubilising group.
[0036] As used herein the term “substituent” or “substituted” means that a hydrogen radical on a compound or group is replaced with any desired group that is substantially stable to reaction conditions in an unprotected form or when protected using a protecting group. Examples of preferred substituents are those found in the exemplary compounds and embodiments disclosed herein, as well as halogen; alkyl as defined above; hydroxy; alkoxy as defined above; nitro; thiol; thioalkyl as defined above; cyano; haloalkyl as defined above; haloalkoxy as defined above; cycloalkyl, which may be monocyclic or fused or non-fused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl) or a solubilising group.
[0037] As used herein, the term “solubilising” group means a group which has a hydrophilic character sufficient to improve or increase the water-solubility of the compound in which it is included, as compared to an analog compound that does not include the group. The hydrophilic character can be achieved by any means, such as by the inclusion of functional groups that ionize under the conditions of use to form charged moieties (e.g., carboxylic acids, sulfonic acids, phosphoric acids, amines, etc.); groups that include permanent charges (e.g., quaternary ammonium groups); and/or heteroatoms or heteroatomic groups (e.g., O, S, N, NH, N—(CH 2 ) z R, N—(CH 2 ) z —C(O)R, N—(CH 2 ) z —C(O)OR, N—(CH 2 ) z —S(O) 2 R, N—(CH 2 ) z —S(O) 2 OR, N—(CH 2 ) z —C(O)NRR′, where z is an integer ranging from 0 to 6, R and R′ each independently are selected from hydrogen, an alkyl group containing from 1 to 10 carbon atoms and optionally substituted with one or more hetereoatoms such as halogen (selected from F, Cl, Br or I), oxygen, and nitrogen; as well as alkoxy group containing from 1 to 10 carbon atoms; as well as aryl and heteroaryl group.
[0038] In some embodiments, the solubilising group is a heterocycloalkyl that optionally includes from 1 to 5 substituents, which may themselves be solubilising groups. In a specific embodiment, the solubilising group is of the formula:
[0000]
[0039] where L is selected from the group consisting of CH and N, M is selected from the group consisting of —CH(R), CH 2 , O, S, NH, N(—(CH 2 ) z —R)—, —N(—(CH 2 ) z —C(O)R)—, —N(—(CH 2 ) z —C(O)OR)—, —N(—(CH 2 ) z —S(O) 2 R)—, —N(—(CH 2 ) z —S(O) 2 OR)— and —N(—(CH 2 ) z —C(O)NRR′)—, where z is an integer ranging from 0 to 6, R and R′ each independently are selected from hydrogen, an alkyl group containing from 1 to 10 carbon atoms and optionally substituted with one or more hetereoatoms such as halogen (selected from F, Cl, Br or I), oxygen, and nitrogen; as well as alkoxy group containing from 1 to 10 carbon atoms, NRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group as defined above optionally substituted with at least one heteroatom, notably oxygen or nitrogen optionally substituted with an alkyl group containing from 1 to 10 carbons optionally substituted; as well as aryl and heteroaryl group, with the proviso that L and M are not both simultaneously CH and CH 2 , respectively.
[0040] In another specific embodiment, the solubilising group is selected from the group consisting of morpholinyl, piperidinyl, N—(C 1 -C 6 )alkyl piperidinyl, in particular N-methyl piperidinyl and N-ethyl piperidinyl, N-(4-piperidinyl)piperidinyl, 4-(1-piperidinyl)piperidinyl, 1-pyrrolidinylpiperidinyl, 4-morpholinopiperidinyl, 4-(N-methyl-1-piperazinyl)piperidinyl, piperazinyl, N—(C 1 -C 6 )alkylpiperazinyl, in particular N-methylpiperazinyl and N-ethyl piperazinyl, N—(C 3 -C 6 )cycloalkyl piperazinyl, in particular N-cyclohexyl piperazinyl, pyrrolidinyl, N—(C 1 -C 6 )alkyl pyrrolidinyl, in particular N-methyl pyrrolidinyl and N-ethyl pyrrolidinyl, diazepinyl, N—(C 1 -C 6 )alkyl azepinyl, in particular N-methyl azepinyl and N-ethyl azepinyl, homopiperazinyl, N-methyl homopiperazinyl, N-ethyl homopiperazinyl, imidazolyl, and the like.
[0041] Among the compounds of formula I in which ring A is depicted above, the present invention is directed to compounds of the following formula II:
[0000]
[0042] Wherein:
[0043] A ring is a five member heterocycle ring;
[0044] R 1 is hydrogen, halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group;
[0045] R 2 is halogen (selected from F, Cl, Br or I), an aryl group, an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group; as well as a —COOR, —NRR′, —NR—CO—R′, —CONRR′ or —NR—SO 2 —R′ group wherein R and R′ are each independently selected from hydrogen, aryl group, heteroaryl group, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group;
[0046] R 3 is hydrogen, halogen (selected from F, Cl, Br or I), cyano, an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group; as well as CF 3 , —NRR′, —NR—CO—R′, —CONRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group;
[0047] Q is O or S;
[0048] W is N or CR 4 ;
[0049] R 4 is hydrogen, cyano, CF 3 , halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group, a solubilising group, an heterocycle, —CO—NRR′, SO 2 —NRR′, —NRR′, —NR—CO—R′ or —NR—SO 2 R′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0050] X is N or CR 5 ;
[0051] R 5 is hydrogen, cyano, halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms, an alkoxy group, —CO—OR, —CO—NRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0052] M is C or N;
[0053] V is CH 2 , CR 2 or NR 2 ;
[0054] R 7 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0055] Y is N, CR 8 or CR 8 R 9 ;
[0056] Z is N, NR B , CR 8 or CR 8 R 9 ;
[0057] R 8 is hydrogen, an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group;
[0058] R 9 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms.
[0059] In one embodiment, the invention relates to compounds of formula II or pharmaceutically acceptable salts thereof, wherein R 2 is halogen (selected from F, Cl, Br or I), an aryl group, an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group; as well as a —NRR′, —NR—CO—R′, —CONRR′ or —NR—SO 2 —R′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group.
[0060] Examples of preferred compounds of the above formula are depicted in table 1 below:
[0000]
TABLE 1
Ex #
Chemical structure
Name
1 H NMR/LCMS
001
1-{3-Chloro-5-[2- (3,5-dimethyl- phenylamino)- oxazol-5-yl]- phenyl}- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 10.26 (br s, 1H), 7.70 (br s, 1H), 7.60-7.53 (d, J = 5.3 Hz, 2H), 7.38- 7.16 (m, 4H), 6.61 (br s, 1H), 3.96-3.82 (m, 2H), 3.52-3.40 (m, 2H), 2.26 (s, 6H). (APCI+) m/z 383 (M + H) + Retention time = 3.76 min (method 2)
002
1-[3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5-(1- methyl-piperidin-4- yloxy)-phenyl]- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.26 (s, 1H), 7.82 (s, 1H), 7.42 (s, 1H), 7.29 (s, 1H), 7.20-7.12 (m, 1H), 7.14 (s, 1H), 7.02 (s, 1H), 6.93 (d, J = 7.6 Hz, 1H), 6.80 (s, 1H), 4.50-435 (m, 1H), 4.41 (s, 3H), 3.96-3.76 (m, 2H), 3.50-3.20 (m, 4H), 2.60-2.50 (m, 2H), 2.27 (s, 3H), 2.20-2.10 (m, 2H), 2.18 (s, 3H), 2.00-1.85 (m, 2H), 1.70-1.55 (m, 2H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z 506 (M + H) + Retention time = 2.36 min (method 2)
003
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- methyl-phenyl}-5- methyl-pyrrolidin-2- one
1 H NMR (300 MHz, CDCl 3 ) ä 7.92 (s, 1H), 7.33 (s, 1H), 7.18-7.09 (m, 3H), 7.05-6.95 (m, 2H), 4.50 (s, 2H), 4.28 (dq, J = 12.2, 6.1 Hz, 1H), 3.58- 3.47 (m, 2H), 2.69-2.43 (m, 2H), 2.34 (s, 3H), 2.30 (s, 3H), 1.81-1.65 (m, 2H), 1.27-1.16 (m, 6H). (APCI+) m/z 421 (M + H) + Retention time = 3.13 min (method 2)
004
4-Methoxy-1-{4-[2- ((5-methoxymethyl)- 2-methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-1,5-dihydro- pyrrol-2-one
(300 MHz, DMSO-d 6 ) δ 9.63 (br s, 1H), 8.43 (s, 1H), 8.27 (dd, J = 5.4, 0.6 Hz, 1H), 7.79 (d, J = 1.3 Hz, 1H), 7.71 (s, 1H), 7.26 (dd, J = 5.4, 1.4 Hz, 1H), 7.19 (d, J = 7.7 Hz, 1H), 6.97 (dd, J = 7.7, 1.4 Hz, 1H), 5.41 (s, 1H), 4.55 (s, 2H), 4.39 (s, 2H), 3.88 (s, 3H), 3.29 (s, 3H), 2.30 (s, 3H). (APCI+) m/z 407 (M + H) + Retention time = 3.13 mins (method 2)
005
1-Methyl-3-(3-{2-[2- methyl-5-(2- pyrrolidin-1-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
1 H NMR (300 MHz, CDCl 3 ) ä 8.09 (d, J = 1.1 Hz, 1H), 8.00 (d, J = 2.5 Hz, 1H), 7.51 (dd, J = 4.1, 1.3 Hz, 2H), 7.42-7.36 (m, 1H), 7.34 (s, 1H), 7.24 (d, J = 8.4 Hz, 1H), 6.92 (s, 1H), 6.74 (dd, J = 8.3, 2.6 Hz, 1H), 4.34 (t, J = 6.1 Hz, 2H), 4.04 (dd, J = 9.0, 6.8 Hz, 2H), 3.73-3.67 (m, 2H), 3.15-3.02 (m, 5H), 2.87-2.77 (m, 4H), 2.45 (s, 3H), 2.03-1.93 (m, 3H). (ES+) m/z 463 (M + H) + Retention time = 2.20 min (method 2)
006
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- thiazol-5-yl]-pyridin- 2-yl}-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.64 (s, 1H), 8.20-8.15 (m, 2H), 7.84 (s, 1H), 7.75 (s, 1H), 7.28-7-18 (m, 3H), 7.02 (d, J = 7.8 Hz, 1H), 4.42 (s, 2H), 4.03- 3.94 (m, 2H), 3.47 (q, J = 7.0 Hz, 2H), 3.39 (t, J = 8.0 Hz, 2H), 2.26 (s, 3H), 1.15 (t, J = 7.0 Hz, 3H). (APCI+) m/z 410 (M + H) + Retention time = 2.69 min (method 2)
007
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- thiazol-5-yl]-5- isopropoxy-phenyl}- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.37 (s, 1H), 7.78 (s, 1H), 7.61 (s, 1H), 7.22-7.16 (m, 2H), 7.04 (s, 1H), 7.03-6.95 (m, 3H), 6.70 (s, 1H), 4.63 (m, 1H), 4.41 (s, 2H), 3.92-3.79 (m, 2H), 3.47 (q, J = 7.0 Hz, 2H), 3.43-3.35 (m, 2H), 2.25 (s, 3H), 1.27 (d, J = 6.0 Hz, 6H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z 467 (M + H) + Retention time = 3.64 min (method 2)
008
1-(3-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-5- methyl-phenyl)-1,3- dihydro-imidazol-2- one
(300 MHz, DMSO-d 6 ) δ 10.35 (br s, 1H), 9.28 (s, 1H), 7.78 (s, 1H), 7.67 (d, J = 2.4 Hz, 1H), 7.47 (s, 1H), 7.41 (s, 1H), 7.29 (s, 1H), 7.07 (d, J = 8.3 Hz, 1H), 6.98 (br s, 1H), 6.70-6.48 (m, 2H), 4.87 (t, J = 5.6 Hz, 1H), 3.95 (t, J = 5.0 Hz, 2H), 3.82-3.65 (m, 2H), 2.37 (s, 3H), 2.23 (s, 3H). (APCI+) m/z 407 (M + H) + Retention time = 2.85 min (method 2)
009
2-[3-[2-(5-Methoxy- 2-methyl- phenylamino)- oxazol-5-yl]-5-(4- methyl-piperazin-1- yl)-phenyl]-2,4- dihydro- [1,2,4]triazol-3-one
(300 MHz, DMSO-d 6 ) δ 12.07 (br s, 1H), 9.30 (s, 1H), 8.13 (s, 1H), 7.64 (d, J = 2.5 Hz, 1H), 7.57 (s, 1H), 7.48 (s, 2H), 7.10-7.04 (m, 2H), 6.54 (dd, J = 8.3, 2.5 Hz, 1H), 3.72 (s, 3H), 3.24 (m, 4H), 2.60 (m, 2H), 2.32 (m, 2H), 2.22 (s, 3H). (APCI+) m/z 462 (M + H) + Retention time = 1.96 min (method 2)
010
2-{5-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 3-yl}-2,4-dihydro- [1,2,4]triazol-3-one
(300 MHz, DMSO-d 6 ) δ 9.50 (s, 1H), 9.00 (s, 1H), 8.72 (s, 1H), 8.38 (s, 1H), 8.21 (s, 1H), 7.83 (s, 1H), 7.66 (s, 1H), 7.17 (d, J = 8.0 Hz, 1H), 6.95 (d, J = 7.5 Hz, 1H), 4.41 (s, 2H), 3.47 (dd, J = 13.9, 6.9 Hz, 2H), 2.28 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (APCI+) m/z 393 (M + H) + Retention time = 4.53 min (method 2)
011
1-(5-{2-[2-Methyl-5- (2-piperidin-1-yl- ethoxy)- phenylamino]- oxazol-5-yl}-pyridin- 3-yl)-1,3-dihydro- imidazol-2-one
(300 MHz, MeOH-d 4 ) δ 8.83 (br s, 1H), 8.76 (br s, 1H), 8.48 (s, 1H), 7.61 (s, 1H), 7.57 (d, J = 2.5 Hz, 1H), 7.22 (d, J = 8.5 Hz, 1H), 7.07 (d, J = 3.1 Hz, 1H), 6.78 (dd, J = 8.3, 2.5 Hz, 1H), 6.70 (d, J = 3.1 Hz, 1H), 4.46-4.36 (m, 2H), 3.71-3.54 (m, 4H), 3.17-3.05 (m, 2H), 2.33 (s, 3H), 2.05-1.80 (m, 6H). (APCI+) m/z 461 (M + H) + Retention time = 0.43 min (method 2)
012
4-Methyl-1-{4-[2-(2- methyl-5-pyrrolidin- 1-ylmethyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-1,3-dihydro- imidazol-2-one
(300 MHz, DMSO-d 6 ) δ 10.89 (br s, 1H), 10.52 (br s, 1H), 9.95 (br s, 1H), 8.50 (s, 1H), 8.36 (d, J = 5.4 Hz, 1H), 7.95 (s, 1H), 7.83 (s, 1H), 7.40 (dd, J = 5.3, 1.5 Hz, 1H), 7.37-7.27 (m, 2H), 7.03 (d, J = 1.4 Hz, 1H), 4.37-4.30 (m, 2H), 3.47-3.24 (m, 2H), 3.19-2.91 (m, 2H), 2.34 (s, 3H), 2.09-1.78 (m, 7H). (APCI+) m/z 431 (M + H) + Retention time = 0.55 min (method 2)
013
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}-3-(2- piperidin-1-yl-ethyl)- 1,3-dihydro- imidazol-2-one
(300 MHz, CDCl 3 ) δ 8.06 (br s, 1H), 7.91 (br s, 1H), 7.47-7.40 (m, 2H), 7.22 (s, 1H), 7.19 (d, J = 7.6 Hz, 1H), 7.03 (d, J = 7.6 Hz, 1H), 6.75 (br s, 1H), 6.63 (d, J = 3.1 Hz, 1H), 6.59 (d, J = 3.0 Hz, 1H), 4.55 (s, 2H), 3.97-3.91 (m, 2H), 3.57 (q, J = 7.0 Hz, 2H), 2.83-2.74 (m, 2H), 2.67 2.57 (m, 4H), 2.35 (s, 3H), ), 1.77-1.65 (m, 4H), 1.55-1.46 (m, 2H), 1.26 (t, J = 7.0 Hz, 3H). (APCI+) m/z 502 (M + H) + Retention time = 2.58 min (method 2)
014
2-(3-{2-[2-Methyl-5- (pyridin-2-ylamino)- phenylamino]- oxazol-5-yl}- phenyl)-2,4-dihydro- [1,2,4]triazol-3-one
(300 MHz, DMSO-d 6 ) δ 9.30 (s, 1H), 8.96 (s, 1H), 8.13 (s, 1H), 8.12-8.06 (m, 2H), 8.01 (d, J = 2.1 Hz, 1H), 7.86-7.80 (m, 1H), 7.56-7.40 (m, 4H), 7.45 (m, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.85 (d, J = 8.4 Hz, 1H), 6.67 (dd, J = 6.3, 5.1 Hz, 1H), 2.23 (s, 3H). (APCI+) m/z 426 (M + H) + Retention time = 2.11 min (method 2)
015
1-(4-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-4-methyl-1,3- dihydro-imidazol-2- one
(300 MHz, MeOH-d 4 ) δ 8.46 (br s, 1H), 8.33 (d, J = 5.1 Hz, 1H), 7.53 (br s, 1H), 7,41 (d, J = 2.4 Hz, 1H), 7.33 (d, J = 4.8 Hz, 1H), 7.14 (d, J = 8.3 Hz, 1H), 7.02 (s, 1H), 6.70 (dd, J = 8.3, 2.4 Hz, 1H), 4.13-4.06 (m, 2H), 3.95-3.87 (m, 2H), 2.29 (s, 3H), 2.12 (s, 3H). (APCI+) m/z 408 (M + H) + Retention time = 2.89 min (method 2)
016
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl)-imidazolidin-2- one
1 H NMR (300 MHz, CDCl 3 ) ä 8.23 (s, 1H), 8.13 (d, J = 5.5 Hz, 1H), 7.73 (s, 1H), 7.33 (s, 1H), 7.13 (d, J = 7.7 Hz, 1H), 6.98 (t, J = 5.1 Hz, 2H), 4.46 (s, 2H), 4.15-4.07 (m, 2H), 3.55-3.42 (m, 4H), 2.26 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (ES+) m/z 394 (M + H) + Retention time = 2.35 min (method 2)
017
1-tert-Butyl-3-{4-[2- ((5-ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.60 (s, 1H), 8.35 (s, 1H), 8.23 (d, J = 5.4 Hz, 1H), 7.80 (s, 1H), 7.67 (s, 1H), 7.23-7.12 (m, 2H), 6.96 (d, J = 7.6 Hz, 1H), 4.42 (s, 2H), 3.85 (t, J = 7.8 Hz, 2H), 3.48 (dt, J = 14.0, 5.4 Hz, 4H), 2.28 (s, 3H), 1.37 (s, 9H), 1.14 (dd, J = 12.3, 5.3 Hz, 3H). (APCI+) m/z 450 (M + H) + Retention time = 3.28 min (method 2)
018
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-6- methyl-pyridin-2- yl}-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.55 (br s, 1H), 8.16 (s, 1H), 7.78 (s, 1H), 7.60 (s, 1H), 7.21 (s, 1H), 7.17 (d, J = 7.6 Hz, 1H), 7.06 (s, 1H), 6.96 (d, J = 7.6 Hz, 1H), 4.42 (s, 2H), 4.00 (t, J = 8.0 Hz, 2H), 3.52-3.36 (m, 4H), 2.39 (s, 3H), 2.28 (s, 3H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z = 408 (M + H) + Retention time = 2.69 min (method 2)
019
1-{6-Isobutyl-4-[2- ((5-methoxymethyl)- 2-methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.54 (br s, 1H), 8.15 (s, 1H), 7.80 (s, 1H), 7.61 (s, 1H), 7.37 (s, 1H), 7.18 (d, J = 7.7 Hz, 1H), 7.02 (s, 1H), 6.95 (d, J = 7.7 Hz, 1H), 4.38 (s, 2H), 4.18-4.09 (m, 1H), 3.89- 3.72 (m, 1H), 3.52 (dd, J = 10.6, 6.4 Hz, 1H), 3.28 (s, 3H), 2.28 (s, 3H), 2.14-2.05 (m, 1H), 1.20 (d, J = 6.1 Hz, 3H), 0.91 (d, J = 6.0 Hz, 6H). (APCI+) m/z 450 (M + H) + Retention time = 3.17 min (method 2)
020
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- methoxy-phenyl}- 4,4-dimethyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.26 (br s, 1H), 7.84 (s, 1H), 7.41 (s, 1H), 7.29 (s, 1H), 7.24 (s, 1H), 7.18- 7.12 (m, 2H), 6.93 (d, J = 7.7 Hz, 1H), 6.79 (s, 1H), 4.41 (s, 2H), 3.78 (s, 3H), 3.62 (s, 2H), 3.47 (q, J = 7.0 Hz, 2H), 2.28 (s, 3H), 1.28 (s, 6H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z 451 (M + H) + Retention time = 3.49 min (method 2)
021
1-(3-Chloro-5-{2-[2- methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.33 (br s, 1H), 7.64 7.62 (m, 2H), 7.60 (d, J = 2.5 Hz, 1H), 7.55 (s, 1H), 7.28 (br s, 1H), 7.21 (s, 1H), 7.07 (d, J = 8.3 Hz, 1H), 6.57 (dd, J = 8.4, 2.5 Hz, 1H), 4.04 (t, J = 5.8 Hz, 2H), 3.94-3.86 (m, 2H), 3.61-3.55 (m, 4H), 3.48-3.40 (m, 2H), 2.68 (t, J = 5.7 Hz, 2H), 2.49-2.44 (m, 4H), 2.22 (s, 3H). (APCI+) m/z 498 (M + H) + Retention time = 2.43 min (method 2)
022
1-{4-[2-(5-Methoxy- 2-methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.58 (br s, 1H), 8.34 (s, 1H), 8.24 (d, J = 5.4 Hz, 1H), 7.68 (s, 1H), 7.54 (d, J = 2.6 Hz, 1H), 7.44 (s, 1H), 7.19 (dd, J = 5.4, 1.4 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 6.60 (dd, J = 8.4, 2.6 Hz, 1H), 4.18-4.08 (m, 1H), 3.88-3.75 (m, 1H), 3.73 (s, 3H), 3.54 (dd, J = 10.6, 6.1 Hz, 1H), 2.23 (s, 3H), 1.21 (d, J = 6.1 Hz, 3H). (APCI+) m/z 380 (M + H) + Retention time = 2.76 min (method 2)
023
1-{5-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-2- methyl-phenyl}- imidazolidin-2-one
1 H NMR (300 MHz, CDCl 3 ) ä 7.92 (s, 1H), 7.40 7.32 (m, 2H), 7.24 (d, J = 9.3 Hz, 2H), 7.16 (d, J = 7.7 Hz, 2H), 7.10 (s, 1H), 7.01 (d, J = 7.5 Hz, 2H), 5.58 (s, 1H), 4.51 (s, 2H), 3.82 (t, J = 7.8 Hz, 2H), 3.64-3.48 (m, 4H), 2.31 (s, 6H), 1.24 (t, J = 7.0 Hz, 3H). (AES+) m/z 407 (M + H) + Retention time = 3.54 min (method 2)
024
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}- imidazolidin-2-one
1 H NMR (300 MHz, DMSO-d 6 ) ä 9.29 (s, 1H), 7.81 (d, J = 6.8 Hz, 2H), 7.46-7.29 (m, 3H), 7.18 (dd, J = 17.6, 7.7 Hz, 2H), 7.02 (s, 1H), 6.93 (d, J = 7.6 Hz, 1H), 4.41 (s, J = 5.3 Hz, 2H), 3.92- 3.83 (m, 2H), 3.45 (m, 4H), 2.28 (s, 3H), 1.14 (t, J = 7.0 Hz, 3H). (ES+) m/z 393 (M + H) + Retention time = 2.76 min (method 2)
025
2-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- pyrazol-1-yl- phenyl}-2,4-dihydro- [1,2,4]triazol-3-one hydrochloride
(300 MHz, DMSO-d 6 ) δ 12.16 (s, 1H), 9.78 (s, 1H), 8.57 (d, J = 2.5 Hz, 1H), 8.35 (t, J = 1.9 Hz, 1H), 8.21 (s, 1H), 8.05 (d, J = 7.4 Hz, 1H), 7.93 (s, 1H), 7.79 (d, J = 1.7 Hz, 2H), 7.70 (s, 1H), 7.19 (d, J = 7.7 Hz, 1H), 6.98 (d, J = 7.5 Hz, 1H), 6.65-6.50 (m, 1H), 4.42 (s, 2H), 3.52-3.39 (m, 2H), 2.29 (s, 3H), 1.12 (t, J = 7.0 Hz, 3H). (APCl+) m/z =458 (M + H) + Retention time = 3.44 min (method 2)
026
2-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}-2,4-dihydro- [1,2,4]triazol-3-one
(300 MHz, DMSO-d 6 ) δ 12.11 (s, 1H), 10.30 (s, 1H), 8.15 (d, J = 12.0 Hz, 2H), 7.88 (d, J = 7.3 Hz, 1H), 7.71 (d, J = 10.1 Hz, 2H), 7.58-7.43 (m, 2H), 7.22 (d, J = 7.7 Hz, 1H), 7.04 (d, J = 7.6 Hz, 1H), 4.43 (s, 2H), 3.48 (q, J = 6.9 Hz, 2H), 2.29 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (APCI+) m/z 392 (M + H) + Retention time = 3.56 min (method 2)
027
1-{5-[2-((5- Methoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 3-yl)-2,4-dihydro- imidazol-2- onehydrochloride
(300 MHz, DMSO-d 6 ) δ 10.64 (br s, 1H), 9.82 (br s, 1H), 8.95 (s, 1H), 8.75 (s, 1H), 8.59 (s, 1H), 7.81 (s, 1H), 7.79 (s, 1H), 7.27-7.15 (m, 2H), 6.99 (d, J = 7.8 Hz, 1H), 6.75 (br s, 1H), 4.39 (s, 3H), 3.28 (s, 3H), 2.29 (s, 3H). (APCI+) m/z 378 (M + H) + Retention time = 4.25 min (method 2)
028
2-{4-[2-(5- Ethoxymethyl-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-2,4-dihydro- [1,2,4]triazol-3-one
(300 MHz, DMSO-d 6 ) δ 9.67 (s, 1H), 8.42 (d, J = 5.3 Hz, 1H), 8.10 (s, 1H), 8.05 (s, 1H), 7.79 (s, 1H), 7.77 (s, 1H), 7.44 (dd, J = 5.2, 1.4 Hz, 1H), 7.18 (d, J = 7.7 Hz, 1H), 6.97 (d, J = 7.2 Hz, IH), 4.42 (s, 2H), 3.47 (t, J =7.0 Hz, 2H), 2.28 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (APCI+) m/z 393 (M + H) + Retention time = 4.49 min (method 2)
029
2-{4-[2-(5-Methoxy- 2-methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl)-2,4-dihydro- [1,2,4]triazol-3- onehydrochloride
(300 MHz, DMSO-d 6 ) δ 12.40 (s, 1H), 10.02 (s, 1H), 8.42 (d, J = 5.5 Hz, 1H), 8.30 (s, 1H), 8.14 (s, 1H), 8.05 (s, 1H), 7.58 (d, J = 5.5 Hz, 2H), 7.46 (s, 1H), 7.12 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 8.3 Hz, 1H), 3.73 (s, 3H), 2.22 (s, 3H). (APCI+) m/z 365 (M + H) + Retention time = 4.82 min (method 2)
030
2-(4-{2-[5-(2- Methoxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-2,4-dihydro- [1,2,4]triazol-3- onehydrochloride
(300 MHz, DMSO-d 6 ) δ 12.38 (s, 1H), 9.98 (s, 1H), 8.43 (d, J = 5.7 Hz, 1H), 8.29 (s, 1H), 8.14 (s, 1H), 8.04 (s, 1H), 7.58 (d, J = 5.7 Hz, 1H), 7.49 (s, 1H), 7.11 (d, J = 8.4 Hz, 1H), 6.65 (d, J = 8.5 Hz, 1H), 4.05 (d, J = 4.5 Hz, 2H), 3.65 (d, J = 4.5 Hz, 2H), 3.30 (s, 3H), 2.22 (s, 3H). (APCI+) m/z = 409 (M + H) + Retention time = 2.52 min (method 2)
031
1-{3-[2-(5-Methoxy- 2- methyl- phenylamino)- oxazol-5-yl]-5- methyl-phenyl}- imidazolidin-2-one
1 H NMR (300 MHz, DMSO-d 6 ) ä 9.25 (s, 1H), 7.62 (d, J = 2.6 Hz, 1H), 7.37 (s, 1H), 7.27 (s, 1H), 7.11-7.04 (m, 1H), 6.99 (s, 1H), 6.55 (dd, J = 8.3, 2.6 Hz, 1H), 3.92-3.81 (m, 2H), 3.72 (s, 3H), 3.45-3.37 (m, 2H), 2.31 (s, 3H), 2.22 (s, 3H). (ES+) m/z 380 (M + H) + Retention time = 3.28 min (method 2)
032
1-{4-[2-(5- (Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-1,3-dihydro- imidazol-2-one hydrochloride
(300 MHz, MeOH-d 4 ) δ 8.40 (d, J = 5.7 Hz, 1H), 8.29 (br s, 1H), 8.00 (br s, 1H), 7.59 (br s, 1H), 7.49 (d, J = 5.4 Hz, 1H), 7.35 (d, J = 7.9 Hz, 1H), 7.25 (d, J = 6.6 Hz, 1H), 7.08 (br s, 1H), 4.55 (s, 2H), 3.63 (q, J = 7.0 Hz, 2H), 2.38 (s, 3H), 2.15 (s, 3H), 1.27 (t, J = 7.0 Hz, 3H). (APCI+) m/z 407 (M + H) + Retention time = 2.99 min (method 2)
033
1-{4-[2-(5-Methoxy- 2-methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-imidazolidin-2- one
1 H NMR (300 MHz, DMSO-d 6 ) ä 9.57 (s, 1H), 8.33 (s, 1H), 8.24 (d, J = 4.8 Hz, 1H), 7.67 (s, 1H), 7.53 (s, 1H), 7.27 (s, 1H), 7.19 (d, J = 5.3 Hz, 1H), 7.09 (d, J = 8.5 Hz, 1H), 4.06-3.96 (m, 2H), 3.72 (s, 3H), 3.46-3.37 (m, 2H), 2.22 (s, 3H). (ES+) m/z = 366 (M + H) + Retention time = 2.36 min (method 2)
034
1-{4-[2-((5- Hydroxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-imidazolidin-2- one
1 H NMR (300 MHz, DMSO-d 6 ) ä 9.55 (s, 1H), 8.33 (s, 1H), 8.23 (d, J = 5.4 Hz, 1H), 7.74 (s, 1H), 7.64 (s, 1H), 7.26 (s, 1H), 7.17 (dd, J = 8.9, 4.7 Hz, 1H), 6.97 (d, J = 8.0 Hz, 1H), 5.12 (t, J = 5.7 Hz, 1H), 4.46 (d, J = 5.7 Hz, 2H), 4.06-3.96 (m, 2H), 3.41 (t, J = 8.0 Hz, 2H), 2.27 (s, 3H). (ES+) m/z 366 (M + H) + Retention time = 1.91 min (method 2)
035
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-pyrrolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.62 (s, 1H), 8.43 (s, 1H), 8.33 (d, J = 5.4 Hz, 1H), 7.75 (s, 1H), 7.70 (s, 1H), 7.31 (dd, J = 5.3, 1.5 Hz, 1H), 7.18 (d, J = 7.7 Hz, 1H), 6.97 (d, J = 7.6 Hz, 1H), 4.42 (s, 2H), 4.00 (t, J = 7.1 Hz, 2H), 3.47 (dd, J = 14.0, 7.0 Hz, 2H), 2.59 (t, J = 8.0 Hz, 2H), 2.28 (s, 3H), 2.04 (dt, J = 15.5, 7.7 Hz, 2H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z 393 (M + H) + Retention time = 3.29 min (method 2)
036
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- methyl-phenyl}- pyrrolidin-2-one
1 H NMR (300 MHz, CDCl 3 ) ä 7.97 (s, 1H), 7.60 (s, 1H), 7.27 (s, 1H), 7.17-7.07 (m, 3H), 6.98 (d, J = 7.7 Hz, 1H), 4.50 (s, 2H), 3.85 (t, J = 7.0 Hz, 2H), 3.52 (q, J = 7.0 Hz, 2H), 2.59 (dd, J = 10.2, 5.9 Hz, 2H), 2.34 (s, 3H), 2.30 (s, 3H), 2.18-2.05 (m, 2H), 1.22 (t, J = 7.1 Hz, 3H). (ES+) m/z 407 (M + H) + Retention time = 2.52 min (method 2)
037
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-3-methyl- imidazolidin-2-one
1 H NMR (300 MHz, CDCl 3 ) ä 8.35 (s, 1H), 8.09 (d, J = 5.4 Hz, 1H), 7.89 (s, 1H), 7.17 (s, 1H), 7.05 (d, J = 7.1 Hz, 2H), 6.90 (dd, J = 5.5, 4.0 Hz, 2H), 4.40 (d, J = 9.9 Hz, 2H), 3.98 (t, J = 7.2 Hz, 2H), 3.45-3.39 (m, 4H), 2.81 (s, 3H), 2.21 (s, 3H), 1.13 (t, J = 7.1 Hz, 3H). (ES+) m/= 409 (M + H) + Retention time = 2.58 min (method 2)
038
1-(3-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-5- methyl-phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.23 (s, 1H), 7.66 (d, J = 2.5 Hz, 1H), 7.61 (s, 1H), 7.37 (s, 1H), 7.28 (s, 1H), 7.06 (d, J = 8.8 Hz, 2H), 7.00 (s, 1H), 6.54 (dd, J = 8.3, 2.6 Hz, 1H), 4.86 (t, J = 5.6 Hz, 1H), 3.94 (t, J = 5.0 Hz, 2H), 3.91-3.81 (m, 2H), 3.71 (dd, J = 10.2, 5.2 Hz, 2H), 3.47-3.37 (m, 2H), 2.30 (d, J = 8.8 Hz, 3H), 2.22 (s, 3H). (APCI+) m/z 409 (M + H) + Retention time = 2.91 min (method 2)
039
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-5-methyl- pyrrolidin-2-one
1 H NMR (300 MHz, CDCl 3 ) ä 8.33 (s, 1H), 8.24 (d, J = 5.3 Hz, 1H), 7.85 (s, 1H), 7.32 (s, 1H), 7.32 (s, 1H), 7.10 (d, J = 7.7 Hz, 1H), 7.04 (dd, J = 5.3, 1.2 Hz, 1H), 6.95 (d, J = 8.2 Hz, 1H), 4.81 (ddq, J = 12.0, 6.1, 3.1 Hz, 1H), 4.45 (s, 2H), 3.49 (q, J = 7.0 Hz, 2H), 2.81-2.41 (m, 2H), 2.26 (s, J = 8.0 Hz, 3H), 1.70 (m, 2H), 1.28 (d, J = 6.3 Hz, 3H), 1.16 (t, J = 7.8 Hz, 3H). (ES+) m/z 407 (M + H) + Retention time = 3.05 min (method 2)
040
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-4-methyl-1,3- dihydro-imidazol-2- one
(300 MHz, MeOH-d 4 ) δ 8.40 (d, J = 5.7 Hz, 1H), 8.20 (br s, 1H), 8.00 (br s, 1H), 7.50 (br s, 1H), 7.49 (d, J = 5.4 Hz, 1H), 7.35 (d, J = 7.9 Hz, 1H), 7.25 (d, J = 6.6 Hz, 1H), 7.08 (br s, 1H), 4.55 (s, 2H), 3.63 (q, J = 7.0 Hz, 2H), 2.38 (s, 3H), 2.15 (s, 3H), 1.27 (t, J = 7.0 Hz, 3H). (APCI+) m/z 407 (M + H) + Retention time = 2.99 min (method 2)
041
1-{4-[2-(2-Methyl-5- pyrrolidin-1- ylmethyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-1,3-dihydro- imidazol-2-one
(300 MHz, DMSO-d 6 ) δ 10.83 (br s, 1H), 10.53 (br s, 1H), 9.91 (br s, 1H), 8.53 (s, 1H), 8.39 (d, J = 4.3 Hz, 1H), 7.95 (s, 1H), 7.82 (s, 1H), 7.53 7.20 (m, 4H), 6.65 (br s, 1H), 4.34 (s, 2H), 3.46 3.30 (m, 2H), 3.14-2.98 (m, 2H), 2.34 (s, 3H), 2.02-1.82 (m, 4H). (APCI+) m/z 417 (M + H) + Retention time = 0.41 min (method 2)
042
1-(4-{2-[2-Methyl-5- (2-morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-1,3-dihydro- imidazol-2-one
(300 MHz, CDCl 3 ) δ 9.15 (br s, 1H) 8.59 (s, 1 H), 8.37 (d, J = 5.2 Hz, 1H), 7.78 (br s, 1H), 7.46 (s, 1H), 7.38 (br s, 1H), 7.22 (d, J = 5.2 Hz, 1H), 7.10( d, J = 8.2 Hz, 1H), 7.04 (br s, 1H), 6.60 (d, J = 8.2 Hz, 1H), 6.45 (br s, 1H), 4.22 (t, J = 5.3 Hz, 1H), 3.86-3.76 (m, 4H), 3.00-2.90 (m, 2H), 2.80-2.65 (m, 4H), 2.31 (s, 3H). (APCI+) m/z 463 (M + H) + Retention time = 0.52 min (method 2)
043
1-(4-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-1,3-dihydro- imidazol-2-one
(300 MHz, MeOD-d 4 ) δ 8.50 (s, 1H), 8.37 (d, J = 5.0 Hz, 1H), 7.55 (s, 1H), 7.42 (d, J = 2.5 Hz, 1H), 7.37 (dd, J = 5.0, 1.5 Hz, 1H), 7.34 (d, J = 3.1 Hz, 1H), 7.15 (d, J = 8.4 Hz, 1H), 6.71 (dd, J = 8.4, 2.5 Hz, 1H), 6.55 (d, J = 3.1 Hz, 1H), 4.11 (t, J = 4.5 Hz, 2H), 3.91 (t, J = 4.5 Hz, 2H), 2.30 (s, 3H). (APCI+) m/z 394 (M + H) + Retention time = 2.45 min (method 2)
044
1-(4-{2-[2-Methyl-5- (1-methyl-piperidin- 4-yloxymethyl)- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-1,3-dihydro- imidazol-2-one
(300 MHz, MeOH-d 4 ) δ 8.48 (br s, 1H), 8.34 (d, J = 5.3 Hz, 1H), 7.70 (br s, 1H), 7.49 (s, 1H), 7.35 - 7.28 (m, 2H), 7.23 (d, J = 7.3 Hz, 1H), 7.08 (d, J = 7.3 Hz, 1H), 6.50 (d, J = 3.1 Hz, 1H), 4.57 (s, 1H), 3.60-3.45 (m, 1H), 2.80-2.66 (m, 2H), 2.35 (s, 3H), 2.29-2.20 (m, 5H), 2.02 1.90 (m, 2H), 1.80-1.66 (m, 2H). (APCl+) m/z 461 (M + H) + Retention time = 2.27 min (method 2)
045
1-{4-[2-(2-Methyl-5- morpholm-4- ylmethyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-1,3-dihydro- imidazol-2-one
(300 MHz, MeOH-d 4 ) δ 8.49 (br s, 1H), 8.36 (d, J = 5.3 Hz, 1H), 7.66 (s, 1H), 7.52 (s, 1H), 7.36- 7.31 (m, 2H), 7.23 (d, J = 7.7 Hz, 1H), 7.09 (d, J = 7.7 Hz, 1H), 6.53 (d, J = 3.1 Hz, 1H), 3.79- 3.66 (m, 4H), 3.57 (s, 2H), 2.57-2.49 (s, 4H), 2.35 (s, 3H). (APCl+) m/z 433 (M + H) + Retention time = 2.21 min (method 2)
046
1-(4-{2-[5-(2- Methoxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-1,3-dihydro- imidazol-2-one
(300 MHz, DMSO-d 6 ) δ 10.49 (br s, 1H), 9.65 (br s, 1H), 8.53 (s, 1H), 8.38 (d, J = 5.4 Hz, 1H), 7.78 (s, 1H), 7.56 (d, J = 2.1 Hz, 1H), 7.42 (d, J = 5.3 Hz, 1H), 7.27 (br s, 1H), 7.10 (d, J = 8.3 Hz, 1H), 6.70-6.55 (m, 2H), 4.12-3.99 (m, 2H), 3.70-3.61 (m, 2H), 3.31 (s, 3H), 2.24 (s, 3H). (APCI+) m/z 408 (M + H) + Retention time = 3.01 min (method 2)
047
4-Methyl-1-(4-{2-[2- methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-1,3-dihydro- imidazol-2-one
(300 MHz, DMSO-d 6 ) δ 10.45 (br s, 1H), 9.63 (br s, 1H), 8.50 (s, 1H), 8.34 (d, J = 5.4 Hz, 1H), 7.76 (s, 1H), 7.55 (d, J = 2.5 Hz, 1H), 7.37 (dd, J = 5.3, 1.5 Hz, 1H), 7.09 (d, J = 8.4 Hz, 1H), 7.01 (br s, 1H), 6.61 (dd, J = 8.4, 2.6 Hz, 1H), 4.05 (t, J = 5.8 Hz, 2H), 3.60-3.54 (m, 4H), 2.68 (t, J = 5.8 Hz, 2H), 2.49-2.42 (m, 4H), 2.23 (s, 3H), 2.00 (s, 3H). (APCI+) m/z 477 (M + H) + Retention time = 2.44 min (method 2)
048
1-(4-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.54 (br s, 1H), 8.35 (br s, 1H), 8.25 (d, J = 5.4 Hz, 1H), 7.67 (s, 1H), 7.57 (d, J = 2.4 Hz, 1H), 7.25 (s, 1H), 7.19 (d, J = 5.3 Hz, 1H), 7.09 (d, J = 8.3 Hz, 1H), 6.60 (d, J = 5.7 Hz, 1H), 4.83 (t, J = 5.6 Hz, 1H), 4.05 3.99 (m, 2H), 3.95 (t, J = 5.0 Hz, 2H), 3.75-3.70 (m, 2H), 3.42 (t, J = 8.0 Hz, 2H), 2.23 (s, 3H). (APCI+) m/z 396 (M + H) + Retention time = 2.44 min (method 2)
049
1-(4-{2-[2-Methyl-5- (2-morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.57 (br s, 1H), 8.35 (br s, 1H), 8.25 (d, J = 5.4 Hz, 1H), 7.68 (s, 1H), 7.56 (br s, 1H), 7.27 (br s, 1H), 7.20 (d, J = 5.3 Hz, 1H), 7.09 (d, J = 8.3 Hz, 1H), 6.61 (d, J = 8.3 Hz, 1H), 4.11-3.93 (m, 4H), 3.63-3.54 (m, 4H), 3.46-3.38 (m, 2H), 2.69 (t, J = 5.7 Hz, 2H), 2.52-2.45 (m, 4H), 2.23 (s, 3H). (APCl+) m/z 465 (M + H) + Retention time = 2.05 min (method 2)
050
1-{4-[2-(2-Methyl-5- morpholin-4- ylmethyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.57 (br s, 1H), 8.32 (br s, 1H), 8.24 (d, J = 5.3 Hz, 1H), 7.72 (s, 1H), 7.66 (s, 1H), 7.26 (br s, 1H), 7.20-7.12 (m, 2H), 6.96 (d, J = 7.5 Hz, 1H), 4.01 (t, J = 7.9 Hz, 2H), 3.60-3.52 (s, 4H), 3.46-3.37 (m, 4H), 2.40- 2.32 (m, 4H), 2.27 (s, 3H). (APCI+) m/z 435 (M + H) + Retention time = 2.00 min (method 2)
051
1-{4-[2-((5- Methoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.59 (br s, 1H), 8.32 (br s, 1H), 8.22 (d, J = 5.5 Hz, 1H), 7.78 (br s, 11H), 7.65 (s, 1H), 7.43 (br s, 1H), 7.20-7.14 (m, 2H), 6.96 (d, J = 7.6 Hz, 1H), 4.38 (s, 2H), 4.17-4.07 (m, 1H), 3.83-3.73 (m, 1H), 3.53 (dd, J = 10.5, 6.0 Hz, 1H), 3.28 (s, 3H), 2.28 (s, 3H), 1.20 (d, J = 6.1 Hz, 3H). (APCI+) m/z 394 (M + H) + Retention time = 2.69 min (method 2)
052
1-(3-{2-[2-Methyl-5- (2-morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.26 (s, 1H), 7.80 (s, 1H), 7.61 (d, J = 2.5 Hz, 1H), 7.43 (d, J = 9.2 Hz, 1H), 7.40 (s, 1H), 7.34 (t, J = 7.9 Hz, 1H), 7.23 (d, J = 7.6 Hz, 1H), 7.06 (d, J = 8.5 Hz, 1H), 7.02 (br s, 1H), 6.55 (dd, J = 8.3, 2.6 Hz, 1H), 4.04 (t, J = 5.8 Hz, 2H), 3.94-3.83 (m, 2H), 3.63-3.52 (m, 4H), 3.42 (t, J = 8.0 Hz, 2H), 2.68 (t, J = 5.8 Hz, 2H), 2.49-2.41 (m, 4H), 2.22 (s, 3H). (APCI+) m/z 464 (M + H) + Retention time = 2.27 min (method 2)
053
4-Methyl-1-(4-{2-[2- methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.56 (br s, 1H), 8.33 (s, 1H), 8.23 (d, J = 5.4 Hz, 1H), 7.68 (s, 1H), 7.55 (d, J = 2.5 Hz, 1H), 7.43 (s, 1H), 7.19 (dd, J = 5.3, 1.5 Hz, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.60 (dd, J = 8.3, 2.5 Hz, 1H), 4.14 (dd, J = 10.5, 8.7 Hz, 1H), 4.05 (t, J = 5.7 Hz, 2H), 3.85-3.75 (m, 1H), 3.60-3.50 (m, 5H), 2.69 (t, J = 5.7 Hz, 2H), 2.49-2.44 (m, 4H), 2.23 (s, 3H), 1.21 (d, J = 6.1 Hz, 3H). (APCI+) m/z 479 (M + H) + Retention time = 2.13 min (method 2)
054
1-(3-Methyl-5-{2-[2- methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl)- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.23 (s, 1H), 7.63 (d, J = 2.6 Hz, 2H), 7.37 (s, 1H), 7.27 (s, 1H), 7.06 (dd, J = 6.0, 4.6 Hz, 2H), 7.00 (s, 1H), 6.55 (dd, J = 8.3, 2.6 Hz, 1H), 4.09-3.99 (m, 2H), 3.92-3.80 (m, 2H), 3.63-3.53 (m, 4H), 3.41 (t, J = 7.9 Hz, 2H), 2.68 (t, J = 5.7 Hz, 2H), 2.48-2.42 (m, 4H), 2.31 (s, 3H), 2.22 (s, 3H). (APCI+) m/z 478 (M + H) + Retention time = 2.33 min (method 2)
055
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.29 (br s, 1H), 7.84 (br s, 1H), 7.77 (s, 1H), 7.44 (d, J = 7.8 Hz, 1H), 7.39 (s, 1H), 7.34 (t, J = 7.8 Hz, 1H), 7.22-7.13 (m, 3H), 6.94 (d, J = 7.5 Hz, 1H), 4.42 (s, 2H), 4.01 (t, J = 8.8 Hz, 1H), 3.88-3.76 (m, IH), 3.54-3.38 (m, 3H), 2.29 (s, 3H), 1.22 (d, J = 6.1 Hz, 3H), 1.15 (t, J = 7.0 Hz, 3H). (APCI+) m/z 407 (M + H) + Retention time = 3.08 min (method 2)
056
1-(3-Methyl-5-{2-[2- methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)-1,3-dihydro- imidazol-2-one
(300 MHz, CDCl 3 ) δ 10.36 (br s, 1H), 7.86 (d, J = 2.1 Hz, 1H), 7.72 (s, 1H), 7.36-7.28 (m, 3H), 7.15 (d, J = 8.4 Hz, 1H), 6.99 (br s, 1H), 6.67- 6.61 (m, 2H), 6.52 (t, J = 2.1 Hz, 1H), 4.29 (t, = 5.3 Hz, 2H), 3.90-3.83 (m, 4H), 3.06-2.95 (m, 2H), 2.88-2.743 (s, 4H), 2.50 (s, 3H), 2.35 (s, 3H). (APCI+) m/z 476 (M + H) + Retention time = 2.17 min (method 2)
057
1-(4-{2-[2-Methyl-5- (3-morpholin-4-yl- propoxy)- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-imidazolidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.57 (br s, 1H), 8.35 (s, 1H), 8.25 (d, J = 5.4 Hz, 1H), 7.68 (s, 1H), 7.54 (d, J = 2.5 Hz, 1H), 7.28 (br s, 1H), 7.20 (dd, J = 5.3, 1.5 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.59 (dd, J = 8.4, 2.5 Hz, 1H), 4.06-3.93 (m, 4H), 3.60-3.54 (m, 4H), 3.47-3.38 (m, 2H), 2.47- 2.32 (m, 6H), 2.23 (s, 3H), 1.93-1.83 (m, 2H). (APCI+) m/z 479 (M + H) + Retention time = 1.95 min (method 2)
058
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- methoxy-phenyl}- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.29 (s, 1H), 7.83 (d, J = 1.2 Hz, 1H), 7.41 (s, 1H), 7.38-7.31 (m, 1H), 7.15 (d, J = 8.0 Hz, 1H), 7.14-7.11 (m, 1H), 7.04 (s, 1H), 6.93 (dd, J = 7.7, 1.4 Hz, 1H), 6.82 6.79 (m, 1H), 4.41 (s, 2H), 3.87 (dd, J = 9.1, 6.7 Hz, 2H), 3.78 (s, 3H), 3.47 (q, J= 7.0 Hz, 2H), 3.43, (m, 1H), 2.28 (s, 3H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z 423 (M + H) + Retention time = 3.03 min (method 2)
059
1-(3-{2-[2-Methyl-5- (3-morpholin-4-yl- propoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, CDCl 3 ) δ 8.05 (s, 1H), 7.89 (d, J = 2.5 Hz, 1H), 7.53-7.43 (m, 2H), 7.38 (dd, J = 7.2, 1.4 Hz, 1H), 7.32 (s, 1H), 7.21 (d, J = 8.4 Hz, 1H), 7.10 (br s, 1H), 6.68 (dd, J = 8.3, 2.5 Hz, 1H), 5.67 (br s, 1H), 4.22 (t, J = 6.1 Hz, 2H), 4.12 (dd, J = 9.1, 6.7 Hz, 2H), 4.00-3.87 (m, 4H), 3.83 3.68 (m, 2H), 2.88-2.60 (m, 6H), 2.42 (s, 3H), 2.28-2.12 (m,2H). (APCI+) m/z 478 (M + H) + Retention time = 2.16 min (method 2)
060
1-(3-Methoxy-5-{2- [2-methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.26 (s, 1H), 7.61 (d, J = 2.5 Hz, 1H), 7.43 (s, 1H), 7.34 (s, 1H), 7.14 (t, J = 2.0 Hz, 1H), 7.06 (d, J = 8.8 Hz, 2H), 6.81 (s, 1H), 6.55 (dd, J = 8.3, 2.5 Hz, 1H), 4.04 (t, J = 5.9 Hz, 2H), 3.86 (dd, J = 14.9, 6.4 Hz, 2H), 3.78 (s, 3H), 3.60-3.53 (m, 4H), 3.41 (t, J = 8.0 Hz, 2H), 2.68 (t, J = 5.7 Hz, 2H), 2.49-2.38 (m, 4H), 2.22 (s, 3H). (APCI+) m/z 494 (M + H) + Retention time = 2.35 min (method 2)
061
1-{3-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- methoxy-phenyl}-4- methyl-imidazolidin- 2-one
(300 MHz, DMSO-d 6 ) δ 9.27 (s, 1H), 7.83 (s, 1H), 7.41 (s, 1H), 7.31 (s, 1H), 7.20 (s, 1H), 7.15 (d, J = 8.3 Hz, 2H), 6.93 (d, J = 7.7 Hz, 1H), 6.80 (d, J = 1.3 Hz, 1H), 4.41 (s, 2H), 4.00 (dd, J = 16.1, 7.9 Hz, 1H), 3.87-3.73 (m, 4H), 3.45 (dt, J = 7.1, 4.9 Hz, 3H), 2.28 (s, 3H), 1.21 (d, J = 6.0 Hz, 3H), 1.18- l.06 (m, 3H). (APCI+) m/z 437(M + H) + Retention time = 3.43 min (method 2)
062
1-{3-tert-Butoxy-5- [2-((5- methoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.43 (s, 1H), 8.00 (s, 1H), 7.57 (s, 1H), 7.55 (d, J = 1.6 Hz, 1H), 7.42 (t, J = 2.0 Hz, 1H), 7.33 (d, J = 7.7 Hz, 1H), 7.19 (s, 1H), 7.09 (dd, J = 7.6, 1.3 Hz, 1H), 7.02 6.96 (m, 1H), 4.54 (s, 2H), 4.10-3.98 (m, 2H), 3.58 (t, J = 7.9 Hz, 2H), 3.45 (s, 3H), 2.45 (s, 3H), 1.51 (s, 9H). (APCI+) m/z 451 (M + H) + Retention time = 3.98 min (method 2)
063
1-(3-{2-[5-(2- Hydroxy-elhoxy)-2- methyl- phenylamino]- oxazol-5-yl}-5- methyl-phenyl)-4- methyl-imidazolidin- 2-one
(300 MHz, MeOH-d 4 ) δ 7.64 (br s, 1H), 7.43 (d, J = 2.5 Hz, 1H), 7.18 (br s, 1H), 7.15 (s, 1H), 7.14-7.08 (m, 2H), 6.65 (dd, J = 8.3, 2.6 Hz, 1H), 4.13-4.04 (m, 3H), 4.00-3.88 (m, 3H), 3.54 (dd, J = 8.8, 6.2 Hz, 1H), 2.38 (s, 3H), 2.28 (s, 3H), 1.36 (d, J = 6.1 Hz, 3H). (APCI+) m/z 422 (M + H) + Retention time = 3.05 min (method 2)
064
1-(3-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-5- methoxy-phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.26 (s, 1H), 7.64 (d, J = 2.6 Hz, 1H), 7.43 (s, 1H), 7.34 (s, 1H), 7.14 (t, J = 2.1 Hz, 1H), 7.08-7.02 (m, 2H), 6.82 (d, J = 1.4 Hz, 1H), 6.55 (dd, J = 8.3, 2.6 Hz, 1H), 4.86 (t, J = 5.6 Hz, 1H), 3.96-3.82 (m, 4H), 3.78 (s, 3H), 3.70 (dd, J = 10.3, 5.2 Hz, 2H), 3.45-3.37 (m, 2H), 2.22 (s, 3H). (APCI+) m/z 425 (M + H) + Retention time = 2.58 min (method 2)
065
4-Methyl-1-(3- methyl-5-{2-[2- methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.24 (br s, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.60 (br s, 1H), 7.38 (s, 1H), 7.28 (br s, 1H), 7.18 (br s, 1H), 7.112-7.03 (m, 2H), 6.56 (d, J = 5.9 Hz, 1H), 4.12-3.92 (m, 3H), 3.91 3.76 (m, 1H), 3.63 3.53 (m, 4H), 3.42 (dd, J = 9.0, 6.2 Hz, 1H), 2.69 (t, J = 5.7 Hz, 2H), 2.50-2.43 (d, J = 4.4 Hz, 2H), 2.32 (s, 3H), 2.23 (s, 3H), 1.22 (d, J = 6.0 Hz, 3H). (APCI+) m/z 492 (M + H) + Retention time = 2.46 min (method 2)
066
1-(3-Methoxy-5-{2- [2-methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.25 (s, 1H), 7.63 (d, J = 2.3 Hz, 1H), 7.43 (s, 1H), 7.32 (s, 1H), 7.21 (s, 1H), 7.15 (s, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.81 (s, 1H), 6.56 (dd, J = 8.3, 2.5 Hz, 1H), 4.11 3.94 (m, 3H), 3.82 (m, 1H), 3.78 (s, 3H), 3.64 3.52 (m, 4H), 3.47-3.37 (m, 1H), 2.68 (m, 2H), 2.50-2.40 (m, 4H), 2.22 (s, 3H), 1.21 (d, J = 6.1 Hz, 3H). (APCI+) m/z 508 (M + H) + Retention time = 2.61 min (method 2)
067
1-{3-Isopropoxy-5- [2-((5- methoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.27 (s, 1H), 7.84 (s, 1H), 7.41 (s, 1H), 7.29 (s, 1H), 7.23-7.09 (m, 2H), 7.02 (s, 1H), 6.92 (d, J = 7.6 Hz, 1H), 6.79 (d, J = 1.3 Hz, 1H), 4.63 (m, 1H), 4.37 (s, 2H), 3.93-3.81 (m, 2H), 3.46-3.36 (m, 2H), 3.28 (s, 3H), 2.28 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (APCI+) m/z 437 (M + H) + Retention time = 3.79 min (method 2)
068
1-{3-[2-((5- Methoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-5- methyl-phenyl}-1,3- dihydro-imidazol-2- one
(300 MHz, DMSO-d 6 ) δ 10.35 (br s, 1H), 9.31 (br s, 1H), 7.88 (s, 1H), 7.77 (s, 1H), 7.45 (s, 1H), 7.41 (s, 1H), 7.28 (s, 1H), 7.17 (d, J = 7.6 Hz, 1H), 7.00-6.96 (m, 1H), 6.93 (d, J = 7.7 Hz, 1H), 6.64-6.59 (m, 1H), 4.38 (s, 2H), 3.28 (s, 3H), 2.37 (s, .3H), 2.29 (s, 3H). (APCI+) m/z 391 (M + H) + Retention time = 3.46 min (method 2)
069
1-{3-[2-((5- Methoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}-4-methyl- 1,3-dihydro- imidazol-2-one
(300 MHz, DMSO-d 6 ) δ 10.34 (br s, 1H), 9.34 (br s, 1H), 7.94 (s, 1H), 7.87 (s, 1H), 7.60-7.34 (m, 4H), 7.17 (d, J = 7.4 Hz, 1H), 6.94 (d, J = 7.4 Hz, 1H), 6.71 (s, 1H), 4.38 (s, 2H), 3.28 (s, 3H), 2.29 (s, 3H), 2.00 (s, 3H). (APCI+) m/z 391 (M + H) + Retention time = 3.17 min (method 2)
070
1-(3-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}- phenyl)-4-methyl- 1,3-dihydro- imidazol-2-one
(300 MHz, DMSO-d 6 ) δ 10.35 (br s, 1H), 9.30 (br s, 1H), 7.95 (s, 1H), 7.67 (s, 1H), 7.57-7.41 (m, 4H), 7.08 (d, J = 8.3 Hz, 1H), 6.72 (br s, 1H), 6.57 (d, J= 8.3 Hz, 1H), 4.87 (t, J = 5.6 Hz, 1H), 3.95 (t, J = 4.9 Hz, 2H), 3.76-3.69 (m, 2H), 2.24 (s, 3H), 2.00 (s, 3H). (APCI+) m/z 407 (M + H) + Retention time = 2.85 min (method 2)
071
1-(3-{2-[5-(2- Hydroxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-5- isopropoxy-phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.23 (s, 1H), 7.63 (d, J = 2.5 Hz, 1H), 7.43 (s, 1H), 7.29 (s, 1H), 7.13 (d, J = 2.0 Hz, 1H), 7.10-6.99 (m, 2H), 6.80 (s, 1H), 6.55 (dd, J = 8.3, 2.5 Hz, 1H), 4.85 (t, J = 5.6 Hz, 1H), 4.63 (m, 1H), 3.94 (t, J = 5.0 Hz, 2H), 3.91 3.82 (m, 2H), 3.71 (m, 2H), 3.45-3.37 (m, 2H), 2.22 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (APCI+) m/z 453 (M + H) + Retention time = 3.12 min (method 2)
072
1-(3-Isopropoxy-5- {2-[2-methyl-5-(2- morpholin-4-yl- ethoxy)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9 35 (s, 1H), 7.74 (s, 1H), 7.55 (s, 1H), 7.42 (s, 1H), 7.24 (s, 1H), 7.21- 7.11 (m, 2H), 6.93 (s, 1H), 6.67 (dd, J = 8.3, 2.3 Hz, 1H), 4.84-4.66 (m, 1H), 4.16 (t, J = 5.8 Hz, 2H), 4.06-3.92 (m, 2H), 3.79-3.64 (m, 4H), 3.52 (dd, J = 15.7, 6.8 Hz, 2H), 2.80 (t, J = 5.7 Hz, 2H), 2.59 (d, J = 4.4 Hz, 4H), 2.34 (s, 3H). 1.42 (t, J = 7.0 Hz, 6H). (APCI+) m/z 522 (M + H) + Retention time = 2.46 min (method 2)
073
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.59 (br s, 1H), 8.32 (br s, 1H), 8.22 (d, J = 5.4 Hz, 1H), 7.76 (s, 1H), 7.65 (s, 1H), 7.43 (br s, 1H), 7.21-7.15 (m, 2H), 6.97 (d, J = 7.5 Hz, 1H), 4.42 (s, 2H), 4.13 (t, J = 9.7 Hz, 1H), 3.85-3.75 (m, 1H), 3.59-3.42 (m, 3H), 2.28 (s, 3H), 1.20 (d, J = 6.0 Hz, 3H), 1.14 (t, J = 7.0 Hz, 3H). (APCI+) m/z 408 (M + H) + Retention time = 2.85 min (method 2)
074
1-{4-[2-((5- Ethoxymethyl)-2- methyl- phenylamino)- oxazol-5-yl]-pyridin- 2-yl}-4,4-dimethyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.59 (br s, 1H), 8.33 (br s, 1H), 8.22 (d, J = 5.4 Hz, 1H), 7.77 (s, 1H), 7.66 (s, 1H), 7.48 (s, 1H), 7.20-7.13 (m, 2H), 6.97 (d, J = 7.8 Hz, 1H), 4.43 (s, 2H), 3.75 (s, 2H), 3.48 (q, J = 7.0 Hz, 2H), 2.29 (s, 3H), 1.29 (s, 6H), 1.15 (t,J = 7.0 Hz, 3H). (APCI+) m/z 422 (M + H) + Retention time = 2.98 min (method 2)
075
1-(3-Methoxy-5-{2- [5-(3-methoxy- propoxy)-2-methyl- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.25 (s, 1H), 7.61 (d, J = 2.5 Hz, 1H), 7.44 (s, 1H), 7.34 (s, 1H), 7.14 (t, J = 2.0 Hz, 1H), 7.08-7.02 (m, 2H), 6.82 (s, 1H), 6.54 (dd, J = 8.3, 2.6 Hz, 1H), 3.97(t, J = 6.4 Hz, 2H), 3.92-3.83 (m, 2H), 3.78 (s, 3H), 3.51- 3.36 (m, 4H), 3.24 (s, 3H), 2.22 (s, 3H), 1.93 (m, 2H). (APCI+) m/z 453 (M + H) + Retention time = 3.38 min (method 2)
076
1-(3-{2-[(5-(2- Hydroxy- ethoxymethyl))-2- methyl- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.30 (br s, 1H), 7.84- 7.78 (m, 2H), 7.43 (d, J = 8.2 Hz, 1H), 7.38 (s, 1H), 7.35 (t, J = 7.6 Hz, 1H), 7.22 (d, J = 7.6 Hz, 1H), 7.17 (d, J = 7.7 Hz, 1H), 7.03 (s, 1H), 6.97 (d, J = 7.8 Hz, 1H), 4.62 (t, J = 5.5 Hz, 1H), 4.46 (s, 2H), 3.94-3.84 (m, 2H), 3.58-3.38 (m, 4H), 2.29 (s, 3H). (APCI+) m/z 409 (M + H) + Retention time = 2.80 min (method 2)
077
1-(3-Isopropoxy-5- {2-[5-(2-methoxy- ethyl)-2-methyl- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(400 MHz, DMSO-d 6 ) δ 9.22 (s, 1H), 7.70 (s, 1H), 7.41 (s, 1H), 7.29 (s, 1H), 7.19-7.06 (m, 2H), 7.03 (s, 1H), 6.86 (d, J = 7.5 Hz, 1H), 6.79 (s, 1H), 4.72-4.57 (m, 1H), 3.98-3.74 (m, 2H), 3.52 (t, J = 6.9 Hz, 2H), 3.46-3.38 (m, 2H), 2.77 (t, J = 6.6 Hz, 2H), 2.25 (s, 3H), 1.29 (d, J = 6.0 Hz, 6H). (ESI+) m/z 451 (M + H) + Retention time = 3.94 min (method 1)
078
1-(4-{2-[5-(2- Methoxy-ethoxy)-2- methyl- phenylamino]- oxazol-5-yl}-pyridin- 2-yl)-4-methyl- imidazolidin-2-one
(300 MHz, DMSO-d 6 ) δ 9.56 (br s, 1H), 8.33 (br s, 1H), 8.23 (d, J = 5.4 Hz, 1H), 7.67 (s, 1H), 7.56 (d, J = 2.5 Hz, 1H), 7.43 (s, 1H), 7.19 (d, J = 4.1 Hz, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.59 (dd, J = 8.3, 2.5 Hz, 1H), 4.17-4.08 (m, 1H), 4.08 4.01 (m, 2H), 3.87-3.73 (m, 1H), 3.67-3.63 (m, 2H), 3.54 (dd, J= 10.6, 6.1 Hz, 1H), 3.31 (s, 3H), 2.22 (s, 3H), 1.20 (d, J = 6.1 Hz, 3H). (APCI+) m/z 424 (M + H) + Retention time = 2.76 min (method 2)
079
1-{3-[2-(5- Hydroxymethyl-2- methyl- phenylamino)- oxazol-5-yl]-5- isopropoxy-phenyl}- imidazolidin-2-one
(300 MHz, DMSO) δ 9.22 (s, 1H), 7.80 (s, 1H), 7.39 (s, 1H), 7.29 (s, 1H), 7.12 (m, 2H), 7.02 (s, 1H), 6.92 (d, J = 7.7 Hz, 1H), 6.79 (s, 1H), 5.12 (t, J = 5.7 Hz, 1H), 4.63 (m, 1H), 4.45 (d, J = 5.7 Hz, 2H), 3.94-3.78 (m, 2H), 3.40 (t, J = 8.0 Hz, 2H), 2.26 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 423 (M + H)+ Retention time = 4.82 min (method 2)
080
3-{5-[3-Isopropoxy- 5-(2-oxo- imidazolidin-1-yl)- phenyl]-oxazol-2- ylamino)-4-methyl- benzoic acid
(300 MHz, DMSO) δ 9.58 (brs, 1H), 8.54 (d, J = 1.5 Hz, 1H), 7.56 (dd, J = 7.8, 1.6 Hz, 1H), 7.49 (s, 1H), 7.36-7.27 (m, 2H), 7.14 (s, 1H), 7.04 (brs, 1H), 6.82 (s, 1H), 4.63 (m, 1H), 3.95-3.80 (m, 2H), 3.49-3.32 (m, 2H), 2.36 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 437 (M + H)+ Retention time = 5.01 min (method 2)
081
1-(3-(2-(2-methyl-5- (2- morpholinoethoxy) phenylamino)oxazol- 5-yl)-5- (trifluoromethoxy) phenyl)imidazolidin- 2-one
1 H NMR (300 MHz, DMSO) δ 9.34 (s, 1H), 7.68 (s, 1H), 7.59 (d, J = 2.5 Hz, 3H), 7.23 (s, 1H), 1.16 (s, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.57 (dd, J = 8.3, 2.6 Hz, 1H), 4.04 (t, J = 5.8 Hz, 2H), 3.97- 3.85 (m, 2H), 3.57 (dd, J = 5.5, 3.8 Hz, 4H), 3.43 (dd, J = 15.9, 8.0 Hz, 2H), 2.68 (t, J = 5.8 Hz, 2H), 2.48-2.43 (m, 4H), 2.22 (s, 3H). (ESI+) m/z 548.2 (M + H) + Retention time = 2.43 min (method 2)
082
1-(3-{2-[5-(1- Ethoxy-ethyl)-2- methyl- phenylamino]- oxazol-5-yl}-5- isopropoxy-phenyl)- imidazolidin-2-one
(300 MHz, DMSO) δ 9.25 (s, 1H), 7.79 (s, 1H), 7.41 (s, 1H), 7.27 (s, 1H), 7.21-7.08 (m, 2H), 7.01 (s, 1H), 6.91 (d, J = 8.1 Hz, 1H), 6.78 (s, 1H), 4.62 (m, 1H), 4.37 (q, J = 6.1 Hz, 1H), 3.94- 3.79 (m, 2H), 3.40 (m, 2H), 3.30 (m, 2H), 2.27 (s, 3H), 1.32 (d, J = 6.4 Hz, 2H), 1.28 (d, J = 6.0 Hz, 3H), 1.08 (t, J = 7.0 Hz, 3H). (ESI+) m/z 465 (M + H)+ Retention time = 3.58 min (method 2)
083
1-(3-(2-(5-methoxy- 2- methylphenylamino) oxazol-5-yl)-5- (trifluoromethoxy) phenyl)imidazolidin- 2-one
(300 MHz, DMSO) δ 9.36 (s, 1H), 7.68 (s, 1H), 7.59 (d, J = 2.0 Hz, 3H), 7.25 (s, 1H), 7.16 (s, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.57 (dd, J = 8.3, 2.6 Hz, 1H), 3.98-3.86 (m, 2H), 3.72 (s, 3H), 3.51-3.38 (m, 2H), 2.22 (s, 3H). (ESI+) m/z 449 (M + H)+ Retention time = 3.55 min (method 2)
084
1-(3-hydroxy-5-(2- (5-methoxymethyl)- 2- methylphenylamino) oxazol-5- yl)phenyl) imidazolidin- 2-one
(300 MHz, DMSO) δ 9.51 (s, 1H), 9.24 (s, 1H), 7.83 (s, 1H), 7.30 (s, 1H), 7.19-7.11 (m, 2H), 7.08 (s, 1H), 6.97 (s, 1H), 6.92 (d, J = 7.7 Hz, 1H), 6.62 (s, 1H), 4.37 (s, 2H), 3.89-3.78 (m, 2H), 3.46-3.36 (m, 2H), , 3.27 (s, 3H), 2.28 (s, 3H). (ESI+) m/z 395 (M + H)+ Retention time = 2.76 min (method 2)
085
1-(3-Isopropoxy-5- {2-[2-methyl-5- (2,2,2-trifluoro- ethoxymethyl)- phenylamino]- oxazol-5-yl)- phenyl)- imidazolidin-2-one
(300 MHz, DMSO) δ 9.30 (s, 1H), 7.88 (s, 1H), 7.41 (s, 1H), 7.31 (s, 1H), 7.20 (d, J = 7.8 Hz, 1H), 7.11 (t, J = 2.1 Hz, 1H), 7.01 (s, 1H), 6.97 (d, J = 7.7 Hz, 1H), 6.79 (s, 1H), 4.62 (s, 2H), 4.62 (m, 1H), 4.08 (q, J = 9.4 Hz, 2H), 3.94 3.81 (m, 2H), 3.40 (m, 2H), 2.29 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 505 (M + H)+ Retention time = 3.63 min (method 2)
086
3-{5-[3-Isopropoxy- 5-(2-oxo- imidazolidin-1-yl)- phenyl]-oxazol-2- ylamino}-4-methyl- benzamide
(300 MHz, DMSO) δ 9.39 (s, 1H), 8.35 (s, 1H), 7.88 (s, 1H), 7.49 (d, J = 7.8 Hz, 1H), 7.43 (s, 1H), 7.27 (m, 3H), 7.13 (s, 1H), 7.04 (s, 1H), 6.80 (s, 1H), 4.71-4.56 (m, 1H), 3.86 (m, 2H), 3.47-3.37 (m, 2H), 2.33 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 436 (M + H)+ Retention time = 2.84 min (method 2)
087
1-(3-{2-[5-(2- Hydroxy- ethoxymethyl)-2- methyl- phenylamino]- oxazol-5-yl}-5- methyl-phenyl)- imidazolidin-2-one
(300 MHz, DMSO) δ 9.26 (s, 1H), 7.84 (s, 1H), 7.62 (s, 1H), 7.34 (s, 1H), 7.26 (s, 1H), 7.16 (d, J = 7.8 Hz, 1H), 7.06 (s, 1H), 7.01-6.90 (m, 2H), 4.61 (t, J = 5.5 Hz, 1H), 4.45 (s, 2H), 3.92-3.82 (m, 2H), 3.53 (dd, J = 10.6, 5.0 Hz, 2H), 3.48- 3.36 (m, 4H), 2.31 (s, J = 6.5 Hz, 3H), 2.28 (s, 3H). (ESI+) m/z 423.2 (M + H) + Retention time = 2.72 min (method 2)
088
3-{5-[3-Isopropoxy- 5-(2-oxo- imidazolidin-1-yl)- phenyl]-oxazol-2- ylamino}-4-methyl- N-(2-morpholin-4-yl- ethyl)-benzamide
(300 MHz, DMSO) δ 9.40 (s, 1H), 8.32 (m, 1H), 8.29 (m, 1H), 7.44 (m, 2H), 7.32-7.23 (m, 2H), 7.13 (t, J = 2.0 Hz, 1H), 7.03 (s, 1H), 6.81 (s, 1H), 4.64 (m, 1H), 3.94-3.81 (m, 2H), 3.64- 3.51 (m, 4H), 3.45-3.30 (m, 4H), 2.45-2.35 (m, 4H), 2.33 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 549 (M + H) + Retention time = 2.32 min (method 2)
089
3-{5-[3-Isopropoxy- 5-(2-oxo- imidazolidin-1-yl)- phenyl]-oxazol-2- ylamino}-N-(2- methoxy-ethyl)-4- methyl-benzamide
(300 MHz, DMSO) δ 9.39 (s, 1H), 8.42 (m, 1H), 8.33 (d, J = 1.4 Hz, 1H), 7.46 (dd, J = 7.9, 1.6 Hz, 1H), 7.43 (s, 1H), 7.30-7.24 (m, 2H), 7.14 (t, J = 2.0 Hz, 1H), 7.02 (s, 1H), 6.80 (s, 1H), 4.63 (m, 1H), 3.94-3.80 (m, 2H), 3.51-3.35 (m, 6H), 3.26 (s, 3H), 2.33 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 494 (M + H)+ Retention time = 2.99 min (method 2)
090
3-{5-[3-Isopropoxy- 5-(2-oxo- imidazolidin-1-yl)- phenyl]-oxazol-2- ylamino}-N- isopropyl-4-methyl- benzamide
(300 MHz, DMSO) δ 9.38 (s, 1H), 8.30 (d, J = 1.5 Hz, 1H), 8.12 (d, J = 7.8 Hz, 1H), 7.47 (dd, J = 7.8, 1.6 Hz, 1H), 7.42 (s, 1H), 7.30-7.24 (m, 2H), 7.14 (s, 1H), 7.02 (s, 1H), 6.79 (s, 1H),4.63 (m, 1H), 4.18-3.97 (m, 1H), 3.93-3.80 (m, 2H), 3.40 (m, 2H), 2.32 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H), 1.15 (d, J = 6.6 Hz, 6H). (ESI+) m/z 478 (M + H)+ Retention time = 3.16 min (method 2)
091
3-{5-[3-Isopropoxy- 5-(2-oxo- imidazolidin-1-yl)- phenyl]-oxazol-2- ylamino}-4,N,N- trimethyl-benzamide
(300 MHz, DMSO) δ 9.41 (s, 1H), 7.99 (d, J = 1.5 Hz, 1H), 7.43 (s, 1H), 7.29 (s, 1H), 7.24 (d, J = 7.8 Hz, 1H), 7.12 (s, 1H), 7.02 (s, 1H), 6.99 (dd, J = 7.6, 1.7 Hz, 1H), 6.80 (s, 1H), 4.63 (m, 1H), 3.93-3.81 (m, 2H), 3.40 (m, 2H), 2.96 (s, 6H), 2.33 (s, 3H), 1.28 (d, J = 6.0 Hz, 6H). (ESI+) m/z 464 (M + H)+ Retention time = 3.02 min (method 2)
092
1-(3-(2-(5- (ethoxymethyl)-2- methylphenylamino) oxazol-5-yl)-5- (trifluoromethoxy) phenyl) imidazolidin-2- one
1 H NMR (400 MHz, DMSO) δ 9.39 (s, 1H), 7.81 (s, 1H), 7.66 (d, J = 6.7 Hz, 1H), 7.57 (d, J = 2.1 Hz, 2H), 7.25 (s, 1H), 7.16 (d, J = 8.0 Hz, 2H), 6.94 (d, J = 7.6 Hz, 1H), 4.41 (s, 2H), 3.98-3.85 (m, 2H), 3.52-3.37 (m, 4H), 2.27 (s, 3H), 1.14 (t, J = 7.0 Hz, 3H). (ESI+) m/z 477.2 (M + H) + Retention time = 3.65 min (method 2)
093
1-(3-Isopropoxy-5- {2-[2-methyl-5- (pyridin-2-ylamino)- phenylamino]- oxazol-5-yl}- phenyl)- imidazolidin-2-one
(300 MHz, DMSO) δ 9.20 (s, 1H), 8.94 (s, 1H), 8.12-8.05 (m, 1H), 8.02 (d, J = 2.0 Hz, 1H), 7.58-7.48 (m, 1H), 7.44 (dd, J = 8.2, 2.1 Hz, 1H), 7.40 (s, 1H), 7.26 (s, 1H), 7.14 (d, J = 2.0 Hz, 1H), 7.06 (d, J = 8.3 Hz, 1H), 7.01 (s, 1H), 6.84 (d, J = 8.5 Hz, 1H), 6.80 (s, 1H), 6.68 (dd, J = 7.0, 5.1 Hz, 1H), 4.60 (m, 1H), 3.83 (m, 2H), 3.43-3.34 (m, 2H), 2.22 (s, 3H), 1.26 (d, J = 6.0 Hz, 6H). (ESI+) m/z 484 (M + H)+ Retention time = 2.55 min (method 2)
094
1-{3-Chloro-5-[2-(5- ethoxymethyl-2- methyl- phenylamino)- oxazol-5-yl]- phenyl}- imidazolidin-2-one
1 H NMR (300 MHz, DMSO) δ 9.41 (s, 1H), 7.86 (s, 1H), 7.66 (d, J = 1.4 Hz, 2H), 7.58 (s, 1H), 7.29 (d, J = 9.4 Hz, 1H), 7.27-7.17 (m, 2H), 6.99 (d, J = 7.7 Hz, 1H), 4.46 (s, 2H), 4.02-3.89 (m, 2H), 3.51-3.48 (m, 4H), 2.32 (s, 3H), 1.18 (t, J = 1.0 Hz, 3H). (ESI+) m/z 427.2 (M + H) + Retention time = 3.50 min (method 2)
095
1-{3-Isopropoxy-5- [2-(2-methyl-5- propoxy- phenylamino)- oxazol-5-yl]- phenyl)- imidazolidin-2-one
(300 MHz, DMSO) δ 9.22 (s, 1H), 7.59 (d, J = 2.4 Hz, 1H), 7.42 (s, 1H), 7.29 (s, 1H), 7.12 (s, 1H), 7.09-6.98 (m, 2H), 6.80 (s, 1H), 6.53 (dd, J = 8.3, 2.5 Hz, 1H), 4.62 (m, 1H), 3.95-3.78 (m, 4H), 3.48-3.37 (m, 2H), 2.21 (s, 3H), 1.72 (m, 2H), 1.28 (d, J = 6.0 Hz, 6H), 0.97 (t, J = 7.4 Hz, 3H). (ESI+) m/z 451 (M + H) + Retention time = 3.76 min (method 2)
096
1-(3-{2-[2-Methyl-5- (pyrimidin-2- ylamino)- phenylamino]- oxazol-5-yl)-5- trifluoromethoxy- phenyl)- imidazolidin-2-one
(300 MHz, DMSO) δ 9.55 (s, 1H), 9.38 (s, 1H), 8.42 (d, J = 4.8 Hz, 2H), 8.14 (d, J = 1.8 Hz, 1H), 7.70 (s, 1H), 7.55 (s, 1H), 7.51 (s, 1H), 7.41 (dd, J = 8.2, 2.0 Hz, 1H), 7.23 (s, 1H), 7.14 (s, 1H), 7.10 (d, J = 8.4 Hz, 1H), 6.79 (t, J = 4.8 Hz, 1H), 3.88 (t, J = 7.7 Hz, 2H), 3.41 (t, J = 7.7 Hz, 2H), 2.22 (s, 3H). (ESI+) m/z 512 (M + H)+ Retention time = 3.32 min (method 2)
097
1-(3-{2-[2-Methyl-5- (pyridin-2-ylamino)- phenylamino]- oxazol-5-yl}-5- trifluoromethoxy- phenyl)- imidazolidin-2-one
(400 MHz, DMSO) δ 9.33 (s, 1H), 8.96 (s, 1H), 8.08 (dd, J = 4.9, 1.2 Hz, 1H), 8.04 (d, J = 1.9 Hz, 1H), 7.70 (s, 1H), 7.57 (s, 1H), 7.55-7.48 (m, 2H), 7.45 (dd, J = 8.3, 2.0 Hz, 1H), 7.24 (s, 1H), 7.16 (s, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 8.4 Hz, 1H), 6.68 (m, 1H), 3.88 (t, J = 7.9 Hz, 2H), 3.41 (t, J = 7.9 Hz, 2H), 2.22 (s, 3H). (ESI+) m/z 511 (M + H)+ Retention time = 2.64 min (method 2)
098
1-{3-[2-5-Butyl-2- methyl- phenylamino)- oxazol-5-yl]-5- isopropoxy-phenyl}- imidazolidin-2-one
1H NMR (400 MHz, DMSO) δ 9.22 (s, 1H), 7.66 (s. 1H), 7.40 (s, 1H), 7.27 (s, 1H), 7.13-7.00 (m, 3H), 6.84-6.72 (m, 2H), 4.67-4.55 (m, 1H), 3.85 (t, J = 7.9 Hz, 2H), 3.45-3.37 (m, 2H), 2.56 2.51 (m, 2H), 2.23 (s, 3H), 1.58-1.48 (m, 2H), 1.36-1.28 (m, 2H), 1.28 (s, 3H), 1.27 (s, 3H), 0.88 (t, J = 7.3 Hz, 3H). (ESI+) m/z 449.3 (M + H)+ Retention time = 4.00 min (method 2)
099
1-{3-[2-(5- Ethoxymethyl-2- methyl- phenylamino)- oxazol-5-yl]-5- morpholin-4- ylmethyl-phenyl}- imidazolidin-2-one
1H NMR (400 MHz, DMSO) δ 9.27 (s, 1H), 7.84 (s, 1H), 7.65 (s, 1H), 7.43 (s, 1H), 7.37 (s, 1H), 7.18-7.14 (m, 2H), 7.00 (s, 1H), 6.94 (d, J = 7.7 Hz, 1H), 4.42 (s, 2H), 3.93-3.84 (m, 2H), 3.62-3.57 (m, 4H), 3.44 (dd, J = 18.4, 7.7 Hz, 5H), 2.38 (s, 4H), 2.28 (s, 3H), 1.19-1.09 (m, 3H). (ESI+) m/z 492.3 (M + H)+ Retention time = 2.29 min (method 2)
100
1-{3-[2-(2-Methyl-5- morpholin-4- ylmethyl- phenylamino)- oxazol-5-yl]-5- trifluoromethoxy- phenyl}- imidazolidin-2-one
1H NMR (300 MHz, DMSO) δ 9.36 (s, 1H), 7.76 (s, 1H), 7.66 (s, 1H), 7.57 (s, 2H), 7.25 (s, 1H), 7.15 (d, J = 7.4 Hz, 2H), 6.94 (d, J = 7.7 Hz, 1H), 3.97-3.86 (m, 2H), 3.60-3.50 (m, 4H), 3.49- 3.37 (m, 4H), 2.35 (s, 4H), 2.27 (s, 3H). (ESI+) m/z 518.3 (M + H)+ Retention time = 2.44 min (method 2)
[0061] Among the compounds of formula I in which ring A is depicted above, the present invention is directed to compounds of the following formula III:
[0000]
[0062] Wherein:
[0063] A ring is a six member heterocycle ring;
[0064] R 1 is hydrogen, halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group;
[0065] R 2 is halogen (selected from F, Cl, Br or I), an aryl group, an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group; as well as a —COOR, —NRR′, —NR—CO—R′, —CONRR′ or —NR—SO 2 —R′ group wherein R and R′ are each independently selected from hydrogen, aryl group, heteroaryl group, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group;
[0066] R 3 is hydrogen, halogen (selected from F, Cl, Br or I), cyano, an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group; as well as CF 3 , —NRR′, —NR—CO—R′, —CONRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group;
[0067] Q is O or S;
[0068] W is N or CR 4 ;
[0069] R 4 is hydrogen, cyano, CF 3 , halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group, a solubilising group, an heterocycle, —CO—NRR′, SO 2 —NRR′, —NRR′, NR—CO—R′ or NR—SO 2 R′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0070] X is N or CR 5 ;
[0071] R 5 is hydrogen, cyano, halogen (selected from F, Cl, Br or I), an alkyl group containing from 1 to 10 carbon atoms, an alkoxy group, —CO—OR, —CO—NRR′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0072] M is C or N;
[0073] V is N, CH 2 , CR 7 or NR 7 ;
[0074] R 7 is hydrogen, cyano or an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group or heterocycle group;
[0075] Y is N, CR 8 or CR 8 R 9 ;
[0076] Z is N, CR 8 or CR 8 R 9 ;
[0077] T is N, C═O, CR 8 or CR 8 R 9 ;
[0078] R 8 is hydrogen, a halogen (selected from F, Cl, Br or I), an hydroxyl group, an alkyl group containing from 1 to 10 carbon atoms or an alkoxy group;
[0079] R 9 is hydrogen or an alkyl group containing from 1 to 10 carbon atoms.
[0080] In one embodiment the invention relates to compounds of formula III or pharmaceutically acceptable salts thereof, wherein R 2 is halogen (selected from F, Cl, Br or I), an aryl group, an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an haloalkyl or alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as an alkoxy group or an haloalkoxy group; as well as a —NRR′, —NR—CO—R′, —CONRR′ or —NR—SO 2 —R′ group wherein R and R′ are each independently selected from hydrogen, alkyl group optionally substituted with at least one heteroatom, notably oxygen or nitrogen, optionally substituted with an alkyl group containing from 1 to 10 carbon atoms optionally substituted with a solubilising group; as well as a heterocycle group or a solubilising group.
[0081] Examples of preferred compounds of the above formula are depicted in table 2 below:
[0000]
TABLE 2
Ex
#
Chemical structure
Name
1 H NMR
101
N-(3-{5-[3-(2,6-Dioxo- piperidin-1-yl)-phenyl]- oxazol-2-yl-amino}-4- methyl-phenyl)-2- pyrrolidin-1-yl- acetamide
(400 MHz, DMSO) δ 9.96 (s, 1H), 9.64 (s, 1H), 9.27 (d, J = 12.2 Hz, 1H), 8.03 (d, J = 10.9 Hz, 1H), 7.94 (s, 1H), 7.54-7.46 (m, 1H), 7.35- 7.27 (m, 3H), 7.10 (d, J = 8.2 Hz, 1H), 3.23 (s, 2H), 2.69 (t, J = 6.5 Hz, 4H), 2.63-2.56 (m, 4H), 2.23 (s, 3H), 2.12 (m, 2H), 1.74 (s, 4H). (ESI+) m/z 488 (M + H) + Retention time = 2.26 min (method 1)
102
N-(3-{5-[3-(4,4- Dimethyl-2,6-dioxo- piperidin-1-yl)-phenyl]- oxazol-2-ylamino}-4- methyl-phenyl)-2- pyrrolidin-1-yl- acetamide
(400 MHz, DMSO) δ 9.94 (s, 1H), 9.66 (s, 1H), 9.27 (d, J = 12.4 Hz, 1H), 8.06 (d, J = 10.7 Hz, 1H), 7.94 (s, 1H), 7.53-7.45 (m, 1H), 7.40- 7.27 (m, 3H), 7.10 (d, J = 8.1 Hz, 1H), 3.22 (s, 2H), 2.69 (s, 4H), 2.63-2.54 (m, 4H), 2.23 (s, 3H), 1.74 (s, 4H), 1.14 (s, 3H), 1.10 (s, 3H). (ESI+) m/z 516 (M + H) + Retention time = 2.72 min (method 1)
103
4-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-2-(2-oxo- piperidin-1-yl)- benzonitrile
(300 MHz, CDCl 3 ) δ 7.93 (s, 1H), 7.67 (d, J = 8.2 Hz, 1H), 7.50 (dd, J = 8.2, 1.5 Hz, 1H), 7.44 (d, J = 1.3 Hz, 1H), 7.30 (s, 2H), 7.18 (d, J = 7.7 Hz, 1H), 7.03 (d, J = 8.0 Hz, 1H), 4.51 (s, 2H), 3.67 (m, 2H), 3.54 (q, J = 7.0 Hz, 2H), 2.61 (m, 2H), 2.31 (s, 3H), 2.01 (m, 4H), 1.20 (t, J = 7.0 Hz, 3H).
104
3-{3-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- thiazol-5-yl]-phenyl}- 1H-pyridin-2-one
(400 MHz, DMSO-d 6 ) δ 11.81 (s, 1H), 9.39 (s, 1H), 7.81 (d, J = 11.8 Hz, 2H), 7.71 (dd, J = 6.9, 2.0 Hz, 1H), 7.63 (s, 1H), 7.56 (d, J = 7.6 Hz, 1H), 7.50-7.31 (m, 3H), 7.20 (d, J = 7.7 Hz, 1H), 6.98 (d, J = 7.6 Hz, 1H), 6.31 (t, J = 6.7 Hz, 1H), 4.42 (s, 2H), 3.48 (q, J = 7.0 Hz, 2H), 2.27 (s, 3H), 1.15 (t, J = 7.0 Hz, 3H). (ESI+) m/z 418 (M + H) + Retention time = 3.53 min (method 1)
105
3-{3-[2-(5-Methoxy-2- methyl-phenylamino)- thiazol-5-yl]-phenyl}- 1H-pyridin-2-one
(400 MHz, DMSO-d 6 ) δ 1 H NMR (400 MHz, DMSO) δ 11.82 (s, 1H), 9.44 (s, 1H), 7.85 (s, 1H), 7.72 (dd, J = 6.9, 1.9 Hz, 1H), 7.65 (s, 1H), 7.62-7.53 (m, 2H), 7.48-7.35 (m, 3H), 7.12 (d, J = 8.3 Hz, 1H), 6.61 (dd, J = 8.3, 2.6 Hz, 1H), 6.31 (t, J = 6.7 Hz, 1H), 3.73 (s, 3H), 2.21 (s, 3H). (ESI+) m/z 390 (M + H) + Retention time = 3.42 min (method 1)
106
1-{3-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-5- trifluoromethyl- phenyl}-1H-pyridin-2- one
(300 MHz, DMSO-d 6 ) δ 9.43 (s, 1H), 7.94-7.91 (m, 1H), 7.86 (s, 1H), 7.81-7.74 (m, 2H), 7.71 (s, 1H), 7.60-7.53 (m, 1H), 7.17 (d, J = 7.8 Hz, 1H), 6.95 (d, J = 9.1 Hz, 1H), 6.53 (d, J = 9.2 Hz, 1H), 6.38 (t, J = 6.6 Hz, 1H), 4.41 (s, 2H), 3.46 (q, J = 6.9 Hz, 2H), 2.28 (s, 3H), 1.12 (t, J = 7.0 Hz, 3H).
107
3-(3-{2-[2-Methyl-5- (1-methyl-piperidin-4- yloxy)-phenylamino]- oxazol-5-yl}-5- trifluoromethyl- phenyl)-1H-pyridin-2- one
(400 MHz, DMSO-d 6 ) δ 12.00 (s, 1H), 9.36 (s, 1H), 8.18 (s, 1H), 8.00 (s, 1H), 7.89-7.82 (m, 2H), 7.71 (s, 1H), 7.62 (s, 1H), 7.52-7.47 (m, 1H), 7.06 (d, J = 8.1 Hz, 1H), 6.58 (d, J = 6.2 Hz, 1H), 6.39-6.33 (m, 1H), 4.32-4.22 (m, 1H), 2.64-2.58 (m, 2H), 2.23 (s, 3H), 2.17 (s, 3H), 2.16-2.06 (m, 2H), 1.96-1.85 (m, 2H), 1.68- 1.56 (m, 2H). (ESI+) m/z 525 (M + H) + Retention time = 3.08 min (method 1)
108
3-[2-(5-Methoxy-2- methyl-phenylamino)- oxazol-5-yl]-5-(2-oxo- 2H-pyridin-1-yl)- benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.40 (s, 1H), 8.10 (s, 1H), 7.93 (t, J = 1.6 Hz, 1H), 7.87-7.85 (m, 1H), 7.77 (dd, J = 6.7, 1.7 Hz, 1H), 7.73 (s, 1H), 7.62-7.53 (m, 2H), 7.09 (d, J = 8.4 Hz, 1H), 6.60-6.51 (m, 2H), 6.38 (td, J = 6.6, 0.9 Hz, 1H), 3.72 (s, 3H), 2.21 (s, 3H). (ESI+) m/z 399 (M + H) + Retention time = 3.56 min (method 1)
109
3-(6-Chloro-2-oxo-2H- pyridin-1-yl)-5-[2-(5- methoxy-2-methyl- phenylamino)-oxazol- 5-yl]-benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.38 (s, 1H), 8.12 (t, J = 1.4 Hz, 1H), 7.89 (d, J = 1.4 Hz, 2H), 7.72 (s, 1H), 7.60-7.54 (m, 2H), 7.09 (d, J = 8.5 Hz, 1H), 6.66 (dd, J = 7.3, 0.9 Hz, 1H), 6.60-6.54 (m, 2H), 3.72 (s, 3H), 2.21 (s, 3H). (ESI+) m/z 433 (M + H) + Retention time = 3.96 min (method 1)
110
3-{2-[5-(2- Dimethylamino- ethoxy)-2-methyl- phenylamino]-oxazol- 5-yl}-5-(2-oxo-1,2- dihydro-pyridin-3-yl)- benzonitrile
(300 MHz, DMSO-d 6 ) δ 12.02 (s, 1H), 9.38 (s, 1H), 8.25 (s, 1H), 8.03 (s, 1H), 7.99 (s, 1H), 7.84 (d, J = 7.2 Hz, 1H), 7.67 (s, 1H), 7.60 (d, J = 2.7 Hz, 1H), 7.50 (d, J = 7.3 Hz, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.54 (dd, J = 8.2, 2.6 Hz, 1H), 6.36 (t, J = 6.8 Hz, 1H), 4.00 (m, 2H), 2.60 (m, 2H), 2.22 (s, 3H), 2.20 (s, 6H).
111
4-{2-[5-(3-Hydroxy- propoxy)-2-methyl- phenylamino]-oxazol- 5-yl}-4′-methyl-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 11.67 (s, 1H), 9.45 (s, 1H), 8.60 (d, J = 5.4 Hz, 1H), 7.78 (s, 1H), 7.58 (d, J = 2.3 Hz, 1H), 7.55 (s, 1H), 7.43 (d, J = 5.5 Hz, 1H), 7.34 (d, J = 6.5 Hz, 1H), 7.08 (d, J = 8.5 Hz, 1H), 6.58 (dd, J = 8.4, 2.2 Hz, 1H), 6.18 (d, J = 6.7 Hz, 1H), 4.54 (t, J = 5.0 Hz, 1H), 3.99 (t, J = 6.5 Hz, 2H), 3.55 (q, J = 6.7 Hz, 2H), 2.22 (s, 3H), 2.03 (s, 3H), 1.85 (quint, J = 6.7 Hz, 2H). (ESI+) m/z 433 (M + H) + Retention time = 2.19 min (method 1)
112
3-[1-(2- Dimethylamino-ethyl)- 2-oxo-1,2-dihydro- pyridin-3-yl]-5-[2-(5- methoxy-2-methyl- phenylamino)-oxazol- 5-yl]-benzonitrile
(400 MHz, DMSO-d 6 ) δ 9.39 (s, 1H), 8.23 (t, J = 1.6 Hz, 1H), 8.01 (t, J = 1.6 Hz, 1H), 7.99 (t, J = 1.5 Hz, 1H), 7.85-7.76 (m, 2H), 7.67 (s, 1H), 7.61 (d, J = 2.7 Hz, 1H), 7.09 (d, J = 8.4 Hz, 1H), 6.58 (dd, J = 8.3, 2.6 Hz, 1H), 6.40 (t, J = 6.9 Hz, 1H), 4.08 (t, J = 6.4 Hz, 2H), 3.73 (s, 3H), 2.55 (t, J = 6.4 Hz, 2H), 2.23 (s, 3H), 2.20 (s, 6H). (ESI+) m/z 470 (M + H) + Retention time = 2.99 min (method 1)
113
1-{3-Dimethylamino-5- [2-(5-(ethoxymethyl)- 2-methyl- phenylamino)-oxazol- 5-yl]-phenyl}-1H- pyridin-2-one
(300 MHz, DMSO-d 6 ) δ 9.25 (s, 1H), 7.88 (s, 1H), 7.65 (d, J = 6.3 Hz, 1H), 7.59-7.44 (m, 2H), 7.16 (d, J = 7.4 Hz, 1H), 7.00-6.84 (m, 3H), 6.56 (s, 1H), 6.47 (d, J = 9.2 Hz, 1H), 6.30 (t, J = 6.6 Hz, 1H), 4.40 (s, 2H), 3.46 (dd, J = 14.0, 6.9 Hz, 2H), 2.98 (s, 6H), 2.28 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (ESI+) m/z 445 (M + H) + Retention time = 3.83 min (method 1)
114
1-{3-[2-(5-Methoxy-2- methyl-phenylamino)- oxazol-5-yl]-5- piperidin-1-yl-phenyl}- 1H-pyridin-2-one
(300 MHz, DMSO-d 6 ) δ 9.20 (s, 1H), 7.69-7.63 (m, 2H), 7.55-7.47 (m, 2H), 7.16 (s, 1H), 7.07 (d, J = 8.3 Hz, 1H), 6.96 (s, 1H), 6.78 (s, 1H), 6.54 (dd, J = 8.2, 2.2 Hz, 1H), 6.47 (d, J = 9.2 Hz, 1H), 6.30 (t, J = 6.6 Hz, 1H), 3.71 (s, 3H), 3.24 (s, 4H), 2.21 (s, 3H), 1.60 (s, 6H). (ESI+) m/z 457 (M + H) + Retention time = 3.94 min (method 1)
115
2-Methyl-propane-1- sulfonic acid (4- methyl-3-{5-[3-(2-oxo- 2H-pyridin-1-yl)-5- pyrrolidin-1-yl- phenyl]-oxazol-2- ylamino}-phenyl)- amide
(300 MHz, DMSO-d 6 ) δ 9.66 (s, 1H), 9.27 (s, 1H), 7.84 (d, J = 1.4 Hz, 1H), 7.64 (dd, J = 6.9, 1.4 Hz, 1H), 7.55-7.46 (m, 2H), 7.11 (d, J = 8.1 Hz, 1H), 6.86-6.75 (m, 3H), 6.46 (d, J = 9.0 Hz, 1H), 6.37 (s, 1H), 6.30 (t, J = 6.6 Hz, 1H), 3.29 (s, 4H), 2.96 (d, J = 6.4 Hz, 2H), 2.23 (s, 3H), 2.18-2.07 (m, 1H), 1.98 (s, 4H), 0.99 (d, J = 6.7 Hz, 6H). (ESI+) m/z 548 (M + H) + Retention time = 4.19 min (method 1)
116
3-(3-{2-[5-(3-Methoxy- propoxy)-2-methyl- phenylamino]-oxazol- 5-yl}-5-morpholin-4- yl-phenyl)-1H-pyridin- 2-one
(300 MHz, DMSO-d 6 ) δ 11.79 (s, 1H), 9.20 (s, 1H), 7.66 (s, 2H), 7.49-7.34 (m, 3H), 7.21- 7.03 (m, 3H), 6.53 (dd, J = 8.3, 2.3 Hz, 1H), 6.30 (t, J = 6.6 Hz, 1H), 3.97 (t, J = 6.2 Hz, 2H), 3.77 (s, 4H), 3.46 (t, J = 6.1 Hz, 2H), 3.24 (s, 3H), 3.18 (s, 4H), 2.22 (s, 3H), 1.99-1.89 (m, 2H). (ESI+) m/z 517 (M + H) + Retention time = 3.56 min (method 1)
117
3-[3-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-5-(4- methyl-piperazin-1-yl)- phenyl]-1H-pyridin-2- one
(400 MHz, DMSO) δ 11.77 (s, 1H), 9.22 (s, 1H), 7.89 (s, 1H), 7.67 (dd, J = 6.8, 2.1 Hz, 1H), 7.42 (s, 1H), 7.41-7.37 (m, 1H), 7.36 (s, 1H), 7.22- 7.12 (m, 2H), 7.09 (s, 1H), 6.91 (d, J = 8.0 Hz, 1H), 6.29 (t, J = 6.8 Hz, 1H), 4.38 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 3.27-3.14 (m, 4H), 2.49- 2.46 (m, 4H), 2.28 (s, 3H), 2.24 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (ESI+) m/z 500 (M + H) + Retention time = 2.65 min (method 1)
118
2-Methyl-propane-1- sulfonic acid (4- methyl-3-{5-[3-(2-oxo- 1,2-dihydro-pyridin-3- yl)-5-piperidin-1-yl- phenyl]-oxazol-2- ylamino}-phenyl)- amide
(400 MHz, DMSO) δ 11.75 (s, 1H), 9.66 (s, 1H), 9.24 (s, 1H), 7.84 (s, 1H), 7.66 (dd, J = 7.2, 2.4 Hz, 1H), 7.41 (s, 1H), 7.38 (dd, J = 7.8, 1.9 Hz, 1H), 7.32 (s, 1H), 7.16 (s, 1H), 7.12-7.03 (m, 2H), 6.78 (dd, J = 8.3, 1.9 Hz, 1H), 6.28 (t, J = 6.5 Hz, 1H), 3.24-3.11 (m, 4H), 2.96 (d, J = 6.7 Hz, 2H), 2.23 (s, 3H), 2.17-2.08 (m, 1H), 1.69- 1.49 (m, 6H), 1.07-0.90 (m, 6H). (ESI+) m/z 562 (M + H) + Retention time = 3.13 min (method 1)
119
3-(3-{2-[2-Methyl-5- (2-piperidin-1-yl- ethoxy)-phenylamino]- oxazol-5-yl}-5- piperidin-1-yl-phenyl)- 1H-pyridin-2-one
(400 MHz, DMSO) δ 11.69 (s, 1H), 9.14 (s, 1H), 7.71-7.61 (m, 2H), 7.42 (s, 1H), 7.41-7.37 (m, 1H), 7.34 (s, 1H), 7.17 (s, 1H), 7.12-7.02 (m, 2H), 6.54 (d, J = 8.3 Hz, 1H), 6.29 (t, J = 6.8 Hz, 1H), 4.07-3.98 (m, 2H), 3.22-3.16 (m, 4H), 2.69-2.59 (m, 2H), 2.45-2.41 (m, 4H), 2.23 (s, 3H), 1.61-1.31 (m, 12H). (ESI+) m/z 554 (M + H) + Retention time = 2.38 min (method 1)
120
3-{3-[2-(5-Methoxy-2- methyl-phenylamino)- oxazol-5-yl]-5- piperidin-1-yl-phenyl}- 1-methyl-1H-pyridin-2- one
(400 MHz, DMSO-d 6 ) δ 9.20 (s, 1H), 7.76 (dd, J = 6.6, 1.9 Hz, 1H), 7.68 (d, J = 2.5 Hz, 1H), 7.65 (dd, J = 7.0, 2.0 Hz, 1H), 7.44 (s, 1H), 7.32 (s, 1H), 7.15 (s, 1H), 7.10 (s, 1H), 7.07 (d, J = 8.3 Hz, 1H), 6.54 (dd, J = 8.3, 2.6 Hz, 1H), 6.33 (t, J = 6.8 Hz, 1H), 3.73 (s, 3H), 3.52 (s, 3H), 3.27- 3.12 (m, 4H), 2.23 (s, 3H), 1.76-1.46 (m, 6H). (ESI+) m/z 471 (M + H) + Retention time = 3.18 min (method 1)
121
3-(3-{2-[2-Methyl-5- (2-oxo-piperidin-1-yl)- phenylamino]-oxazol- 5-yl}-5-pyrrolidin-1-yl- phenyl)-1H-pyridin-2- one
(400 MHz, DMSO) δ 11.75 (s, 1H), 9.28 (s, 1H), 7.84 (s, 1H), 7.68 (d, J = 1.9 Hz, 1H), 7.64 (dd, J = 6.9, 2.0 Hz, 1H), 7.37 (s, 1H), 7.18 (d, J = 7.9 Hz, 1H), 7.14 (d, J = 7.8 Hz, 1H), 6.86 (dd, J = 5.9, 2.3 Hz, 1H), 6.78 (d, J = 8.2 Hz, 1H), 6.69 (dd, J = 8.0, 2.0 Hz, 1H), 6.35-6.29 (m, 1H), 3.59 (t, J = 5.3 Hz, 2H), 3.28-3.18 (m, 4H), 2.38 (t, J = 6.0 Hz, 2H), 2.32 (s, 3H), 1.99-1.88 (m, 4H), 1.83-1.72 (m, 4H). (ESI+) m/z 510 (M + H) + Retention time = 3.44 min (method 1)
122
3-{3-[2-(3,5- Dimethoxy- phenylamino)-oxazol- 5-yl]-5-[(2-methoxy- ethyl)-methyl-amino]- phenyl}-1H-pyridin-2- one
(300 MHz, CDCl 3 ) δ 12.44 (s, 1H), 7.61 (s, 1H), 7.58 (d, J = 6.9 Hz, 1H), 7.32 (d, J = 6.1 Hz, 1H), 7.18 (s, 1H), 7.12 (s, 1H), 6.89 (s, 1H), 6.84 (s, 1H), 6.74 (s, 2H), 6.32 (t, J = 6.7 Hz, 1H), 6.14 (s, 1H), 3.79 (s, 6H), 3.64-3.48 (m, 4H), 3.37 (s, 3H), 3.03 (s, 3H). (ESI+) m/z 411 (M + H) + Retention time = 3.38 min (method 1)
123
3-{3-[2-(2,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-[methyl-(2- pyrrolidin-1-yl-ethyl)- amino]-phenyl}-1H- pyridin-2-one
(300 MHz, CDCl 3 ) δ 11.30 (s, 1H), 7.92 (s, 1H), 7.62 (d, J = 6.7 Hz, 1H), 7.34-7.30 (m, 1H), 7.18 (s, 1H), 7.15 (s, 1H), 7.07 (d, J = 7.5 Hz, 1H), 6.99 (s, 1H), 6.91 (s, 1H), 6.80 (d, J = 7.2 Hz, 1H), 6.70 (s, 1H), 6.35 (t, J = 6.7 Hz, 1H), 3.70-3.55 (m, 2H), 3.06 (s, 3H), 2.86-2.55 (m, 6H), 2.37 (s, 3H), 2.32 (s, 3H), 1.91-1.78 (m, 4H). (ESI+) m/z 484 (M + H) + Retention time = 2.89 min (method 1)
124
4-Methyl-3-{5-[3- [methyl-(2-pyrrolidin- 1-yl-ethyl)-amino]-5- (2-oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- oxazol-2-ylamino}- benzamide
(300 MHz, DMSO) δ 11.75 (s, 1H), 9.33 (s, 1H), 8.38 (s, 1H), 7.87 (s, 1H), 7.65 (d, J = 6.6 Hz, 1H), 7.48 (d, J = 7.3 Hz, 1H), 7.43-7.34 (m, 2H), 7.30-7.21 (m, 2H), 7.17 (s, 1H), 6.97 (s, 1H), 6.83 (s, 1H), 6.30 (t, J = 6.6 Hz, 1H), 3.53- 3.44 (m, 2H), 2.97 (s, 3H), 2.74-2.53 (m, 6H), 2.33 (s, 3H), 1.75-1.56 (m, 4H). (ESI+) m/z 513 (M + H) + Retention time = 2.17 min (method 1)
125
1-{3-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-5- morpholin-4-ylmethyl- phenyl}-1H-pyridin-2- one
(300 MHz, DMSO-d 6 ) δ 9.32 (s, 1H), 7.86 (s, 1H), 7.70 (dd, J = 6.7, 1.6 Hz, 1H), 7.59-7.49 (m, 4H), 7.21-7.14 (m, 2H), 6.96-6.91 (m, 1H), 6.50 (d, J = 9.7 Hz, 1H), 6.37-6.31 (m, 1H), 4.40 (s, 2H), 3.62-3.55 (m, 4H), 3.53 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 2.41 (s, 4H), 2.28 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (ESI+) m/z 501 (M + H) + Retention time = 2.65 min (method 1)
126
6-Chloro-1-{3-[2-(5- methoxy-2-methyl- phenylamino)-oxazol- 5-yl]-5-morpholin-4- ylmethyl-phenyl}-1H- pyridin-2-one
(300 MHz, DMSO-d 6 ) δ 9.27 (s, 1H), 7.65-7.57 (m, 2H), 7.57-7.51 (m, 2H), 7.46 (t, J = 1.7 Hz, 1H), 7.14-7.10 (m, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.62 (dd, J = 7.3, 1.0 Hz, 1H), 6.57 (d, J = 2.7 Hz, 1H), 6.55-6.50 (m, 1H), 3.72 (s, 3H), 3.63-3.56 (m, 4H), 3.54 (s, 2H), 2.39 (s, 4H), 2.22 (s, 3H).
127
3-(3-Isobutyl-5-{2-[2- methyl-5-(2-pyrrolidin- 1-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-phenyl)-1H- pyridin-2-one
(400 MHz, DMSO) δ 11.82 (s, 1H), 9.22 (s, 1H), 7.79 (s, 1H), 7.73-7.62 (m, 2H), 7.44 (s, 1H), 7.41 (d, J = 7.3 Hz, 1H), 7.37 (d, J = 10.2 Hz, 2H), 7.06 (d, J = 8.5 Hz, 1H), 6.60-6.49 (m, 1H), 6.31 (t, J = 6.7 Hz, 1H), 4.02 (t, J = 5.8 Hz, 2H), 2.78 (t, J = 5.8 Hz, 2H), 2.50-2.49 (m, 4H), 2.48-2.37 (m, 2H), 2.23 (s, 3H), 1.93- 1.86 (m, 1H), 1.78-1.55 (m, 4H), 0.92 (s, 3H), 0.89 (s, 3H).
128
3-{3-[2-(5-Methoxy-2- methyl-phenylamino)- oxazol-5-yl]-5- morpholin-4-ylmethyl- phenyl}-1H-pyridin-2- one
(300 MHz, DMSO-d 6 ) δ 11.84 (s, 1H), 9.26 (s, 1H), 7.85 (s, 1H), 7.67 (s, 2H), 7.56-7.26 (m, 4H), 7.07 (d, J = 8.1 Hz, 1H), 6.55 (d, J = 7.0 Hz, 1H), 6.32 (t, J = 6.3 Hz, 1H), 3.73 (s, 3H), 3.59 (s, 4H), 3.50 (s, 2H), 2.39 (s, 4H), 2.23 (s, 3H). (ESI+) m/z 473 (M + H) + Retention time = 2.52 min (method 1)
129
N-{3-[5-(2-Oxo-2H- [1,3′]bipyridinyl-5′-yl)- oxazol-2-yl-amino]-5- trifluoromethyl- phenyl}-2-pyrrolidin-1- yl-acetamide
(300 MHz, DMSO-d 6 ) δ 10.93 (s, 1H), 10.11 (s, 1H), 8.88 (s, 1H), 8.54 (s, 1H), 8.24 (s, 1H), 8.15 (s, 1H), 7.87-7.75 (m, 3H), 7.70 (s, 1H), 7.63- 7.48 (m, 1H), 6.55 (d, J = 9.3 Hz, 1H), 6.40 (t, J = 6.5 Hz, 1H), 3.26 (s, 2H), 2.59 (s, 4H), 1.75 (s, 4H). (ESI+) m/z 525 (M + H) + Retention time = 2.48 min (method 1)
130
N-{3-[5-(2-Oxo-2H- [1,3′]bipyridinyl-5′-yl)- oxazol-2-yl-amino]-5- methyl-phenyl}-2- pyrrolidin-1-yl- acetamide
(300 MHz, DMSO-d 6 ) δ 10.43 (s, 1H), 9.64 (s, 1H), 8.87 (s, 1H), 8.51 (s, 1H), 8.13 (s, 1H), 7.86 (s, 1H), 7.80 (d, J = 6.6 Hz, 1H), 7.74 (s, 1H), 7.58 (t, J = 7.3 Hz, 1H), 7.14 (s, 1H), 7.07 (s, 1H), 6.55 (d, J = 9.3 Hz, 1H), 6.39 (t, J = 6.4 Hz, 1H), 3.21 (s, 2H), 2.58 (s, 4H), 2.26 (s, 3H), 1.75 (s, 4H). (ESI+) m/z 471 (M + H) + Retention time = 2.10 min (method 1)
131
N-{4-Methyl-3-[5-(4- methyl-2-oxo-2H- [1,3′]bipyridinyl-5′-yl)- oxazol-2-ylamino]- phenyl}-2-pyrrolidin-1- yl-acetamide
(300 MHz, DMSO-d 6 ) δ 9.66 (s, 1H), 9.44 (s, 1H), 8.86 (d, J = 2.0 Hz, 1H), 8.47 (d, J = 2.2 Hz, 1H), 8.13 (d, J = 1.7 Hz, 1H), 8.07 (t, J = 2.1 Hz, 1H), 7.70-7.66 (m, 2H), 7.29 (dd, J = 8.1, 2.0 Hz, 1H), 7.11 (d, J = 8.4 Hz, 1H), 6.35 (s, 1H), 6.25 (dd, J = 7.0, 1.7 Hz, 1H), 3.19 (s, 2H), 2.57 (s, 4H), 2.23 (s, 3H), 2.21 (s, 3H), 1.76-1.70 (m, 4H).
132
2-Methyl-propane-1- sulfonic acid {4- methyl-3-[5-(2′-oxo- 1′,2′-dihydro- [3,3′]bipyridinyl-5-yl)- oxazol-2-yl-amino]- phenyl}-amide
(300 MHz, DMSO-d 6 ) δ 11.98 (s, 1H), 9.70 (s, 1H), 9.46 (s, 1H), 8.77 (d, J = 11.8 Hz, 2H), 8.31 (s, 1H), 7.84 (d, J = 6.7 Hz, 1H), 7.80 (s, 1H), 7.61 (s, 1H), 7.49 (s, 1H), 7.13 (d, J = 8.1 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 6.36 (t, J = 6.7 Hz, 1H), 2.97 (d, J = 6.4 Hz, 2H), 2.25 (s, 3H), 2.17- 2.09 (m, 1H), 0.99 (d, J = 6.6 Hz, 6H). (ESI+) m/z 480 (M + H) + Retention time = 2.84 min (method 1)
133
5′-[2-(5- (Isopropoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-1H- [3,3′]bipyridinyl-2-one
(300 MHz, DMSO-d 6 ) δ 11.98 (s, 1H), 9.41 (s, 1H), 8.76 (s, 1H), 8.73 (s, 1H), 8.31 (s, 1H), 7.92- 7.71 (m, 2H), 7.60 (s, 1H), 7.49 (d, J = 5.4 Hz, 1H), 7.16 (d, J = 7.7 Hz, 1H), 6.95 (d, J = 7.7 Hz, 1H), 6.36 (t, J = 6.5 Hz, 1H), 4.43 (s, 2H), 3.63 (q, J = 6.0 Hz, 1H), 2.28 (s, 3H), 1.12 (d, J = 6.0 Hz, 6H). (ESI+) m/z 417 (M + H) + Retention time = 3.02 min (method 1)
134
1-(2-Dimethylamino- ethyl)-5′-[2-(5- methoxy-2-methyl- phenylamino)-oxazol- 5-yl]-1H- [3,3′]bipyridinyl-2-one
(300 MHz, CDCl 3 ) δ 8.66 (d, J = 2.2 Hz, 1H), 8.56 (d, J = 1.9 Hz, 1H), 8.08 (t, J = 2.2 Hz, 1H), 7.70 (m, 1H), 7.59 (s, 1H), 7.51 (dd, J = 7.0, 1.9 Hz, 1H), 7.43 (dd, J = 7.1, 1.9 Hz, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.96 (m, 1H), 6.65 (dd, J = 8.4, 2.6 Hz, 1H), 6.34 (t, J = 6.8 Hz, 1H), 4.12 (t, J = 6.3 Hz, 2H), 3.77 (s, 3H), 2.68 (t, J = 6.3 Hz, 2H), 2.29 (s, 6H), 2.15 (s, 3H).
135
3-(3-{2-[2-Methyl-5- (2-morpholin-4-yl- ethoxy)-phenylamino]- oxazol-5-yl}-5- trifluoromethoxy- phenyl)-1H-pyridin-2- one
(400 MHz, DMSO-d 6 ) δ 11.98 (s, 1H), 9.36 (s, 1H), 7.97 (s, 1H), 7.84 (d, J = 7.0 Hz, 1H), 7.76- 7.57 (m, 3H), 7.50 (br s, 2H), 7.08 (d, J = 8.2 Hz, 1H), 6.58 (d, J = 8.2 Hz, 1H), 6.36 (t, J = 6.7 Hz, 1H), 4.05 (t, J = 5.7 Hz, 2H), 3.58 (d, J = 4.1 Hz, 4H), 2.68 (t, J = 5.7 Hz, 2H), 2.47 (s, 4H), 2.23 (s, 3H). (ESI+) m/z 557 (M + H) + Retention time = 3.06 min (method 1)
136
3-{3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5- trifluoromethoxy- phenyl}-4-methyl-1H- pyridin-2-one
(400 MHz, DMSO) δ 11.65 (s, 1H), 10.21 (s, 1H), 7.64 (s, 1H), 7.50 (s, 1H), 7.46 (s, 1H), 7.33 (d, J = 6.6 Hz, 1H), 7.26 (s, 2H), 7.09 (s, 1H), 6.62 (s, 1H), 6.20 (d, J = 6.7 Hz, 1H), 2.25 (s, 6H), 2.05 (s, 3H). (ESI+) m/z 456 (M + H) + Retention time = 4.66 min (method 1)
137
3-{3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-methoxy- phenyl}-1H-pyridin-2- one
(400 MHz, DMSO) δ 11.85 (s, 1H), 10.22 (s, 1H), 7.73 (dd, J = 6.9, 2.0 Hz, 1H), 7.56 (d, J = 1.4 Hz, 1H), 7.50 (s, 1H), 7.43 (d, J = 4.6 Hz, 1H), 7.25 (s, 2H), 7.19 (d, J = 1.4 Hz, 1H), 7.09 (s, 1H), 6.60 (s, 1H), 6.32 (t, J = 6.7 Hz, 1H), 3.82 (s, 3H), 2.17 (s, 6H). (ESI+) m/z 388 (M + H) + Retention time = 3.90 min (method 1)
138
3-(3-{2-[5-(2-Hydroxy- ethoxy)-2-methyl- phenylamino]-oxazol- 5-yl}-5-methoxy- phenyl)-1H-pyridin-2- one
(400 MHz, DMSO-d 6 ) δ 11.84 (s, 1H), 9.26 (s, 1H), 7.71 (dd, J = 6.9, 2.0 Hz, 1H), 7.69 (d, J = 2.5 Hz, 1H), 7.54 (s, 1H), 7.49 (s, 1H), 7.43 (d, J = 4.9 Hz, 1H), 7.19 (br s, 1H), 7.11 (br s, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.54 (dd, J = 8.3, 2.5 Hz, 1H), 6.32 (t, J = 6.6 Hz, 1H), 4.88 (t, J = 5.5 Hz, 1H), 3.94 (t, J = 5.0 Hz, 2H), 3.83 (s, 3H), 3.70 (q, J = 5.1 Hz, 2H), 2.23 (s, 3H). (ESI+) m/z 448 (M + H) + Retention time = 3.07 min (method 1)
139
3-{3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-isopropoxy- phenyl}-4-methyl-1H- pyridin-2-one
1H NMR (400 MHz, DMSO-d 6 ) δ 11.57 (s, 1H), 10.18 (s, 1H), 7.50 (s, 1H), 7.29 (d, J = 6.7 Hz, 1H), 7.25 (s, 2H), 7.05 (s, 1H), 6.99 (s, 1H), 6.63 (s, 1H), 6.61 (s, 1H), 6.17 (d, J = 6.8 Hz, 1H), 4.75-4.59 (m, 1H), 2.25 (s, 6H), 2.03 (s, 3H), 1.31 (d, J = 6.0 Hz, 6H). (ESI+) m/z 430 (M + H) + Retention time = 4.45 min (method 1)
140
4-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-4′-methyl- 1′H-[2,3′]bipyridinyl- 2′-one
(300 MHz, DMSO-d 6 ) δ 11.67 (s, 1H), 9.51 (s, 1H), 8.59 (d, J = 5.3 Hz, 1H), 7.79 (s, 1H), 7.77 (s, 1H), 7.53 (s, 1H), 7.42 (dd, J = 5.3, 1.7 Hz, 1H), 7.34 (d, J = 6.6 Hz, 1H), 7.18 (d, J = 7.7 Hz, 1H), 6.96 (d, J = 7.6 Hz, 1H), 6.18 (d, J = 6.7 Hz, 1H), 4.40 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 2.26 (s, 3H), 2.03 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (ESI+) m/z 417 (M + H) + Retention time = 2.53 min (method 1)
141
3-{3-[2-(3,5-Dichloro- phenylamino)-oxazol- 5-yl]-5-methoxy- phenyl}-4-methyl-1H- pyridin-2-one
(400 MHz, DMSO-d 6 ) δ 11.56 (s, 1H), 10.82 (s, 1H), 7.70 (s, 2H), 7.57 (s, 1H), 7.28 (d, J = 6.3 Hz, 1H), 7.14 (s, 1H), 7.08 (s, 1H), 7.05 (s, 1H), 6.68 (s, 1H), 6.16 (d, J = 6.7 Hz, 1H), 3.81 (s, 3H), 2.01 (s, 1H). (ESI+) m/z 442 (M + H) + Retention time = 4.60 min (method 1)
142
3-[3-Methoxy-5-(2-m- tolylamino-oxazol-5- yl)-phenyl]-4-methyl- 1H-pyridin-2-one
(400 MHz, DMSO-d 6 ) δ 11.53 (s, 1H), 10.19 (s, 1H), 7.48 (s, 2H), 7.41 (d, J = 8.2 Hz, 1H), 7.28 (d, J = 6.6 Hz, 1H), 7.19 (t, J = 7.8 Hz, 1H), 7.07 (s, 1H), 7.03 (s, 1H), 6.77 (d, J = 7.3 Hz, 1H), 6.65 (s, 1H), 6.16 (d, J = 6.7 Hz, 1H), 3.82 (s, 3H), 2.30 (s, 3H), 2.02 (s, 3H). (ESI+) m/z 388 (M + H) + Retention time = 3.74 min (method 1)
143
3-[3-[2-(5- (Methoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-5-(2- morpholin-4-yl- ethoxy)-phenyl]-4- methyl-1H-pyridin-2- one
(400 MHz, DMSO) δ 11.58 (s, 1H), 9.22 (s, 1H), 7.89 (s, 1H), 7.49 (s, 1H), 7.29 (d, J = 6.6 Hz, 1H), 7.16 (d, J = 7.7 Hz, 1H), 7.10 (s, 1H), 7.01 (s, 1H), 6.91 (d, J = 8.6 Hz, 1H), 6.65 (s, 1H), 6.16 (d, J = 6.7 Hz, 1H), 4.36 (s, 2H), 4.13 (t, J = 5.7 Hz, 2H), 3.64-3.49 (m, 4H), 3.26 (s, 3H), 2.72 (t, J = 5.6 Hz, 2H), 2.50-2.46 (m, 4H), 2.26 (s, 3H), 2.01 (s, 3H). (ESI+) m/z 529 (M + H) + Retention time = 2.61 min (method 1)
144
3-[3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-(2-morpholin-4- yl-ethoxy)-phenyl]-4- methyl-1H-pyridin-2- one
(400 MHz, DMSO) δ 11.54 (s, 1H), 10.10 (s, 1H), 7.49 (s, 1H), 7.28 (d, J = 6.7 Hz, 1H), 7.25 (s, 2H), 7.08 (s, 1H), 7.01 (s, 1H), 6.66 (s, 1H), 6.60 (s, 1H), 6.16 (d, J = 6.7 Hz, 1H), 4.14 (t, J = 5.7 Hz, 2H), 3.64-3.49 (m, 4H), 2.72 (t, J = 5.7 Hz, 2H), 2.58-2.53 (m, 4H), 2.24 (s, 6H), 2.00 (s, 3H). (ESI+) m/z 501 (M + H) + Retention time = 2.97 min (method 1)
145
3-{3-Chloro-5-[2-(5- (methoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-phenyl}- 4-methyl-1H-pyridin-2- one
(400 MHz, DMSO) δ 11.62 (s, 1H), 9.29 (s, 1H), 7.86 (s, 1H), 7.66-7.50 (m, 2H), 7.38 (s, 1H), 7.32(d, J = 6.7 Hz, 1H), 7.17 (d, J = 7.6 Hz, 1H), 7.14 (s, 1H), 6.93 (d, J = 7.1 Hz, 1H), 6.19 (d, J = 6.7 Hz, 1H), 4.37 (s, 2H), 3.27 (s, 3H), 2.28 (s, 3H), 2.02 (s, 3H). (ESI+) m/z 436 (M + H) + Retention time = 3.86 min (method 1)
146
4-Methyl-3-(3-methyl- 5-{2-[2-methyl-5-(2- pyrrolidin-1-yl- ethoxy)-phenylamino]- oxazol-5-yl}-phenyl)- 1H-pyridin-2-one
(300 MHz, DMSO) δ 11.54 (s, 1H), 9.16 (s, 1H), 7.66 (s, 1H), 7.43 (s, 1H), 7.36 (s, 1H), 7.30- 7.22 (m, 2H), 7.05 (d, J = 8.3 Hz, 1H), 6.90 (s, 1H), 6.53 (dd, J = 8.2, 2.2 Hz, 1H), 6.16 (d, J = 6.6 Hz, 1H), 4.01 (t, J = 5.8 Hz, 2H), 2.76 (t, J = 5.8 Hz, 2H), 2.49 (m, 4H), 2.35 (s, 3H), 2.21 (s, 3H), 1.99 (s, 3H), 1.75-1.61 (m, 4H). (ESI+) m/z 485 (M + H) + Retention time = 2.85 min (method 1)
147
3-{3-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-5-methyl- phenyl}-4-methyl-1H- pyridin-2-one
(300 MHz, DMSO-d 6 ) δ 11.55 (s, 1H), 9.19 (s, 1H), 7.87 (s, 1H), 7.41 (s, 1H), 7.35 (s, 1H), 7.28 (d, J = 6.6 Hz, 1H), 7.22 (s, 1H), 7.15 (d, J = 7.6 Hz, 1H), 6.96-6.86 (m, 2H), 6.16 (d, J = 6.7 Hz, 1H), 4.40 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 2.36 (s, 3H), 2.27 (s, 3H), 2.00 (s, 3H), 1.12 (t, J = 7.0 Hz, 3H). (ESI+) m/z 430 (M + H) + Retention time = 3.84 min (method 1)
148
4-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-2-(2-oxo- 2H-pyridin-1-yl)- benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.55 (s, 1H), 8.05 (d, J = 8.1 Hz, 1H), 7.77 (dd, J = 16.5, 10.7 Hz, 5H), 7.61 (t, J = 7.0 Hz, 1H), 7.18 (d, J = 7.6 Hz, 1H), 6.97 (d, J = 7.7 Hz, 1H), 6.57 (d, J = 9.2 Hz, 1H), 6.41 (t, J = 6.6 Hz, 1H), 4.41 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 2.27 (s, 3H) ), 1.13 (t, J = 7.0 Hz, 3H). (ESI+) m/z 427 (M + H) + Retention time = 3.61 min (method 1)
149
N-(3-{5-[4-Cyano-3- (2-oxo-2H-pyridin-1- yl)-phenyl]-oxazol-2- ylamino}-4-methyl- phenyl)-3-(4-methyl- piperazin-1-yl)- propionamide
(300 MHz, DMSO-d 6 ) δ 10.11 (s, 1H), 9.52 (s, 1H), 8.08 (s, 1H), 8.04 (d, J = 8.2 Hz, 1H), 7.90- 7.69 (m, 4H), 7.60 (t, J = 7.1 Hz, 1H), 7.28 (d, J = 7.9 Hz, 1H), 7.11 (d, J = 8.1 Hz, 1H), 6.56 (d, J = 9.1 Hz, 1H), 6.41 (t, J = 6.5 Hz, 1H), 2.57 (d, J = 6.2 Hz, 2H), 2.43-2.05 (m, 16H). (ESI+) m/z 538 (M + H) + Retention time = 2.17 min (method 1)
150
4-{2-[2-Methyl-5- (pyrrolidine-1- carbonyl)- phenylamino]-oxazol- 5-yl}-2-(2-oxo-2H- pyridin-1-yl)- benzonitrile
(400 MHz, DMSO-d 6 ) δ 9.67 (s, 1H), 8.13-7.99 (m, 2H), 7.84 (s, 1H), 7.83-7.70 (m, 3H), 7.62 (t, J = 7.9 Hz, 1H), 7.27 (d, J = 7.8 Hz, 1H), 7.16 (d, J = 6.6 Hz, 1H), 6.57 (d, J = 9.2 Hz, 1H), 6.42 (t, J = 6.4 Hz, 1H), 3.54-3.37 (m, 4H), 2.33 (s, 3H), 1.99-1.68 (m, 4H). (ESI+) m/z 466 (M + H) + Retention time = 3.09 min (method 1)
151
4-[2-(2-Methyl-5- pyrrolidin-1-ylmethyl- phenylamino)-oxazol- 5-yl]-2-(2-oxo-2H- pyridin-1-yl)- benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.53 (s, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.81 (s, 1H), 7.77-7.64 (m, 4H), 7.61 (t, J = 7.9 Hz, 1H), 7.14 (d, J = 7.8 Hz, 1H), 6.95 (d, J = 7.8 Hz, 1H), 6.56 (d, J = 9.3 Hz, 1H), 6.40 (t, J = 6.6 Hz, 1H), 3.51 (s, 2H), 2.46-2.34 (m, 4H), 2.25 (s, 3H), 1.72-1.60 (m, 4H). (ESI+) m/z 452 (M + H) + Retention time = 2.35 min (method 1)
152
4-[2-(5-{[(2- Dimethylamino-ethyl)- methyl-amino]- methyl}-2-methyl- phenylamino)-oxazol- 5-yl]-2-(2-oxo-2H- pyridin-1-yl)- benzonitrile
(300 MHz, CDCl 3 ) δ 7.87 (s, 1H), 7.76 (d, J = 8.2 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.56 (s, 1H), 7.45 (m, 1H), 7.34 (s, 1H), 7.28 (m, 1H), 7.14 (d, J = 7.7 Hz, 1H), 7.02 (d, J = 7.8 Hz, 1H), 6.70 (m, 2H), 6.32 (t, J = 6.8 Hz, 1H), 3.49 (s, 2H), 2.56-2.41 (m, 4H), 2.28 (s, 3H), 2.22 (s, 9H). (ESI+) m/z 483 (M + H) + Retention time = 1.88 min (method 1)
153
N-(3-{5-[4-Cyano-3- (2-oxo-2H-pyridin-1- yl)-phenyl]-oxazol-2- ylamino}-5- trifluoromethyl- phenyl)-2-pyrrolidin-1- yl-acetamide
(400 MHz, DMSO) δ 10.99 (s, 1H), 10.13 (s, 1H), 8.29 (s, 1H), 8.08 (d, J = 8.1 Hz, 1H), 7.92 (s, 1H), 7.90 (d, J = 1.5 Hz, 1H), 7.84-7.72 (m, 3H), 7.69 (s, 1H), 7.66-7.58 (m, 1H), 6.58 (d, J = 9.3 Hz, 1H), 6.43 (dd, J = 7.2, 6.0 Hz, 1H), 3.27 (s, 2H), 2.60 (s, 4H), 1.76 (s, 4H). (ESI+) m/z 549 (M + H) + Retention time = 2.82 min (method 1)
154
N-(3-{5-[4-Cyano-3- (2-oxo-2H-pyridin-1- yl)-phenyl]-oxazol-2- ylamino}-5-methyl- phenyl)-2- dimethylamino- acetamide
(300 MHz, DMSO-d 6 ) δ 10.55 (s, 1H), 9.67 (s, 1H), 8.09 (d, J = 8.3 Hz, 1H), 7.98-7.87 (m, 3H), 7.82 (d, J = 8.5 Hz, 2H), 7.65 (t, J = 7.1 Hz, 1H), 7.16 (s, 1H), 7.11 (s, 1H), 6.61 (d, J = 9.4 Hz, 1H), 6.45 (t, J = 6.6 Hz, 1H), 3.07 (s, 2H), 2.31 (s, 6H), 2.29 (s, 3H). (ESI+) m/z 469 (M + H) + Retention time = 2.34 min (method 1)
155
N-(3-{5-[4-Cyano-3- (2-oxo-2H-pyridin-1- yl)-phenyl]-oxazol-2- ylamino}-phenyl)-2- diethylamino- acetamide
(300 MHz, DMSO-d6) δ 10.57 (s, 1H), 9.61 (s, 1H), 8.09 (s, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.86 (s, 2H), 7.77 (d, J = 7.9 Hz, 2H), 7.61 (t, J = 7.1 Hz, 1H), 7.32-7.08 (m, 3H), 6.57 (d, J = 9.3 Hz, 1H), 6.42 (t, J = 6.7 Hz, 1H), 3.12 (s, 2H), 2.60 (q, J = 7.0 Hz, 4H), 1.02 (t, J = 7.0 Hz, 6H). (ESI+) m/z 483 (M + H) + Retention time = 2.30 min (method 1)
156
4-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-2-(3- methyl-2-oxo-2H- pyridin-1-yl)- benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.55 (s, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.83-7.68 (m, 4H), 7.61 (d, J = 6.7 Hz, 1H), 7.48 (d, J = 6.6 Hz, 1H), 7.18 (d, J = 7.8 Hz, 1H), 6.97 (d, J = 7.4 Hz, 1H), 6.33 (t, J = 6.8 Hz, 1H), 4.41 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 2.27 (s, 3H), 2.06 (d, J = 7.1 Hz, 3H), 1.12 (t, J = 7.0 Hz, 3H). (ESI+) m/z 441 (M + H) + Retention time = 3.90 min (method 1)
157
N-(3-{5-[4-Cyano-3- (3-methyl-2-oxo-2H- pyridin-1-yl)-phenyl]- oxazol-2-ylamino}-4- methyl-phenyl)-2- piperidin-1-yl- acetamide
(300 MHz, DMSO-d 6 ) δ 9.62 (s, 1H), 9.55 (s, 1H), 8.13 (d, J = 1.5 Hz, 1H), 8.03 (d, J = 8.3 Hz, 1H), 7.83-7.75 (m, 3H), 7.61 (d, J = 6.7 Hz, 1H), 7.48 (d, J = 6.6 Hz, 1H), 7.27 (dd, J = 8.1, 1.8 Hz, 1H), 7.12 (d, J = 8.2 Hz, 1H), 6.33 (t, J = 6.8 Hz, 1H), 3.01 (s, 2H), 2.44 (s, 4H), 2.23 (s, 3H), 2.07 (s, 3H), 1.55 (s, 4H), 1.41-1.37 (m, 2H).
158
2-(3-Methyl-2-oxo-2H- pyridin-1-yl)-4-[2-(2- methyl-5-pyrrolidin-1- ylmethyl- phenylamino)-oxazol- 5-yl]-benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.53 (s, 1H), 8.04 (d, J = 8.3 Hz, 1H), 7.81 (s, 1H), 7.77-7.68 (m, 3H), 7.61 (d, J = 6.5 Hz, 1H), 7.48 (d, J = 6.0 Hz, 1H), 7.14 (d, J = 7.6 Hz, 1H), 6.95 (d, J = 7.6 Hz, 1H), 6.33 (t, J = 6.7 Hz, 1H), 3.51 (s, 2H), 2.46-2.34 (m, 4H), 2.25 (s, 3H), 2.07 (s, 3H), 1.71-1.59 (m, 4H). (ESI+) m/z 466 (M + H) + Retention time = 2.58 min (method 1)
159
3-{5-[4-Cyano-3-(3- methyl-2-oxo-2H- pyridin-1-yl)-phenyl]- oxazol-2-ylamino}-N- (2-methoxy-ethyl)-4,N- dimethyl-benzamide
(400 MHz, DMSO) δ 9.67 (s, 1H), 8.07 (d, J = 8.1 Hz, 1H), 7.95 (s, 1H), 7.84 (s, 1H), 7.80- 7.72 (m, 2H), 7.63 (d, J = 5.4 Hz, 1H), 7.49 (d, J = 6.6 Hz, 1H), 7.34-7.16 (m, 1H), 7.02 (d, J = 7.5 Hz, 1H), 6.34 (t, J = 6.8 Hz, 1H), 3.68-3.38 (m, 5H), 3.15 (m, 2H), 2.96 (s, 3H), 2.33 (s, 3H), 2.08 (s, 3H). (ESI+) m/z 498 (M + H) + Retention time = 3.22 min (method 1)
160
2-(3-Methyl-2-oxo-2H- pyridin-1-yl)-4-{2-[2- methyl-5-(2-piperidin- 1-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.50 (s, 1H), 8.05 (d, J = 8.1 Hz, 1H), 7.83 (s, 1H), 7.76 (d, J = 9.8 Hz, 2H), 7.62 (d, J = 6.1 Hz, 1H), 7.55 (d, J = 2.3 Hz, 1H), 7.49 (d, J = 6.1 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.59 (dd, J = 8.4, 2.4 Hz, 1H), 6.34 (t, J = 6.8 Hz, 1H), 4.01 (t, J = 5.9 Hz, 2H), 2.62 (t, J = 5.9 Hz, 2H), 2.41 (s, 4H), 2.20 (s, 3H), 2.07 (s, 3H), 1.48 (d, J = 5.0 Hz, 4H), 1.37 (d, J = 4.6 Hz, 2H). (ESI+) m/z 510 (M + H) + Retention time = 2.77 min (method 1)
161
N-(3-{5-[4-Cyano-3- (4-methyl-2-oxo-2H- pyridin-1-yl)-phenyl]- oxazol-2-ylamino}-4- methyl-phenyl)-2- pyrrolidin-1-yl- acetamide
(300 MHz, DMSO-d 6 ) δ 9.66 (s, 1H), 9.55 (s, 1H), 8.14 (d, J = 1.5 Hz, 1H), 8.02 (d, J = 8.2 Hz, 1H), 7.84-7.79 (m, 2H), 7.76 (dd, J = 8.3, 1.3 Hz, 1H), 7.65 (d, J = 7.0 Hz, 1H), 7.28 (dd, J = 8.1, 1.9 Hz, 1H), 7.12 (d, J = 8.3 Hz, 1H), 6.37 (s, 1H), 6.28 (dd, J = 7.1, 1.6 Hz, 1H), 3.18 (s, 2H), 2.57 (s, 4H), 2.23 (s, 6H), 1.74 (s, 4H). (ESI+) m/z 509 (M + H) + Retention time = 2.50 min (method 1)
162
2-(4-Methyl-2-oxo-2H- pyridin-1-yl)-4-[2-(2- methyl-5-pyrrolidin-1- ylmethyl- phenylamino)-oxazol- 5-yl]-benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.53 (s, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.80 (s, 1H), 7.74-7.68 (m, 3H), 7.65 (d, J = 7.0 Hz, 1H), 7.14 (d, J = 7.6 Hz, 1H), 6.95 (d, J = 7.4 Hz, 1H), 6.38 (s, 1H), 6.28 (d, J = 7.0 Hz, 1H), 3.52 (s, 2H), 2.47-2.36 (m, 4H), 2.25 (s, 3H), 2.23 (s, 3H), 1.72-1.60 (m, 4H). (ESI+) m/z 466 (M + H) + Retention time = 2.53 min (method 1)
163
2-(4-Methyl-2-oxo-2H- pyridin-1-yl)-4-{2-[2- methyl-5-(2-piperidin- 1-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.50 (s, 1H), 8.04 (d, J = 8.5 Hz, 1H), 7.82 (s, 1H), 7.78-7.72 (m, 2H), 7.65 (d, J = 7.0 Hz, 1H), 7.55 (d, J = 2.1 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.59 (dd, J = 8.3, 2.2 Hz, 1H), 6.38 (s, 1H), 6.29 (d, J = 7.0 Hz, 1H), 4.01 (t, J = 5.8 Hz, 2H), 2.63 (t, J = 5.3 Hz, 2H), 2.42 (s, 4H), 2.23 (s, 3H), 2.21 (s, 3H), 1.54- 1.44 (m, 4H), 1.39-1.31 (m, 2H). (ESI+) m/z 510 (M + H) + Retention time = 2.70 min (method 1)
164
4-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-2-(5- methyl-2-oxo-2H- pyridin-1-yl)- benzonitrile
(300 MHz, DMSO-d 6 ) δ 9.56 (s, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.83-7.70 (m, 4H), 7.57 (s, 1H), 7.49 (dd, J = 9.4, 2.3 Hz, 1H), 7.18 (d, J = 7.7 Hz, 1H), 6.97 (d, J = 7.8 Hz, 1H), 6.51 (d, J = 9.4 Hz, 1H), 4.41 (s, 2H), 3.46 (q, J = 7.0 Hz, 2H), 2.27 (s, 3H), 2.08 (s, 3H), 1.13 (t, J = 7.0 Hz, 3H). (ESI+) m/z 441 (M + H) + Retention time = 3.83 min (method 1)
165
4′-{2-[2-Methyl-5-(1- methyl-piperidin-4- yloxy)-phenylamino]- oxazol-5-yl}- [1,2′]bipyridinyl-2-one
(300 MHz, DMSO-d 6 ) δ 9.58 (s, 1H), 8.57 (d, J = 5.4 Hz, 1H), 7.93-7.83 (m, 3H), 7.62-7.51 (m, 3H), 7.07 (d, J = 8.4 Hz, 1H), 6.61 (dd, J = 8.3, 2.5 Hz, 1H), 6.53 (d, J = 9.1 Hz, 1H), 6.38 (td, J = 6.9, 1.1 Hz, 1H), 4.37-4.10 (m, 1H), 2.68- 2.53 (m, 2H), 2.21 (s, 3H), 2.15 (s, 3H), 2.13 (s, 2H), 1.89 (s, 2H), 1.76-1.49 (m, 2H). (ESI+) m/z 458 (M + H) + Retention time = 2.31 min (method 1)
166
4′-[2-(3-Methyl-5- pyrrolidin-1-ylmethyl- phenylamino)-oxazol- 5-yl]-[1,2′]bipyridinyl- 2-one
(300 MHz, DMSO-d6) δ 10.51 (s, 1H), 8.58 (d, J = 5.1 Hz, 1H), 8.03-7.76 (m, 3H), 7.71-7.46 (m, 2H), 7.40 (s, 1H), 7.35 (s, 1H), 6.75 (s, 1H), 6.54 (d, J = 9.1 Hz, 1H), 6.39 (t, J = 6.6 Hz, 1H), 3.50 (s, 2H), 2.42 (s, 4H), 2.28 (s, 3H), 1.68 (s, 4H). (ESI+) m/z 428 (M + H) + Retention time = 2.27 min (method 1)
167
4′-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-[1,2′]bipyridinyl- 2-one
(300 MHz, DMSO-d 6 ) δ 10.48 (s, 1H), 8.58 (d, J = 5.2 Hz, 1H), 7.91 (s, 3H), 7.71-7.42 (m, 2H), 7.27 (s, 2H), 6.64 (s, 1H), 6.54 (d, J = 9.2 Hz, 1H), 6.39 (t, J = 6.7 Hz, 1H), 2.26 (s, 6H). (ESI+) m/z 359 (M + H) + Retention time = 3.65 min (method 1)
168
4-[2-(5- (Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 11.91 (s, 1H), 9.61 (s, 1H), 8.73 (s, 1H), 8.58 (d, J = 5.0 Hz, 1H), 8.43 (d, J = 7.0 Hz, 1H), 7.78 (s, 1H), 7.71 (s, 1H), 7.55 (d, J = 5.0 Hz, 1H), 7.45 (d, J = 4.6 Hz, 1H), 7.18 (d, J = 7.4 Hz, 1H), 6.97 (d, J = 7.4 Hz, 1H), 6.41 (t, J = 6.6 Hz, 1H), 4.43 (s, 2H), 3.47 (q, J = 6.9 Hz, 2H), 2.29 (s, 3H), 1.14 (t, J = 6.9 Hz, 3H). (ESI+) m/z 403 (M + H) + Retention time = 2.58 min (method 1)
169
N-{4-Methyl-3-[5-(2′- oxo-1′,2′-dihydro- [2,3']bipyridinyl-4-yl)- oxazol-2-ylamino]- phenyl}-2-pyrrolidin-1- yl-acetamide
(300 MHz, DMSO-d 6 ) δ 12.04 (s, 1H), 9.67 (s, 1H), 9.60 (s, 1H), 8.73 (s, 1H), 8.58 (d, J = 5.2 Hz, 1H), 8.43 (dd, J = 7.1, 2.0 Hz, 1H), 8.04 (d, J = 1.7 Hz, 1H), 7.70 (s, 1H), 7.55 (d, J = 4.9 Hz, 1H), 7.47 (dd, J = 5.1, 1.3 Hz, 1H), 7.37 (dd, J = 8.1, 1.7 Hz, 1H), 7.12 (d, J = 8.2 Hz, 1H), 6.41 (t, J = 6.7 Hz, 1H), 3.22 (s, 2H), 2.58 (s, 4H), 2.24 (s, 3H), 1.73 (s, 4H). (ESI+) m/z 471 (M + H) + Retention time = 1.62 min (method 1)
170
4-{2-[2-Methyl-5-(1- methyl-piperidin-4- yloxy)-phenylamino]- oxazol-5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 12.04 (s, 1H), 9.57 (s, 1H), 8.69 (s, 1H), 8.59 (d, J = 5.3 Hz, 1H), 8.42 (dd, J = 7.1, 2.1 Hz, 1H), 7.71 (s, 1H), 7.61- 7.49 (m, 2H), 7.46 (dd, J = 5.1, 1.7 Hz, 1H), 7.07 (d, J = 8.3 Hz, 1H), 6.60 (dd, J = 8.3, 2.5 Hz, 1H), 6.41 (t, J = 6.7 Hz, 1H), 4.39-4.16 (m, 1H), 2.67-2.53 (m, 2H), 2.24 (s, 3H), 2.14 (s, 3H), 2.14-2.01 (m, 2H), 2.00-1.81 (m, 2H), 1.75- 1.48 (m, 2H). (ESI+) m/z 458 (M + H) + Retention time = 1.74 min (method 1)
171
4-{2-[5-(5- Dimethylaminomethyl- furan-2-yl)-2-methyl- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.05 (s, 1H), 9.70 (s, 1H), 8.74 (s, 1H), 8.59 (d, J = 5.1 Hz, 1H), 8.43 (dd, J = 7.1, 2.1 Hz, 1H), 8.12 (d, J= 1.4 Hz, 1H), 7.73 (s, 1H), 7.55 (d, J = 4.5 Hz, 1H), 7.46 (dd, J = 5.1, 1.6 Hz, 1H), 7.34 (dd, J = 7.9, 1.4 Hz, 1H), 7.26 (d, J = 7.9 Hz, 1H), 6.79 (d, J = 3.2 Hz, 1H), 6.50-6.31 (m, 2H), 3.48 (s, 2H), 2.31 (s, 3H), 2.19 (s, 6H). (ESI+) m/z 468 (M + H) + Retention time = 1.89 min (method 1)
172
4-[2-(3,5-Dimethoxy- phenylamino)-oxazol- 5-yl]-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.04 (s, 1H), 10.60 (s, 1H), 8.77 (s, 1H), 8.59 (d, J = 5.2 Hz, 1H), 8.45 (d, J = 5.3 Hz, 1H), 7.77 (s, 1H), 7.53 (m, 1H), 7.47 (d, J = 5.2 Hz, 1H), 6.90 (m, 2H), 6.41 (m, 1H), 6.16 (s, 1H), 3.74 (s, 6H). (ESI+) m/z 391 (M + H) + Retention time = 2.48 min (method 1)
173
4-{2-[3-(3- Dimethylamino- propoxy)-5-methoxy- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.05 (s, 1H), 10.58 (s, 1H), 8.77 (s, 1H), 8.60 (d, J = 5.0 Hz, 1H), 8.45 (d, J = 7.0 Hz, 1H), 7.77 (s, 1H), 7.55 (d, J = 5.9 Hz, 1H), 7.47 (d, J = 5.1 Hz, 1H), 6.91 (s, 1H), 6.87 (s, 1H), 6.41 (t, J = 6.3 Hz, 1H), 6.14 (s, 1H), 3.97 (t, J = 6.1 Hz, 2H), 3.73 (s, 3H), 2.35 (t, J = 7.0 Hz, 2H), 2.15 (s, 6H), 1.90-1.78 (m, 2H). (ESI+) m/z 462 (M + H) + Retention time = 1.76 min (method 1)
174
4-[2-(3-Bromo-5- pyrrolidin-1-ylmethyl- phenylamino)-oxazol- 5-yl]-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.04 (s, 1H), 10.85 (s, 1H), 8.79 (s, 1H), 8.61 (d, J = 5.0 Hz, 1H), 8.46 (d, J = 6.9 Hz, 1H), 7.89 (s, 1H), 7.80 (s, 1H), 7.61-7.43 (m, 3H), 7.10 (s, 1H), 6.42 (t, J = 6.5 Hz, 1H), 3.55 (s, 2H), 2.45 (s, 4H), 1.71 (s, 4H). (ESI+) m/z 492 (M + H) + Retention time = 1.85 min (method 1)
175
4-[2-(3-Methyl-5- pyrrolidin-1-ylmethyl- phenylamino)-oxazol- 5-yl]-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.03 (s, 1H), 10.51 (s, 1H), 8.77 (s, 1H), 8.59 (d, J = 5.2 Hz, 1H), 8.45 (d, J = 5.7 Hz, 1H), 7.76 (s, 1H), 7.55 (d, J = 4.5 Hz, 1H), 7.47 (d, J = 5.3 Hz, 1H), 7.41 (s, 1H), 7.38 (s, 1H), 6.75 (s, 1H), 6.41 (t, J = 6.6 Hz, 1H), 3.51 (s, 2H), 2.43 (s, 4H), 2.29 (s, 3H), 1.69 (s, 4H). (ESI+) m/z 428 (M + H) + Retention time = 1.70 min (method 1)
176
N-(2-Methoxy-ethyl)- 4,N-dimethyl-3-[5-(2′- oxo-1′,2′-dihydro- [2,3′]bipyridinyl-4-yl)- oxazol-2-ylamino]- benzamide
(300 MHz, DMSO-d 6 ) δ 12.01 (s, 1H), 9.73 (s, 1H), 8.74 (s, 1H), 8.59 (d, J = 5.3 Hz, 1H), 8.43 (d, J = 7.1 Hz, 1H), 7.95 (s, 1H), 7.73 (s, 1H), 7.55 (d, J = 4.8 Hz, 1H), 7.47 (d, J = 5.0 Hz, 1H), 7.26 (d, J = 7.6 Hz, 1H), 7.01 (d, J = 7.8 Hz, 1H), 6.41 (t, J = 6.3 Hz, 1H), 3.72-3.08 (m, 7H), 2.97 (s, 3H), 2.34 (s, 3H). (ESI+) m/z 460 (M + H) + Retention time = 2.14 min (method 1)
177
4-(2-{5-[(2-Methoxy- ethyl)-methyl-amino]- 2-methyl- phenylamino}-oxazol- 5-yl)-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.01 (s, 1H), 9.73 (s, 1H), 8.74 (s, 1H), 8.59 (d, J = 5.3 Hz, 1H), 8.43 (d, J = 7.1 Hz, 1H), 7.95 (s, 1H), 7.73 (s, 1H), 7.55 (d, J = 4.8 Hz, 1H), 7.47 (d, J = 5.0 Hz, 1H), 7.26 (d, J = 7.6 Hz, 1H), 7.01 (d, J = 7.8 Hz, 1H), 6.41 (t, J = 6.3 Hz, 1H), 3.64-3.08 (m, 7H), 2.97 (s, 3H), 2.34 (s, 3H). (ESI+) m/z 432 (M + H) + Retention time = 2.01 min (method 1)
178
4-[2-(2-Chloro-5- (methoxymethyl)- phenylamino)-oxazol- 5-yl]-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 12.01 (s, 1H), 9.93 (s, 1H), 8.75 (s, 1H), 8.60 (d, J = 5.2 Hz, 1H), 8.43 (dd, J = 7.1, 2.0 Hz, 1H), 8.06 (s, 1H), 7.74 (s, 1H), 7.54 (d, J = 5.3 Hz, 1H), 7.47 (d, J = 7.4 Hz, 2H), 7.06 (d, J = 8.2 Hz, 1H), 6.41 (t, J = 6.7 Hz, 1H), 4.43 (s, 2H), 3.31 (s, 3H). (ESI+) m/z 409 (M + H) + Retention time = 2.53 min (method 1)
179
1-{3-[2-((5- Methoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-phenyl}- tetrahydro-pyrimidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.32 (s, 1H), 7.88 (br s, 1H), 7.52 (br s, 1H), 7.43 (s, 1H), 7.35 (d, J = 4.2 Hz, 1H), 7.34 (s, 1H), 7.18 (s, 1H), 7.16 (s, 1H), 6.93 (dd, J = 7.9, 1.4 Hz, 1H), 6.64 (br s, 1H), 4.37 (s, 2H), 3.69-3.61 (m, 2H), 3.28 (s, 3H), 3.24 (t, J = 5.7 Hz, 2H), 2.28 (s, 3H), 1.96 (quint, J = 5.7 Hz, 2H). (ESI+) m/z 393 (M + H) + Retention time = 3.15 min (method 1)
180
4′,6′-Dimethyl-4-{2-[2- methyl-5- (ethoxymethyl)- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.53 (s, 1H), 9.39 (s, 1H), 8.57 (d, J = 5.3 Hz, 1H), 7.76 (s, 1H), 7.70 (s, 1H), 7.52 (s, 1H), 7.39 (dd, J = 5.3, 1.7 Hz, 1H), 7.18 (d, J = 7.6 Hz, 1H), 6.98 (d, J = 6.3 Hz, 1H), 5.98 (s, 1H), 4.42 (s, 2H), 3.49 (q, J = 7.0 Hz, 2H), 2.29 (s, 3H), 2.20 (s, 3H), 2.01 (s, 3H), 1.14 (t, J = 7.0 Hz, 3H). (ESI+) m/z 431 (M + H) + Retention time = 2.64 min (method 1)
181
4′,6′-Dimethyl-4-{2-[2- methyl-5-(2-morpholin- 4-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 1 H NMR (400 MHz, DMSO) δ 11.68 (s, 1H), 9.48 (s, 1H), 8.58 (d, J = 5.2 Hz, 1H), 7.77 (s, 1H), 7.59 (d, J = 2.2 Hz, 1H), 7.54 (s, 1H), 7.42 (dd, J = 5.2, 1.4 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.59 (dd, J = 8.3, 2.3 Hz, 1H), 6.00 (s, 1H), 4.04 (t, J = 5.6 Hz, 2H), 3.57 (t, J = 4.3 Hz, 4H), 2.67 (t, J = 5.5 Hz, 2H), 2.48-2.43 (m, 4H), 2.20 (d, J = 10.5 Hz, 6H), 1.99 (s, 3H). (ESI+) m/z 502 (M + H) + Retention time = 1.75 min (method 1)
182
4′-Methyl-4-{2-[2- methyl-5-(2-morpholin- 4-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 11.67 (s, 1H), 9.46 (s, 1H), 8.59 (d, J = 5.4 Hz, 1H), 7.78 (s, 1H), 7.59 (s, 1H), 7.55 (s, 1H), 7.43 (d, J = 5.1 Hz, 1H), 7.34 (d, J = 6.8 Hz, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.59 (d, J = 6.4 Hz, 1H), 6.18 (d, J = 6.7 Hz, 1H), 4.04 (t, J = 5.6 Hz, 2H), 3.64-3.50 (m, 4H), 2.67 (t, J = 5.6 Hz, 2H), 2.46 (s, 4H), 2.21 (s, 3H), 2.03 (s, 3H). (ESI+) m/z 488 (M + H) + Retention time = 1.65 min (method 1)
183
4-[2-(2-Chloro-5- ethoxymethyl- phenylamino)-oxazol- 5-yl]-4′-methyl-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 1 H NMR (400 MHz, DMSO) δ 11.69 (s, 1H), 9.84 (s, 1H), 8.61 (d, J = 5.2 Hz, 1H), 8.09 (d, J = 1.5 Hz, 1H), 7.82 (s, 1H), 7.56 (s, 1H), 7.50-7.43 (m, 2H), 7.35 (d, J = 6.6 Hz, 1H), 7.06 (dd, J = 8.2, 1.8 Hz, 1H), 6.19 (d, J = 6.7 Hz, 1H), 4.46 (s, 2H), 3.49 (q, J = 7.0 Hz, 2H), 2.03 (s, 3H), 1.15 (dd, J = 8.4, 5.5 Hz, 3H). (ESI+) m/z 437 (M + H) + Retention time = 2.73 min (method 1)
184
4-[2-(5-Ethoxymethyl- 2-methyl- phenylamino)-oxazol- 5-yl]-5′-methyl-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.82 (s, 1H), 9.61 (s, 1H), 8.76 (s, 1H), 8.58 (d, J = 5.2 Hz, 1H), 8.32 (d, J = 2.6 Hz, 1H), 7.79 (s, 1H), 7.70 (s, 1H), 7.45 (dd, J = 5.2, 1.6 Hz, 1H), 7.35 (s, 1H), 7.18 (d, J = 7.7 Hz, 1H), 6.98 (d, J = 7.7 Hz, 1H), 4.43 (s, 2H), 3.48 (q, J = 7.0 Hz, 2H), 2.29 (s, 3H), 2.13 (s, 3H), 1.14 (t, J = 7.0 Hz, 3H). (ESI+) m/z 417 (M + H) + Retention time = 2.16 min (method 1)
185
5′-Methyl-4-{2-[2- methyl-5-(2-morpholin- 4-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.84 (s, 1H), 9.55 (s, 1H), 8.76 (s, 1H), 8.58 (d, J = 5.2 Hz, 1H), 8.31 (d, J = 2.7 Hz, 1H), 7.71 (s, 1H), 7.55 (d, J = 2.4 Hz, 1H), 7.45 (dd, J = 5.2, 1.5 Hz, 1H), 7.34 (s, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.60 (dd, J = 8.3, 2.4 Hz, 1H), 4.05 (t, J = 5.7 Hz, 2H), 3.58-3.54 (m, 4H), 2.68 (t, J = 5.7 Hz, 2H), 2.49-2.40 (m, 4H), 2.23 (s, 3H), 2.12 (s, 3H). (ESI+) m/z 488 (M + H) + Retention time = 1.78 min (method 1)
186
4-[2-((5- Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-6′-methyl- 1′H-[2,3′]bipyridinyl- 2′-one
(400 MHz, DMSO) δ 11.95 (s, 1H), 9.60 (s, 1H), 8.73 (s, 1H), 8.55 (d, J = 5.1 Hz, 1H), 8.36 (d, J = 7.3 Hz, 1H), 7.77 (s, 1H), 7.68 (s, 1H), 7.41 (d, J = 5.1 Hz, 1H), 7.18 (d, J = 7.6 Hz, 1H), 6.97 (d, J = 7.6 Hz, 1H), 6.22 (d, J = 7.2 Hz, 1H), 4.42 (s, 2H), 3.47 (q, J = 7.0 Hz, 2H), 2.29 (s, 2H), 2.27 (s, 3H), 1.13 (t, J = 6.9 Hz, 3H). (ESI+) m/z 417 (M + H) + Retention time = 2.71 min (method 1)
187
1-{3-[2-((5- Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-phenyl}- tetrahydro-pyrimidin-2- one
(300 MHz, DMSO-d 6 ) δ 9.26 (s, 1H), 7.86 (s, 1H), 7.53 (s, 1H), 7.47-7.25 (m, 3H), 7.17 (s, 1H), 7.15 (s, 1H), 6.93 (d, J = 7.2 Hz, 1H), 6.65 (s, 1H), 4.41 (s, 2H), 3.65 (t, J = 6.5 Hz, 2H), 3.47 (q, J = 6.9 Hz, 2H), 3.24 (br t, J = 6.3 Hz, 2H), 2.28 (s, 3H), 2.04-1.84 (m, 2H), 1.15 (t, J = 7.0 Hz, 3H). (ESI+) m/z 407 (M + H) + Retention time = 3.41 min (method 1)
188
6′-Methyl-4-{2-[2- methyl-5-(2-morpholin- 4-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.98 (s, 1H), 9.57 (s, 1H), 8.74 (s, 1H), 8.55 (d, J = 5.2 Hz, 1H), 8.36 (d, J = 7.3 Hz, 1H), 7.70 (s, 1H), 7.55 (s, 1H), 7.42 (dd, J = 5.1, 1.6 Hz, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.60 (d, J = 8.3 Hz, 1H), 6.22 (d, J = 7.3 Hz, 1H), 4.05 (t, J = 5.6 Hz, 2H), 3.60-3.51 (m, 4H), 2.67 (t, J = 5.7 Hz, 2H), 2.45 (s, 4H), 2.27 (s, 3H), 2.23 (s, 3H). (ESI+) m/z 488 (M + H) + Retention time = 1.74 min (method 1)
189
4-[2-(2-Chloro-(5- ethoxymethyl)- phenylamino)-oxazol- 5-yl]-6′-methyl-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 1 H NMR (400 MHz, DMSO) δ 11.95 (s, 1H), 9.90 (s, 1H), 8.75 (s, 1H), 8.57 (d, J = 5.2 Hz, 1H), 8.36 (d, J = 7.3 Hz, 1H), 8.04 (s, 1H), 7.72 (s, 1H), 7.53-7.38 (m, 2H), 7.07 (dd, J = 8.1, 1.7 Hz, 1H), 6.22 (d, J = 7.2 Hz, 1H), 4.47 (s, 2H), 3.50 (q, J = 7.0 Hz, 2H), 2.27 (s, 3H), 1.15 (t, J = 7.0 Hz, 3H). (ESI+) m/z 437 (M + H) + Retention time = 2.89 min (method 1)
190
6′-Chloro-4-{2-[5-(2- dimethylamino- ethoxy)-2-methyl- phenylamino]-oxazol- 5-yl}-1′-methyl-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 9.59 (s, 1H), 8.65 (s, 1H), 8.60 (d, J = 5.2 Hz, 1H), 8.37 (d, J = 8.0 Hz, 1H), 7.75 (s, 1H), 7.57 (br s, 1H), 7.49 (d, J = 4.5 Hz, 1H), 7.09 (d, J = 8.2 Hz, 1H), 6.73 (d, J = 7.9 Hz, 1H), 6.60 (br d, J = 6.3 Hz, 1H), 4.01 (t, J = 5.6 Hz, 2H), 3.71 (s, 3H), 2.62 (t, J = 5.4 Hz, 2H), 2.23 (s, 3H), 2.21 (s, 6H). (ESI+) m/z 480 (M + H) + Retention time = 1.94 min (method 1)
191
4-{2-[2-Methyl-5-(2- pyrrolidin-1-yl- propyloxy)- phenylamino]-oxazol- 5-yl}-2-(2-oxo-1,2- dihydro-pyridin-3-yl)- benzoic acid ethyl ester
(300 MHz, DMSO-d 6 ) δ 11.72 (s, 1H), 9.35 (s, 1H), 7.81 (dd, J = 8.1, 3.6 Hz, 1H), 7.70-7.57 (m, 3H), 7.52 (brs, 1H), 7.50 (brs, 1H), 7.40 (d, J = 4.3 Hz, 1H), 7.07 (d, J = 8.1 Hz, 1H), 6.55 (d, J = 8.1 Hz, 1H), 6.29 (t, J = 6.7 Hz, 1H), 4.07 (q, J = 7.3 Hz, 2H), 3.97 (t, J = 6.2 Hz, 2H), 3.54- 3.34 (m, 2H), 2.43 (s, 4H), 2.22 (s, 3H), 1.94- 1.79 (m, 2H), 1.67 (s, 4H), 1.09 (t, J = 7.3 Hz, 3H). (ESI+) m/z 543 (M + H) + Retention time = 2.82 min (method 1)
192
2-Dimethylamino-N- (3-{5-[4-methyl-3-(2- oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- oxazol-2-ylamino}- phenyl)-acetamide
(300 MHz, DMSO-d 6 ) δ 11.78 (s, 1H), 9.63 (s, 1H), 9.16 (s, 1H), 8.11 (s, 1H), 7.54-7.17 (m, 7H), 7.09 (d, J = 8.5 Hz, 1H), 6.28 (t, J = 6.6 Hz, 1H), 3.04 (s, 2H), 2.27 (s, 6H), 2.23 (s, 3H), 2.16 (s, 3H). (ESI+) m/z 458 (M + H) + Retention time = 2.42 min (method 1)
193
3-{5-[2-(5-Methoxy-2- methyl-phenylamino)- oxazol-5-yl]-2-methyl- phenyl}-1H-pyridin-2- one
(300 MHz, DMSO-d6) δ 11.79 (s, 1H), 9.16 (s, 1H), 7.66 (d, J = 2.5 Hz, 1H), 7.51-7.36 (m, 5H), 7.28 (d, J = 7.9 Hz, 1H), 7.07 (d, J = 8.6 Hz, 1H), 6.53 (dd, J = 8.4, 2.6 Hz, 1H), 6.29 (t, J = 6.5 Hz, 1H), 3.72 (s, 3H), 2.21 (s, 3H), 2.16 (s, 3H). (ESI+) m/z 388 (M + H) + Retention time = 3.50 min (method 1)
194
4-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-4′-methyl-6-(2- morpholin-4-yl- ethoxy)-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.64 (s, 1H), 10.29 (s, 1H), 7.77 (s, 1H), 7.33 (d, J = 6.7 Hz, 1H), 7.26 (s, 2H), 7.23 (d, J = 1.1 Hz, 1H), 6.83 (d, J = 1.2 Hz, 1H), 6.63 (s, 1H), 6.17 (d, J = 6.7 Hz, 1H), 4.36 (t, J = 5.8 Hz, 2H), 3.65-3.47 (m, 4H), 2.69 (t, J = 5.8 Hz, 2H), 2.49-2.39 (m, 4H), 2.25 (s, 6H), 2.09 (s, 3H). (ESI+) m/z 502 (M + H) + Retention time = 2.94 min (method 1)
195
4-{2-[2-Methyl-5-(1- methyl-piperidin-4- yloxymethyl)- phenylamino]-oxazol- 5-yl}-1′H- [2,3′]bipyridinyl-2′-one
(300 MHz, DMSO-d 6 ) δ 12.03 (s, 1H), 9.60 (s, 1H), 8.73 (s, 1H), 8.58 (d, J = 5.1 Hz, 1H), 8.43 (d, J = 7.3 Hz, 1H), 7.78 (s, 1H), 7.69 (s, 1H), 7.55 (br d, J = 5.3 Hz, 1H), 7.45 (d, J = 4.6 Hz, 1H), 7.18 (d, J = 7.5 Hz, 1H), 6.98 (d, J = 7.3 Hz, 1H), 6.41 (t, J = 6.4 Hz, 1H), 4.47 (s, 2H), 2.69- 2.58 (m, 2H), 2.29 (s, 3H), 2.16 (s, 3H), 2.11- 1.96 (m, 2H), 1.92-1.76 (m, 2H), 1.60-1.41 (m, 2H). (ESI+) m/z 472 (M + H) + Retention time = 1.76 min (method 1)
196
4-[2-(5-Methoxy-2- methyl-phenylamino)- oxazol-5-yl]-4′-methyl- 6-(2-morpholin-4-yl- ethoxy)-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.63 (s, 1H), 9.40 (s, 1H), 7.75 (s, 1H), 7.57 (d, J = 2.5 Hz, 1H), 7.33 (d, J = 6.7 Hz, 1H), 7.21 (d, J = 0.9 Hz, 1H), 7.10 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 0.8 Hz, 1H), 6.59 (dd, J = 8.3, 2.6 Hz, 1H), 6.17 (d, J = 6.7 Hz, 1H), 4.35 (t, J = 5.8 Hz, 2H), 3.73 (s, 3H), 3.63- 3.48 (m, 4H), 2.69 (t, J = 5.8 Hz, 2H), 2.49- 2.43 (m, 4H), 2.22 (s, 3H), 2.07 (s, 3H). (ESI+) m/z 518 (M + H) + Retention time = 2.64 min (method 1)
197
4-[2-((5- Methoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-4′-methyl- 6-(2-morpholin-4-yl- ethoxy)-1′H- [2,3′]bipyridinyl-2′-one
(400 MHz, DMSO-d 6 ) δ 11.62 (s, 1H), 9.44 (s, 1H), 7.82 (s, 1H), 7.74 (s, 1H), 7.33 (d, J = 6.7 Hz, 1H), 7.19 (s, 1H), 7.19-7.15 (m, 1H), 6.95 (d, J = 7.5 Hz, 1H), 6.83 (s, 1H), 6.17 (d, J = 6.7 Hz, 1H), 4.41-4.28 (m, 4H), 3.61-3.52 (m, 4H), 3.27 (s, 3H), 2.68 (t, J = 5.7 Hz, 2H), 2.48- 2.42 (m, 4H), 2.28 (s, 3H), 2.07 (s, 3H). (ESI+) m/z 532 (M + H) + Retention time = 2.656 min (method 1)
198
1-{4-[2-((5- Ethoxymethyl)-2- methyl-phenylamino)- oxazol-5-yl]-pyridin-2- yl}-tetrahydro- pyrimidin-2-one
(300 MHz, DMSO) δ 9.54 (s, 1H), 8.28 (d, J = 5.2 Hz, 1H), 7.99 (s, 1H), 7.79 (s, 1H), 7.66 (s, 1H), 7.24-7.10 (m, 2H), 7.00-6.86 (m, 2H), 4.41 (s, 2H), 3.92-3.80 (m, 2H), 3.47 (q, J = 6.9 Hz, 2H), 3.26-3.19 (m, 2H), 2.27 (s, 3H), 2.03- 1.80 (m, 2H), 1.14 (t, J = 7.0 Hz, 3H). (ESI+) m/z 408 (M + H) + Retention time = 2.78 min (method 1)
199
3-[3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-(2-methoxy- ethoxy)-phenyl]-4- methyl-1H-pyridin-2- one hydrochloride
1H NMR (400 MHz, DMSO) δ 11.57 (br s, 1H), 10.21 (s, 1H), 7.52 (s, 1H), 7.29 (d, J = 6.8 Hz, 1H), 7.25 (s, 2H), 7.09 (s, 1H), 7.02 (s, 1H), 6.67 (s, 1H), 6.61 (s, 1H), 6.17 (d, J = 6.7 Hz, 1H), 4.41 (br s, 1H), 4.19-4.11 (m, 2H), 3.74-3.63 (m, 2H), 3.33 (s, 3H), 2.25 (s, 6H), 2.03 (s, 3H) (ESI+) m/z 446 (M + H) + Retention time = 3.95 min (method 1)
200
3-[3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-(2-hydroxy- ethoxy)-phenyl]-4- methyl-1H-pyridin-2- one hydrochloride
1H NMR (400 MHz, DMSO) δ 11.53 (br s, 1H), 10.21 (s, 1H), 7.51 (s, 1H), 7.29 (d, J = 6.4 Hz, 1H), 7.25 (s, 2H), 7.09 (s, 1H), 7.02 (s, 1H), 6.66 (s, 1H), 6.62 (s, 1H), 6.18 (d, J = 6.3 Hz, 1H), 4.07-4.04 (m, 2H), 3.98 (br s, 1H), 3.79-3.71 (m, 2H), 2.28 (s, 6H), 2.03 (s, 3H). (ESI+) m/z 432 (M + H) + Retention time = 3.50 min (method 1)
201
3-{3-[2-(3,5-Difluoro- phenylamino)-oxazol- 5-yl]-5-methoxy- phenyl}-4-methyl-1H- pyridin-2-one
1H NMR (400 MHz, DMSO) δ 11.54 (s, 1H), 10.83 (s, 1H), 7.55 (s, 1H), 7.34 (d, J = 9.1 Hz, 2H), 7.28 (d, J = 5.9 Hz, 1H), 7.07 (s, 1H), 7.04 (s, 1H), 6.76 (t, J = 9.3 Hz, 1H), 6.67 (s, 1H), 6.16 (d, J = 5.1 Hz, 1H), 3.81 (s, 3H), 2.01 (s, 3H).
202
3-[3-[2-(3,5-Dimethyl- phenylamino)-oxazol- 5-yl]-5-(3-hydroxy- propoxy)-phenyl]-4- methyl-1H-pyridin-2- one
1 H NMR (400 MHz, DMSO) δ 11.53 (s, 1H), 10.10 (s, 1H), 7.48 (s, 1H), 7.34-7.21 (m, 3H), 7.07 (s, 1H), 7.01 (s, 1H), 6.64 (s, 1H), 6.60 (s, 1H), 6.16 (d, J = 6.7 Hz, 1H), 4.56 (t, J = 5.1 Hz, 1H), 4.09 (t, J = 6.3 Hz, 2H), 3.59 (dd, J = 11.5, 6.0 Hz, 2H), 2.27 (s, 6H), 2.01 (s, 3H), 1.95- 1.82 (m, 2H). (ESI+) m/z 446 (M + H) + Retention time = 3.63 min (method 1)
203
3-{3-(3-Amino- propoxy)-5-[2-(3,5- dimethyl- phenylamino)-oxazol- 5-yl]-phenyl}-4- methyl-1H-pyridin-2- one
1 H NMR (400 MHz, DMSO) δ 11.57 (s, 1H), 10.15 (s, 1H), 7.49 (s, 1H), 7.37-7.20 (m, 3H), 7.09 (s, 1H), 7.04 (s, 1H), 6.69 (s, 1H), 6.60 (s, 1H), 6.17 (d, J = 6.6 Hz, 1H), 4.22-4.02 (m, 2H), 3.10-3.03 (m, 2H), 2.22 (s, 6H), 2.02 (s, 3H), 1.85-1.70 (m, 2H).
204
2-Methyl-propane-1- sulfonic acid [3-[2-(3- methyl-(5-morpholin-4- ylmethyl)- phenylamino)-oxazol- 5-yl]-5-(4-methyl-2- oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- amide
1 H NMR (400 MHz, DMSO) δ 11.59 (s, 1H), 10.25 (s, 1H), 9.91 (s, 1H), 7.46 (s, 1H), 7.44- 7.34 (m, 3H), 7.31 (d, J = 6.5 Hz, 1H), 7.22 (s, 1H), 6.90 (s, 1H), 6.74 (s, 1H), 6.18 (d, J = 6.7 Hz, 1H), 3.66-3.52 (m, 4H), 3.41 (s, 2H), 3.04 (d, J = 6.4 Hz, 2H), 2.43-2.32 (m, 4H), 2.29 (s, 3H), 2.21-2.14 (m, 1H), 2.01 (s, 3H), 1.03 (d, J = 9.2 Hz, 6H). (ESI+) m/z 592 (M + H) + Retention time = 2.77 min (method 1)
205
2-Methyl-propane-1- sulfonic acid [3-[2- (3,5-dimethoxy- phenylamino)-oxazol- 5-yl]-5-(4-methyl-2- oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- amide
1 H NMR (400 MHz, DMSO) δ 11.58 (s, 1H), 10.31 (s, 1H), 9.92 (s, 1H), 7.46 (s, 1H), 7.36 (s, 1H), 7.30 (d, J = 6.8 Hz, 1H), 7.20 (s, 1H), 6.93- 6.85 (m, 3H), 6.18 (d, J = 6.8 Hz, 1H), 6.14 (t, J = 2.2 Hz, 1H), 3.73 (s, 6H), 3.03 (d, J = 6.4 Hz, 2H), 2.19-2.11 (m, 1H), 2.02 (s, 3H), 1.01 (d, J = 6.7 Hz, 6H). (ESI+) m/z 539 (M + H) + Retention time = 3.72 min (method 1)
206
2-Methyl-propane-1- sulfonic acid [3-[2- (3,5-dimethyl- phenylamino)-oxazol- 5-yl]-5-(4-methyl-2- oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- amide
1 H NMR (400 MHz, DMSO) δ 11.62 (s, 1H), 10.22 (s, 1H), 9.94 (s, 1H), 7.46 (s, 1H), 7.39- 7.34 (m, 1H), 7.31 (d, J = 6.7 Hz, 1H), 7.29- 7.24 (m, 2H), 7.21 (s, 1H), 6.88 (s, 1H), 6.61 (s, 1H), 6.18 (d, J = 6.7 Hz, 1H), 3.03 (d, J = 6.3 Hz, 2H), 2.22 (s, 6H), 2.17-2.11 (m, 1H), 2.01 (s, 3H), 1.03 (d, J = 6.9 Hz, 6H). (ESI+) m/z 507 (M + H) + Retention time = 4.10 min (method 1)
207
3-[3-[2-(2,3-Dimethyl- phenylamino)-oxazol- 5-yl]-5-(2-methoxy- ethoxy)-phenyl]-4- methyl-1H-pyridin-2- one
1 H NMR (400 MHz, DMSO) δ 11.55 (s, 1H), 9.19 (s, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.41 (s, 1H), 7.28 (d, J = 6.7 Hz, 1H), 7.13-7.02 (m, 2H), 6.98 (s, 1H), 6.93 (d, J = 7.5 Hz, 1H), 6.63 (s, 1H), 6.16 (d, J = 6.7 Hz, 1H), 4.19-4.08 (m, 2H), 3.73-3.63 (m, 2H), 3.33 (s, 4H), 2.26 (s, 3H), 2.16 (s, 3H), 2.01 (s, 3H). (ESI+) m/z 446 (M + H) + Retention time = 3.56 min (method 1)
208
3-{5-[3-(2-Methoxy- ethoxy)-5-(4-methyl-2- oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- oxazol-2-ylamino}-5- methyl-benzonitrile hydrochloride
1H NMR (400 MHz, DMSO) δ 11.64 (br s, 1H), 10.74 (s, 1H), 7.92 (s, 1H), 7.70 (s, 1H), 7.57 (s, 1H), 7.30 (d, J = 6.7 Hz, 1H), 7.25 (s, 1H), 7.11 (d, J = 2.2 Hz, 1H), 7.04 (s, 1H), 6.69 (d, J = 1.2 Hz, 1H), 6.18 (d, J = 6.8 Hz, 1H), 5.12 (br s, 1H), 4.29-4.05 (m, 2H), 3.78-3.60 (m, 2H), 2.35 (s, 3H), 2.03 (s, 3H). (ESI+) m/z 457 (M + H) + Retention time = 3.77 min (method 1)
209
3-{5-[3-(2-Methoxy- ethoxy)-5-(4-methyl-2- oxo-1,2-dihydro- pyridin-3-yl)-phenyl]- oxazol-2-ylamino}-5- methyl-benzamide
1 H NMR (400 MHz, DMSO) δ 11.55 (s, 1H), 10.32 (s, 1H), 7.89 (s, 1H), 7.86-7.78 (m, 1H), 7.62 (s, 1H), 7.52 (s, 1H), 7.35-7.20 (m, 3H), 7.11 (s, 1H), 7.03 (s, 1H), 6.66 (s, 1H), 6.17 (d, J = 6.6 Hz, 1H), 4.23-4.10 (m, 2H), 3.74-3.65 (m, 2H), 3.34 (s, 3H), 2.35 (s, 3H), 2.03 (s, 3H). (ESI+) m/z 475 (M + H) + Retention time = 2.91 min (method 1)
210
4-Methyl-5′-{2-[2- methyl-5-(2-morpholin- 4-yl-ethoxy)- phenylamino]-oxazol- 5-yl}-1H- [3,3′]bipyridinyl-2-one
1H NMR (400 MHz, DMSO) δ 11.68 (s, 1H), 9.30 (s, 1H), 8.76 (s, 1H), 8.29 (s, 1H), 7.84 (s, 1H), 7.61 (s, 2H), 7.34 (d, J = 6.6 Hz, 1H), 7.07 (d, J = 8.3 Hz, 1H), 6.57 (d, J = 8.2 Hz, 1H), 6.22 (d, J = 6.7 Hz, 1H), 4.04 (t, J = 5.5 Hz, 2H), 3.64- 3.52 (m, 4H), 2.68 (t, J = 5.4 Hz, 2H), 2.46 (s, 4H), 2.22 (s, 3H), 2.06 (s, 3H). (ESI+) m/z 488 (M + H) + Retention time = 2.04 min (method 1)
211
3-{3-[2-(5-Methoxy-2- methyl-phenylamino)- thiazol-5-yl]-phenyl}- 4-methyl-1H-pyridin-2- one
1H NMR (400 MHz, DMSO) δ 11.53 (s, 1H), 9.35 (s, 1H), 7.64 (s, 1H), 7.57 (d, J = 2.4 Hz, 2H), 7.45-7.35 (m, 2H), 7.32 (s, 1H), 7.27 (d, J = 6.8 Hz, 1H), 7.11 (d, J = 8.3 Hz, 1H), 7.06 (d, J = 7.3 Hz, 1H), 6.59 (dd, J = 8.4, 2.7 Hz, 1H), 6.16 (d, J = 6.7 Hz, 1H), 3.71 (s, 3H), 2.20 (s, 3H), 2.00 (s, 3H). (ESI+) m/z 404 (M + H) + Retention time = 3.49 min (method 1)
212
3-{3-[2-(2,3-Dimethyl- (5-morpholin-4- ylmethyl)- phenylamino)-oxazol- 5-yl]-5-methoxy- phenyl}-4-methyl-1H- pyridin-2-one
1 H NMR (400 MHz, DMSO) δ 11.56 (s, 1H), 9.22 (s, 1H), 7.51 (s, 1H), 7.43 (s, 1H), 7.28 (d, J = 6.8 Hz, 1H), 7.04 (s, 1H), 6.97 (d, J = 1.2 Hz, 1H), 6.87 (s, 1H), 6.69-6.57 (m, 1H), 6.16 (d, J = 6.7 Hz, 1H), 3.80 (s, 3H), 3.63-3.48 (m, 4H), 3.36 (s, 2H), 2.41-2.27 (m, 4H), 2.25 (s, 3H), 2.14 (s, 3H), 2.01 (s, 3H). (ESI+) m/z 501 (M + H) + Retention time = 2.74 min (method 1)
213
4-[2-(2,3-Dimethyl-5- (morpholin-4- ylmethyl)- phenylamino)-oxazol- 5-yl]-4′,6′-dimethyl- 1′H-[2,3′]bipyridinyl- 2′-one
1 H NMR (400 MHz, DMSO) δ 11.67 (s, 1H), 9.51 (s, 1H), 8.55 (d, J = 5.3 Hz, 1H), 7.72 (s, 1H), 7.45 (d, J = 8.3 Hz, 2H), 7.36 (dd, J = 5.2, 1.6 Hz, 1H), 6.91 (s, 1H), 5.99 (s, 1H), 3.60- 3.49 (m, 4H), 3.37 (s, 2H), 2.41-2.29 (m, 4H), 2.25 (s, 3H), 2.18 (s, 3H), 2.13 (s, 3H), 1.99 (s, 3H). (ESI+) m/z 486 (M + H) + Retention time = 1.82 min (method 1)
[0082] In one embodiment, which can be combined with other embodiments of the invention, the invention relates to compounds of formula I or pharmaceutically acceptable salts thereof wherein:
[0083] Ri is H or a (C 1 -C 6 )alkyl;
[0084] R 2 is H;
a halogen; COOH; a (C 1 -C 6 )alkyl optionally substituted by a group —NR 10 R 11 , by OH or by a (C 1 -C 4 )alkoxy optionally substituted by OH where R 10 and R 11 are each independently H or (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino or di(C 1 -C 4 )alkylamino; or R 10 and R 11 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine; a (C 1 -C 6 )alkoxy optionally substituted by OH, a (C 1 -C 4 )alkoxy or a group —NR 12 R 13 where R 12 and R 13 are each independently H or (C 1 -C 4 )alkyl; or R 12 and R 13 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; a group —OR 14 where R 14 is a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; a group —CONR 15 R 16 where R 15 and R 16 are each independently H or a (C 1 -C 4 )alkyl optionally substituted with a (C 1 -C 4 )alkoxy or with a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular morpholine; or R 15 and R 16 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine; a group —NR 17 R 18 where R 17 is H or (C 1 -C 4 )alkyl and R 18 is H; a (C 1 -C 4 )alkyl optionally substituted with a (C 1 -C 4 )alkoxy; or a 5- or 6-membered heteroaryl containing 1 to 3 heteroatoms selected from O, S and N, in particular pyridine, pyrimidine and thiazole; a group —NR 19 COR 20 where R 19 is H or (C 1 -C 4 )alkyl and R 20 is H or a (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino or di(C 1 -C 4 )alkylamino or with a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; or a 5- or 6-membered heterocycloalkyl or heteroaryl containing 1 or 2 heteroatoms selected from O and N, in particular piperidine and furane, said heterocycloalkyl or heteroaryl being optionally substituted with an oxo group or with a (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino or di(C 1 -C 4 )alkylamino;
[0094] R 3 is H; cyano; CF 3 ; a halogen; a (C 1 -C 4 )alkyl; or a (C 1 -C 4 )alkoxy;
[0095] Q is O or S, preferably Q is O;
[0096] W is N or CR 21 where R 21 is
H; a halogen; CN; CF 3 ; OCF 3 ; a (C 1 -C 4 )alkyl optionally substituted with a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O and N, in particular pyrrolidine, piperidine, piperazine and morpholine; a (C 1 -C 4 )alkoxy; a group —O(CH 2 ) n R 22 where n is 0, 1, 2 or 3 and R 22 is H; a (C 1 -C 4 )alkoxy; a group —NR 22a R 22b where R 22a and R 22b are each independently H or a (C 1 -C 4 )alkyl; or a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; a group —NR 23 R 24 where R 23 and R 24 are each independently H or a (C 1 -C 4 )alkyl optionally substituted with a (C 1 -C 4 )alkoxy; R 24 can also represent a group —SO 2 (C 1 -C 4 )alkyl; or R 23 and R 24 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl or heteroaryl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine, morpholine and pyrazole, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls;
[0106] X is N or CR 25 where R 25 is H; CN; a (C 1 -C 4 )alkyl; or a group —COO(C 1 -C 4 )alkyl; and
[0107] A is a 5- or 6-membered heterocycloalkyl or heteroaryl containing 1 to 3 heteroatoms selected from O and N, in particular piperidine, piperazine, pyrrolidine, morpholine, imidazolidine, dihydroimidazole, triazole, dihydropyridine and tetrahydropyridine, said heterocycloalkyl or heteroaryl being optionally substituted with 1 to 3 substituents selected from: an oxo group; a halogen; a (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino, di(C 1 -C 4 )alkylamino or a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O and N, in particular piperidine; and a (C 1 -C 4 )alkoxy. Within this family of compounds those where R 2 , R 3 and W are as defined below are preferred:
[0108] R 2 is H;
a halogen; a (C 1 -C 6 )alkyl optionally substituted by a group —NR 10 R 11 or by a (C 1 -C 4 )alkoxy optionally substituted by OH where R 10 and R 11 are each independently H or (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino or di(C 1 -C 4 )alkylamino; or R 10 and R 11 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine; a (C 1 -C 6 )alkoxy optionally substituted by OH, a (C 1 -C 4 )alkoxy or a group —NR 12 R 13 where R 12 and R 13 are each independently H or (C 1 -C 4 )alkyl; or R 12 and R 13 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; a group —OR 14 where R 14 is a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; a group —CONR 15 R 16 where R 15 and R 16 are each independently H or a (C 1 -C 4 )alkyl optionally substituted with a (C 1 -C 4 )alkoxy; or R 15 and R 16 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine; a group —NR 17 R 18 where R 17 is H or (C 1 -C 4 )alkyl and R 18 is H; a (C 1 -C 4 )alkyl optionally substituted with a (C 1 -C 4 )alkoxy; or a 5- or 6-membered heteroaryl containing 1 to 3 heteroatoms selected from O and N, in particular pyridine; a group —NR 19 COR 20 where R 19 is H or (C 1 -C 4 )alkyl and R 20 is H or a (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino or di(C 1 -C 4 )alkylamino or with a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; or a 5- or 6-membered heterocycloalkyl or heteroaryl containing 1 or 2 heteroatoms selected from O and N, in particular piperidine and furane, said heterocycloalkyl or heteroaryl being optionally substituted with an oxo group or with a (C 1 -C 4 )alkyl optionally substituted with amino, (C 1 -C 4 )alkylamino or di(C 1 -C 4 )alkylamino;
[0117] R 3 is H; CF 3 ; a halogen; a (C 1 -C 4 )alkyl; or a (C 1 -C 4 )alkoxy;
[0118] W is N or CR 21 where R 21 is
H; a halogen; CN; CF 3 ; OCF 3 ; a (C 1 -C 4 )alkyl optionally substituted with a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O and N, in particular pyrrolidine, piperidine, piperazine and morpholine; a (C 1 -C 4 )alkoxy; a group —O(CH 2 ) n R 22 where n is 0, 1 or 2 and R 22 is a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O and N, in particular pyrrolidine, piperidine, piperazine and morpholine, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls; a group —NR 23 R 24 where R 23 and R 24 are each independently H or a (C 1 -C 4 )alkyl optionally substituted with a (C 1 -C 4 )alkoxy; or R 23 and R 24 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl or heteroaryl containing 1 or 2 heteroatoms selected from O, S and N, in particular pyrrolidine, piperidine, piperazine, morpholine and pyrazole, said heterocycloalkyl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls.
[0128] In another embodiment, which can be combined with other embodiments of the invention, compounds of formula I or pharmaceutically acceptable salts thereof are contemplated wherein:
[0129] R 1 is H or a (C 1 -C 4 )alkyl;
[0130] R 2 is H; a (C 1 -C 4 )alkyl optionally substituted by a (C 1 -C 4 )alkoxy; a (C 1 -C 4 )alkoxy optionally substituted by OH or a group —NR 12 R 13 where R 12 and R 13 are each independently H or (C 1 -C 4 )alkyl or R 12 and R 13 form, together with the nitrogen atom to which they are bonded, a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O, and N, in particular morpholine; or a group —CONR 15 R 16 where R 15 and R 16 are each independently H or a (C 1 -C 4 )alkyl;
[0131] R 3 is H or a (C 1 -C 4 )alkyl;
[0132] Q is O;
[0133] W is N or CR 21 where R 21 is H; OCF 3 ; a (C 1 -C 4 )alkyl; a (C 1 -C 4 )alkoxy; or a group —O(CH 2 ) n R 22 where n is 0, 1 or 2, preferably n is 2, and R 22 is a 5- or 6-membered heterocycloalkyl containing 1 or 2 heteroatoms selected from O and N, in particular morpholine;
[0134] X is N or CH; and
[0135] A is a 5- or 6-membered heterocycloalkyl or heteroaryl containing 1 or 2 nitrogen atoms, in particular imidazolidine and dihydropyridine, said heterocycloalkyl or heteroaryl being optionally substituted with 1 to 3 (C 1 -C 4 )alkyls.
[0136] Preferred compounds of the invention are selected from those of examples 1 to 225 and pharmaceutically acceptable salts thereof.
[0137] The following compounds are especially preferred:
1-{4-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-pyridin-2-yl}-imidazolidin-2-one; 1-{3-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-5-methoxy-phenyl}-4,4-dimethyl-imidazolidin-2-one; 1-(3-{2-[5-(2-Hydroxy-ethoxy)-2-methyl-phenylamino]-oxazol-5-yl}-5-methyl-phenyl)-imidazolidin-2-one; 1-(4-{2-[5-(2-Hydroxy-ethoxy)-2-methyl-phenylamino]-oxazol-5-yl}-pyridin-2-yl)-imidazolidin-2-one; 1-(4-{2-[2-Methyl-5-(2-morpholin-4-yl-ethoxy)-phenylamino]-oxazol-5-yl}-pyridin-2-yl)-imidazolidin-2-one; 1-[4-[2-((5-Methoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-pyridin-2-yl]-4-methyl-imidazolidin-2-one; 4-Methyl-1-(4-{2-[2-methyl-5-(2-morpholin-4-yl-ethoxy)-phenylamino]-oxazol-5-yl}-pyridin-2-yl)-imidazolidin-2-one; 1-(3-Methyl-5-{2-[2-methyl-5-(2-morpholin-4-yl-ethoxy)-phenylamino]-oxazol-5-yl}-phenyl)-imidazolidin-2-one; 1-(4-{2-[2-Methyl-5-(3-morpholin-4-yl-propoxy)-phenylamino]-oxazol-5-yl}-pyridin-2-yl)-imidazolidin-2-one; 1-{3-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-5-methoxy-phenyl}-imidazolidin-2-one; 1-(3-Methoxy-5-{2-[2-methyl-5-(2-morpholin-4-yl-ethoxy)-phenylamino]-oxazol-5-yl}-phenyl)-imidazolidin-2-one; 1-{3-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-5-methoxy-phenyl}-4-methyl-imidazolidin-2-one; 1-{3-tert-Butoxy-5-[2-((5-methoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-phenyl}-imidazolidin-2-one; 1-(3-{2-[5-(2-Hydroxy-ethoxy)-2-methyl-phenylamino]-oxazol-5-yl}-5-methoxy-phenyl)-imidazolidin-2-one; 1-(3-Methoxy-5-{2-[2-methyl-5-(2-morpholin-4-yl-ethoxy)-phenylamino]-oxazol-5-yl}-phenyl)-4-methyl-imidazolidin-2-one; 1-{3-Isopropoxy-5-[2-((5-methoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-phenyl}-imidazolidin-2-one; 1-(3-{2-[5-(2-Hydroxy-ethoxy)-2-methyl-phenylamino]-oxazol-5-yl}-5-isopropoxy-phenyl)-imidazolidin-2-one; 1-(3-Isopropoxy-5-{2-[5-(2-methoxy-ethyl)-2-methyl-phenylamino]-oxazol-5-yl}-phenyl)-imidazolidin-2-one; 1-(3-(2-(2-methyl-5-(2-morpholinoethoxy)phenylamino)oxazol-5-yl)-5-(trifluoromethoxy)phenyl)imidazolidin-2-one; 1-(3-(2-(5-methoxy-2-methylphenylamino)oxazol-5-yl)-5-(trifluoromethoxy)phenyl)imidazolidin-2-one; 1-(3-{2-[5-(2-Hydroxy-ethoxymethyl)-2-methyl-phenylamino]-oxazol-5-yl}-5-methyl-phenyl)-imidazolidin-2-one; 3-{5-[3-Isopropoxy-5-(2-oxo-imidazolidin-1-yl)-phenyl]-oxazol-2-ylamino}-N-(2-methoxy-ethyl)-4-methyl-benzamide; 1-(3-(2-(5-(ethoxymethyl)-2-methylphenylamino)oxazol-5-yl)-5-(trifluoromethoxy)phenyl)imidazolidin-2-one; 3-{3-[2-(3,5-Dimethyl-phenylamino)-oxazol-5-yl]-5-trifluoromethoxy-phenyl}-4-methyl-1H-pyridin-2-one; 3-{3-[2-(3,5-Dimethyl-phenylamino)-oxazol-5-yl]-5-methoxy-phenyl}-1H-pyridin-2-one; 3-{3-[2-(3,5-Dimethyl-phenylamino)-oxazol-5-yl]-5-isopropoxy-phenyl}-4-methyl-1H-pyridin-2-one; 4-[2-(5-(Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-4′-methyl-1′H-[2,3]bipyridinyl-2′-one; 3-[3-[2-(3,5-Dimethyl-phenylamino)-oxazol-5-yl]-5-(2-morpholin-4-yl-ethoxy)-phenyl]-4-methyl-1H-pyridin-2-one; 4′-Methyl-4-{2-[2-methyl-5-(2-morpholin-4-yl-ethoxy)-phenylamino]-oxazol-5-yl}-1′H-[2,3]bipyridinyl-2′-one; 4-[2-(3,5-Dimethyl-phenylamino)-oxazol-5-yl]-4′-methyl-6-(2-morpholin-4-yl-ethoxy)-1′H-[2,3]bipyridinyl-2′-one; 1-{3-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-5-isopropoxy-phenyl}-imidazolidin-2-one; 4′-Methyl-4-{2-[2-methyl-5-(3-morpholin-4-yl-propoxy)-phenylamino]-oxazol-5-yl}-1′H-[2,3]bipyridinyl-2′-one; and pharmaceutically acceptable salts thereof.
[0171] The compounds of the present invention may be prepared using the general protocol as follows.
[0172] The synthesis of the aminooxazole derivatives was undergone by firstly reacting aromatic aldehydes I with p-toluenesulfonylmethyl isocyanide (TosMIC) to prepare the corresponding arylsubstitued oxazole derivatives II using the method of Van Leusen et. al. ( Tetrahedron Lett., 1972, 23, 2369) (Scheme 1). The non-commercial aldehydes were prepared using literature methods to introduce the aldehyde group either from the corresponding brominated aromatic compound using an organometallic reagent and DMF or from the oxidation of corresponding toluene according the method of Frey et. al. ( Tetrahedron Lett., 2001, 39, 6815).
[0173] Secondly, those compounds II were then further functionalised by deprotonation of the oxazole moiety by a suitable organic base and subsequent electrophilic chlorination was used to prepare the 2-chlorooxazole coumpounds III. A direct nucleophilic displacement reaction by aniline compounds IV (wherein R′ is hydrogen), in the presence of a suitable solvent such as alcohol and with heating in elevated temperature, should generally afford the final target compounds V. Compounds V can also obtained by reacting compounds IV (wherein R′ is an acetyl group) and compounds III in the presence of sodium hydride and in a suitable solvent such as tetrahydrofurane or dimethylformamide (WO 2007/131953).
[0000]
[0174] Scheme 2 depicts the synthesis of the aminothiazole derivatives VIII undergone firstly by reacting aromatic aldehydes I with (methoxymethyl)triphenyl phosphonium chloride to prepare the corresponding arylsubstitued enol ether derivatives VI using Wittig reaction described by Iwao et. al. ( J. Org. Chem. 2009, 74, 8143). Secondly, a cyclisation was perfomed with the enol ether VI, thiourea derivatives VII and N-bromosuccinimide (NBS) using the method of Zhao et. al. ( Tetrahedron Lett., 2001, 42, 2101).
[0000]
[0175] The invention is now illustrated by Examples which represent currently preferred embodiments which make up a part of the invention but which in no way are to be used to limit the scope of it.
EXAMPLES OF COMPOUND SYNTHESIS
[0176] The invention will be more fully understood by reference to the following preparative examples, but they should not be construed as limiting the scope of the invention.
[0177] General: All chemicals used were commercial reagent grade products. Solvents were of anhydrous commercial grade and were used without further purification. The progress of the reactions was monitored by thin layer chromatography using precoated silica gel 60F 254, Merck TLC plates, which were visualized under UV light. Multiplicities in 1 H NMR spectra are indicated as singlet (s), broad singlet (br s), doublet (d), triplet (t), quadruplet (q), and multiplet (m) and the NMR spectrum were performed either on a Bruker Avance 300, 360 or 400 MHz spectrometer. Mass spectra were performed by Electrospray Ionisation Mass Spectrometry (ESI MS) in positive mode or by Atmospheric Pressure Chemical Ionization Mass Spectrometry (APCI MS) in positive mode.
[0178] LCMS methods: Method 1: This method was run on a Ultra-high performance liquid chromatography (UPLC) ACQUITY Waters instrument coupled to a TQD mass spectrometer. The gradient used was: starting at t=0.0 min with 5% of CH 3 CN+0.1% Formic acid in Water+0.1% Formic acid until t=0.5 min; then a linear gradient from t=0.5 min to t=7.0 min reaching 100% CH 3 CN+0.1% Formic acid; then staying at this state from t=7.0 min until t=10.0 min. The column used was a Waters HSS C18 1.8 μm, 2.1×50 mm. The detection instrument used was the triple quadrupole mass spectrometer (TQD) using ESI positive mode.
[0179] Method 2: This method was run on HPLC 2695 Alliance, Waters coupled to a ZMD mass spectrometer instrument. The gradient used was: starting at t=0.0 min with 0% of CH 3 CN+0.04% Formic acid in water (10 mM); then a linear gradient to t=3.1 min reaching 100% of CH 3 CN+0.04% Formic acid; then staying at this state to t=3.8 min and decreasing to =4.8 min to 0% of CH 3 CN+0.04% Formic acid in water. The column used was a Sunfire 2.1×50 mm dp: 3.5 μm.
ABBREVIATIONS
[0180] AcCl Acetyl chloride
[0181] Al 2 O 3 Alumina gel
[0182] APCI MS Atmospheric Pressure Chemical Ionization Mass Spectrometer
[0183] BINAP 2,2′-Bis(diphenylphosphino)-1,1′-binaphthalene
[0184] nBuLi n-Butyllithium
[0185] tBuONO Tert-butylnitrite
[0186] C 2 Cl 6 Hexachloroethane
[0187] CDCl 3 Deuterochloroform
[0188] CH 3 I Iodomethane
[0189] mCPBA 3-Chloroperoxybenzoic acid
[0190] Davephos 2-Dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl
[0191] DCM Dichloromethane
[0192] DCE 1,2-Dichloroethylene
[0193] DMF N,N-Dimethylformamide
[0194] DMSO-d 6 Hexadeuterodimethyl sulfoxide
[0195] EDCI 1-Ethyl-3-(3-Dimethylaminopropyl)carbodiimide
[0196] EI-MS Electron impact ionisation mass spectrometry
[0197] ES-MS Electrospray mass spectrometry
[0198] Et 2 O Diethylether
[0199] EtOAc Ethyl acetate
[0200] EtOH Ethanol
[0201] h Hour(s)
[0202] H 2 O 2 Hydrogen peroxyde
[0203] HOBT N-Hydroxybenzotriazole
[0204] K 2 CO 3 Potassium carbonate
[0205] K 3 PO 4 Potassium phosphate tribasic
[0206] KOtBu Potassium tert-butoxide
[0207] KSCN Potassium thiocyanate
[0208] LiHMDS Lithium bis(trimethylsilyl)amide
[0209] MeOH Methanol
[0210] MgSO 4 Magnesium sulfate
[0211] min Minutes
[0212] NaH Sodium hydride
[0213] NaHCO 3 Sodium bicarbonate
[0214] NaI Sodium iodide
[0215] NaOH Sodium hydroxyde
[0216] NaOtBu Sodium tert-butoxide
[0217] NaOEt Sodium ethoxide
[0218] NaOMe Sodium methoxide
[0219] NBS N-bromosuccinimide
[0220] NEt 3 Triethylamine
[0221] Pd 2 (dba) 3 Tris(dibenzylideneacetone)palladium(0)
[0222] Pd(PPh 3 ) 4 Tetrakis(triphenylphoshine)palladium(0)
[0223] iPrOH 2-Propanol
[0224] SiO 2 Silica gel
[0225] SnCl 2 .2H 2 O Tin(II) chloride dihydrate
[0226] TosMIC p-Toluenesulfonylmethyl isocyanide
[0227] THF Tetrahydrofuran
[0228] Xantphos 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene
Example 214
Synthetic Approach of Example 214
[0229]
Synthetic Approach of Intermediate I-e
[0230]
Synthesis of intermediate I-a: 1,3-dibromo-5-isopropoxy-benzene
[0231] To a solution of NaH 60% dispersion in mineral oil (1.89 g, 47.25 mmol) in dry DMF (20 mL) under inert atmosphere was added dropwise at 0° C. i-PrOH (3.62 mL, 47.25 mmol). The mixture was stirred at 0° C. for 15 min. Then, a solution of 1,3-dibromo-5-fluoro-benzene (1.98 mL, 15.75 mmol) in dry DMF (20 mL) was added dropwise at 0° C. The reaction mixture was stirred for 16 h at room temperature. A saturated solution of NaHCO 3 was added dropwise and the crude product was extracted with Et 2 O (2 times), the organic layer was washed with a saturated solution of NaHCO 3 (3 times), then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give I-a as yellow oil in quantitative yield. 1 H RMN (300 MHz, CDCl 3 ) δ 7.21 (t, J=1.4 Hz, 1H), 6.97 (d, J=1.5 Hz, 2H), 4.61-4.40 (m, 1H), 1.32 (d, J=6.0 Hz, 6H).
Synthesis of intermediate I-b: 3-bromo-5-isopropoxy-benzaldehyde
[0232] To a solution of I-a (4.630 g, 15.75 mmol) in dry Et 2 O (60 mL) under inert atmosphere was added dropwise at −78° C. a solution of n-butyl lithium in dry Et 2 O (6.3 mL, 15.75 mmol). The reaction mixture was stirred at −78° C. for 0.5 h. Then, dry DMF (1.35 mL) was added dropwise at −78° C. and the temperature was allowed to reach −40° C. over 1.5 h. A solution of HCl (3N) was added and the crude product was extracted with Et 2 O (2 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give I-b as yellow oil in 82% yield. 1 H RMN (300 MHz, CDCl 3 ) δ 9.89 (s, 1H), 7.54 (m, 1H), 7.29 (m, 2H), 4.60 (dt, J=12.1, 6.0 Hz, 1H), 1.36 (t, J=6.0 Hz, 6H).
Synthesis of intermediate I-c: 5-(3-bromo-5-isopropoxy-phenyl)-oxazole
[0233] To a solution of I-b (6.925 g, 28.50 mmol) in MeOH (125 mL) were added successively K 2 CO 3 (11.811 g, 85.50 mmol) and TosMIC (6.674 g, 34.20 mmol). The reaction mixture was stirred at room temperature for 16 h. Then, the solvent was removed under reduce pressure, water was added and the crude product was extracted with EtOAc (2 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 5 to 30% EtOAc/cyclohexane as eluent to give I-c as yellow oil in 86% yield. 1 H RMN (300 MHz, CDCl 3 ) δ 7.90 (s, 1H), 7.34 (m, 2H), 7.09 (m, 1H), 7.00 (m, 1H), 4.56 (dt, J=12.1, 6.0 Hz, 1H), 1.49-1.26 (m, 6H).
Synthesis of intermediate I-d: 5-(3-bromo-5-isopropoxy-phenyl)-2-chloro-oxazole
[0234] To a solution of I-c (6.921 g, 24.50 mmol) in dry THF (130 mL) under inert atmosphere was added dropwise at −78° C. a solution of LiHMDS in dry THF (29 mL, 29.00 mmol). The reaction mixture was stirred at −78° C. for 0.5 hour. Then, C 2 Cl 6 (8.712 g, 36.75 mmol) was added at −78° C. and the reaction mixture was stirred at room temperature for 16 h. Water was added and the crude product was extracted with EtOAc (2 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 20% EtOAc/cyclohexane as eluent to give I-d as yellow oil in 92% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 7.29 (t, J=1.5 Hz, 1H), 7.27 (s, 1H), 7.02 (d, J=1.4 Hz, 2H), 4.57 (dt, J=12.1, 6.0 Hz, 1H), 1.36 (s, 3H), 1.34 (s, 3H).
Synthesis of intermediate I-f: [5-(3-Bromo-5-isopropoxy-phenyl)-oxazol-2-yl]-((5-ethoxymethyl)-2-methyl-phenyl)-amine
[0235] To a solution of I-d (1.556 g, 4.915 mmol) and I-e (0.812 g, 4.915 mmol) in i-PrOH (45 mL) under inert atmosphere was added dropwise a solution of HCl in dry Et 2 O (0.98 mL, 0.98 mmol). The reaction mixture was stirred at 80° C. for 16 h. Then, the solvent was removed under reduced pressure and a solution of NaOH (2.5 N) was added. The crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 30% EtOAc/cyclohexane as eluent to give I-f as white solid in 64% yield. 1 H RMN (300 MHz, DMSO-d 6 ) δ 9.30 (s, 1H), 7.81 (s, 1H), 7.56 (s, 1H), 7.30 (s, 1H), 7.16 (d, J=7.7 Hz, 1H), 7.09 (d, J=1.4 Hz, 1H), 7.00 (d, J=1.7 Hz, 1H), 6.94 (d, J=7.8 Hz, 1H), 4.69 (dt, J=12.0, 5.9 Hz, 1H), 4.41 (s, 2H), 3.47 (q, J=7.0 Hz, 2H), 2.27 (s, 3H), 1.39 (s, 3H), 1.27 (d, J=6.0 Hz, 6H), 1.14 (t, J=7.0 Hz, 3H).
Synthesis of intermediate I-g: 4-ethoxymethyl-1-methyl-2-nitro-benzene
[0236] To a solution of NaOEt in dry EtOH (45 mL, 114.90 mmol) under inert atmosphere was added 4-chloromethyl-1-methyl-2-nitro-benzene (7.0 g, 38.30 mmol). The reaction mixture was stirred at room temperature for 16 hours. Water was added and ethanol was removed under reduced pressure. The crude product was extracted with DCM (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give I-g as brown oil in 96% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 7.95 (s, 1H), 7.48 (d, J=7.8 Hz, 1H), 7.31 (d, J=7.9 Hz, 1H), 4.52 (s, 2H), 3.56 (q, J=7.0 Hz, 2H), 2.57 (d, J=10.1 Hz, 3H), 1.26 (t, J=7.0 Hz, 3H).
Synthesis of intermediate I-e: 5-ethoxymethyl-2-methyl-phenylamine
[0237] To a solution of I-g (7.21 g, 36.93 mmol) in EtOH (238 mL) were added successively Pd/C (2.432 g) and at 0° C. hydrazine monohydrate (4.84 mL, 99.71 mmol) dropwise. The reaction mixture was stirred at 80° C. for 2 h. Then, the hot mixture was filtrated over celite pad and washed with EtOH. The filtrate was concentrated under reduced pressure to give I-e as yellow oil in quantitative yield. 1 H NMR (300 MHz, CDCl 3 ) δ 6.99 (d, J=7.6 Hz, 1H), 6.67 (d, J=7.5 Hz, 2H), 4.41 (s, 2H), 3.52 (q, J=7.0 Hz, 3H), 2.18 (s, 3H), 1.04 (t, J=8.5 Hz, 3H).
Synthesis of example 214: 1-{3-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-5-isopropoxy-phenyl}-imidazolidin-2-one
[0238] In a sealed tube, to a solution of I-f (872 mg, 1.56 mmol) in dry dioxane (13 mL) were added successively imidazolidin-2-one (674 mg, 7.84 mmol), cesium carbonate (1.595 g, 4.90 mmol), Pd 2 (dba) 3 (113 mg, 0.20 mmol), and Xantphos (54 mg, 0.06 mmol). The reaction mixture was stirred at 110° C. for 16 h. Water was added, the crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 50 to 100% EtOAc/cyclohexane as eluent to give compound 214 as white solid in 50% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.26 (s, 1H), 7.81 (s, 1H), 7.40 (s, 1H), 7.29 (s, 1H), 7.15 (d, J=7.7 Hz, 1H), 7.11 (t, J=2.0 Hz, 1H), 7.01 (s, 1H), 6.92 (d, J=7.7 Hz, 1H), 6.78 (s, 1H), 4.62 (dt, J=12.1, 6.0 Hz, 1H), 4.41 (s, 2H), 3.92-3.81 (m, 2H), 3.53-3.34 (m, 4H), 2.27 (s, 3H), 1.29 (s, 3H), 1.27 (s, 3H), 1.14 (t, J=7.0 Hz, 3H).
[0239] (ESI+) m/z 451.2 (M+H) + .
[0240] Retention time=3.52 min (method 2).
Example 215
Synthetic Approach of Example 215
[0241]
Synthesis of intermediate II-a: 2-Bromo-pyridine-4-carbaldehyde oxime
[0242] To a solution of 2-bromo-4-methylpyidine (10.0 g, 58.13 mmol) in dry THF (60 mL) under inert atmosphere were added successivelly dropwise at −10° C. tert-butylnitrite (12.5 mL, 104.63 mmol) and a solution of KOtBu in dry THF (88 mL, 87.20 mmol). The reaction mixture was stirred at −10° C. for 3 h. Then, a saturated solution of NH 4 Cl was added and a solution of HCl (4N) was added until pH=6-7. The crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give II-a as yellow oil in 90% yield. The crude product was directly engaged in the next step. 1 H NMR (300 MHz, DMSO-d 6 ) δ 12.47 (s, 1H), 8.49 (d, J=5.1 Hz, 1H), 8.12 (s, 1H), 7.90 (dd, J=5.1, 1.0 Hz, 1H), 7.55 (s, 1H).
Synthesis of intermediate II-b: 2-Bromo-pyridine-4-carbaldehyde
[0243] To a suspension of II-a (10.5 g, 52.23 mmol) in water (50 mL) were added successively dropwise at −10° C. concentrated solution of HCl (50 mL) and a solution of formaldehyde (50 mL) in water (37% w/w). The reaction mixture was stirred at −10° C. for 4 h. Then, a solution of NaOH (2 N) was added until pH=6-7. The crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give II-b as brownish oil in 97% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 10.03 (s, 1H), 8.68 (d, J=4.9 Hz, 1H), 8.07 (s, 1H), 7.84 (d, J=4.9 Hz, 1H).
Synthesis of intermediate II-c: 2-Bromo-4-oxazol-5-yl-pyridine
[0244] To a solution of II-b (9.4 g, 50.53 mmol) in MeOH (100 mL) were added successively K 2 CO 3 (13.97 g, 101.06 mmol) and TosMIC (14.80 g, 75.8 mmol). The reaction mixture was stirred at room temperature for 16 h. Then, the solvent was removed under reduce pressure, water was added and the crude product was extracted with EtOAc (2 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The dark brown solid was triturated in cold ether, filtered and washed with more ether to get the final product II-c as pale brown solid in 73% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 8.42 (d, J=5.2 Hz, 1H), 8.02 (s, 1H), 7.73 (s, 1H), 7.60 (s, 1H), 7.48 (dd, J=5.2, 1.3 Hz, 1H).
Synthesis of intermediate II-d: 2-Methylsulfanyl-1H-imidazole
[0245] To a solution of 2-mercaptoimidazole (5.0 g, 49.93 mmol) in water (200 mL) was added NaOH (2.4 g, 59.91 mmol). The reaction mixture was stirred at room temperature for 0.5 h. Then, acetone (200 mL) and MeI (3.4 mL, 54.92 mmol) were added. The reaction mixture was stirred at room temperature for 16 h. Then, the solvent was removed under reduce pressure, water was added and the crude product was extracted with EtOAc (5 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The orange solid was triturated several times with petroleum ether and filtered to give compound II-d as pale brown solid in 88% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 12.16 (s, 1H), 7.14 (s, 1H), 6.91 (s, 1H), 2.50 (s, 3H).
Synthesis of intermediate II-e: 2-(2-Methylsulfanyl-imidazol-1-yl)-4-oxazol-5-yl-pyridine
[0246] In a sealed tube were charged II-d (1.98 g, 17.33 mmol), II-c (3.0 g, 13.33 mmol), K 2 CO 3 (3.87 g, 27.99 mmol), CuI (253 mg, 1.33 mmol), N,N′-dimethylcyclohexane-1,2-diamine (420 μL, 2.66 mmol) in dry toluene (19 mL). The reaction mixture was stirred at 110° C. for 4 days. Then, water was added and the crude product was extracted with EtOAc (2 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The brown solid was triturated in cold ether, filtered and washed with more ether to get the final product We as pale brown solid in 70% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.67 (s, 1H), 8.60 (d, J=5.2 Hz, 1H), 8.13 (s, 1H), 7.97 (s, 1H), 7.96 (s, 1H), 7.70 (dd, J=5.2, 1.4 Hz, 1H), 7.15 (d, J=1.5 Hz, 1H), 2.52 (s, 3H).
Synthesis of intermediate II-f: 2-(2-Methanesulfonyl-imidazol-1-yl)-4-oxazol-5-yl-pyridine
[0247] To a solution of II-e (2.17 g, 7.83 mmol) in DCM (260 mg) was added mCPBA (2.97 g, 17.23 mmol). The mixture was stirred at room temperature for 16 h. Then, a saturated solution of NaHCO 3 was added and the crude product was extracted with DCM (2 times) and the organic layer was washed with saturated solution of NaHCO 3 (3 times), with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 5 to 10% MeOH/EtOAc as eluent to give II-f as solid in 84% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.69 (m, 2H), 8.14 (s, 1H), 8.06 (d, J=0.7 Hz, 1H), 8.00 (d, J=1.2 Hz, 1H), 7.89 (dd, J=5.2, 1.5 Hz, 1H), 7.38 (d, J=1.2 Hz, 1H), 3.53 (s, 3H).
Synthesis of intermediate II-g: 2-(2-Methoxy-imidazol-1-yl)-4-oxazol-5-yl-pyridine
[0248] To a solution of II-f (600 mg, 2.07 mmol) in dry MeOH/THF (1/1, 6 mL) was added at 0° C. a solution of NaOMe in MeOH (6.2 mL, 3.10 mmol). The reaction mixture was stirred at 50° C. for 16 h. Water was added and the crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give compound II-g as pale brown solid in 98% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.66 (s, 1H), 8.58 (d, J=5.3 Hz, 1H), 8.11 (s, 1H), 8.03 (s, 1H), 7.68 (dd, J=5.2, 1.4 Hz, 1H), 7.51 (d, J=1.9 Hz, 1H), 6.70 (d, J=1.9 Hz, 1H), 4.09 (s, 3H).
Synthesis of intermediate II-h: 4-(2-Chloro-oxazol-5-yl)-2-(2-methoxy-imidazol-1-yl)-pyridine
[0249] To a solution of intermediate II-g (366 mg, 1.51 mmol) in dry THF (15 mL) under inert atmosphere was added dropwise at −78° C. a solution of LiHMDS in dry THF (2.3 mL, 2.27 mmol). The reaction mixture was stirred at −78° C. for 0.5 h. Then, C 2 Cl 6 (537 mg, 2.27 mmol) was added at −78° C. and the reaction mixture was stirred at room temperature for 16 h. Water was added and the crude product was extracted with EtOAc (2 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 10% MeOH/EtOAc as eluent to give intermediate II-h as white solid in 74% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 8.51 (dd, J=5.2, 0.8 Hz, 1H), 7.95 (dd, J=1.4, 0.8 Hz, 1H), 7.55 (s, 1H), 7.52 (d, J=1.9 Hz, 1H), 7.33 (dd, J=5.2, 1.5 Hz, 1H), 6.75 (d, J=2.0 Hz, 1H), 4.21 (s, 3H).
Synthesis of intermediate II-l: 4 -Methoxymethyl-1-methyl-2-nitro-benzene
[0250] To a solution of NaOMe (1.6 g, 29.63 mmol) in dry MeOH (40 mL) under inert atmosphere was added 4-chloromethyl-1-methyl-2-nitro-benzene (5.0 g, 26.94 mmol). The reaction mixture was stirred at room temperature for 16 h. Water was added and EtOH was removed under reduced pressure. The crude product was extracted with DCM (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated to give intermediate II-l as yellow oil. 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (s, 1H), 7.47 (d, J=7.8 Hz, 1H), 7.32 (d, J=7.8 Hz, 1H), 4.48 (s, 2H), 3.41 (s, 3H), 2.58 (s, 3H).
Synthesis of intermediate II-m: 5-Methoxymethyl-2-methyl-phenylamine
[0251] To a solution of intermediate II-l (4.77 g, 26.32 mmol) in EtOH/H 2 O: 9/1 (150 mL) were added successively, SnCl 2 .2H 2 O (29.70 g, 131.60 mmol) and hydrochloric acid 37% (15 mL) dropwise. The reaction mixture was stirred at room temperature for 16 h. EtOH was removed under reduced pressure and to the resulting aqueous solution was added a solution of NaOH (10 N) until pH=6-7. Then, the crude product was extracted with DCM (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 30% EtOAc/cyclohexane as eluent to give intermediate II-m as yellow oil. 1 H NMR (300 MHz, DMSO-d 6 ) δ 6.88 (d, J=7.5 Hz, 1H), 6.58 (s, J=17.6 Hz, 1H), 6.41 (d, J=7.5 Hz, 1H), 4.80 (s, 2H), 4.24 (s, 2H), 3.23 (s, 3H), 2.03 (s, 3H).
Synthesis of intermediate II-i: N-(5-Methoxymethyl-2-methyl-phenyl)-acetamide
[0252] To a solution of II-m (2.0 g, 13.23 mmol) in dry DCM (45 mL) was added successively dry NEt 3 (2.3 mL, 15.88 mmol) and at 0° C. AcCl (1.0 mL, 14.55 mmol) dropwise. The reaction mixture was stirred at room temperature for 2 h. Water was added and the crude product was extracted with DCM (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 50 to 80% EtOAc/cyclohexane as eluent to give intermediate II-i as pale yellow solid in 88% yield over the 3 steps. 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.27 (s, 1H), 7.36 (s, 1H), 7.16 (d, J=7.7 Hz, 1H), 7.00 (d, J=7.6 Hz, 1H), 4.34 (s, 2H), 3.26 (s, 3H), 2.18 (s, 3H), 2.05 (s, 4H).
Synthesis of intermediate II-j: {5-[2-(2-Methoxy-imidazol-1-yl)-pyridin-4-yl]-oxazol-2-yl}-(5-methoxymethyl-2-methyl-phenyl)-amine
[0253] To a solution of NaH 60% dispersion in mineral oil (237 mg, 6.16 mmol) in dry DMF (20 mL) was added dropwise at 0° C. a solution of intermediate II-i (595 mg, 3.08 mmol) in dry DMF (20 mL). The reaction mixture was stirred at room temperature for 1 h and a solution of intermediate II-h (852 mg, 3.08 mmol) in dry DMF (20 mL) was added dropwise at 0° C. The reaction mixture was stirred for 3 h at 0° C. Water was added and the crude product was extracted with EtOAc (2 times), the organic layer was washed with a saturated solution of NaHCO 3 (3 times), then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 20% EtOAc/cyclohexane as eluent to give intermediate II-j as white solid in 44% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.65 (s, 1H), 8.45 (d, J=5.3 Hz, 1H), 7.86 (s, 1H), 7.79 (s, 1H), 7.72 (s, 1H), 7.46 (dd, J=5.1, 3.6 Hz, 2H), 7.21 (d, J=7.7 Hz, 1H), 7.00 (d, J=7.7 Hz, 1H), 6.68 (d, J=1.8 Hz, 1H), 4.38 (s, 2H), 4.05 (s, 3H), 3.28 (s, 3H), 2.29 (s, 3H).
Synthesis of example 215: 1-{4-[2-((5-Methoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-pyridin-2-yl}-1,3-dihydro-imidazol-2-one hydrochloride
[0254] To a solution of II-j (100 mg, 0.26 mmol) in dry dioxane (4 mL) was added dropwise at 0° C. a solution of HCl in dry ether (546 μL, 0.55 mmol). The reaction mixture was stirred at 60° C. for 2 h and at room temperature for 16 h. Then, the solvent was removed under reduce pressure, the crude product was triturated with ether and filtrated to give compound 215 as white solid in 57% yield. 1 H NMR (300 MHz, CD 3 OD) δ 10.04-9.95 (m, 1H), 9.46 (s, 1H), 9.15 (s, 1H), 9.03 (d, J=4.6 Hz, 1H), 8.95-8.87 (m, 1H), 8.78 (d, J=7.8 Hz, 1H), 8.19 (d, J=3.2 Hz, 1H), 6.04 (s, 2H), 4.97 (s, 3H), 3.91 (s, 3H).
Example 216
Synthetic Approach of Compound 216
[0255]
Synthesis of intermediate III-a: 1-Bromo-3-(2-methoxy-vinyl)-benzene
[0256] To a solution of (methoxymethyl)triphosphonium chloride (5.56 g, 16.21 mmol) in dry THF (13 mL) under inter atmosphere was added dropwise at 0° C. a solution of nBuLi in dry THF (22 mL, 21.62 mmol). The reaction mixture was stirred at room temperature for 1 h. Then, a solution of 3-bromobenzaldehyde (2.0 g; 10.81 mmol) in dry THF (20 mL) was added dropwise at 0° C. The reaction mixture was stirred at room temperature for 16 h. A saturated solution of NH 4 Cl was added and the crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 10 to 15% EtOAc/cyclohexane as eluent to give III-a as yellow oil in 66% yield. 1 H NMR (300 MHz, CDCl 3 ) δ 7.79 (s, J=1.5 Hz, 1H), 7.48-7.24 (m, 5H), 7.20-7.12 (m, 2H), 7.06 (d, J=13.0 Hz, 1H), 6.19 (d, J=7.0 Hz, 1H), 5.75 (d, J=13.0 Hz, 1H), 5.17 (d, J=7.0 Hz, 1H), 3.82 (s, 3H), 3.71 (s, 3H).
Synthesis of intermediate III-b: (5-Methoxy-2-methyl-phenyl)-thiourea
[0257] To a solution of KSCN (780 mg, 8.02 mmol) in acetone (10 mL) was added dropwise at room temperature as solution of AcCl (900 μL, 8.02 mmol) in acetone (10 mL). The reaction mixture was stirred for 15 min at 50° C. Then, a solution of 5-methoxy-2-methylaniline (1.0 g, 7.29 mmol) in acetone (10 mL) was added and the reaction mixture was stirred at 50° C. for 15 min. Water was added and the solid was filtered, washed with more water and ether to give a white solid. A solution of the latter with K 2 CO 3 (2.0 g, 14.58 mmol) in MeOH (20 mL) was stirred at room temperature for 3 h. MeOH was removed under reduced pressure and the solid was washed with water and ether to give III-b as a white solid in 78% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.20 (s, 1H), 7.13 (d, J=8.4 Hz, 1H), 6.81 (d, J=2.4 Hz, 1H), 6.75 (dd, J=8.3, 2.6 Hz, 1H), 3.71 (s, 3H), 2.10 (s, 3H).
Synthesis of intermediate III-c: [5-(3-Bromo-phenyl)-thiazol-2-yl]-(5-methoxy-2-methyl-phenyl)-amine
[0258] To a solution of III-a (300 mg, 1.41 mmol) in dioxane/water (1/1, 6 mL) was added NBS (276 mg, 1.55 mmol). The reaction mixture was stirred at room temperature for 1 h. Then, III-b (277 mg, 1.41 mmol) was added and the reaction mixture was stirred at 80° C. for 16 h. Water followed by saturated solution of NH 4 Cl were added and the crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 35% EtOAc/cyclohexane as eluent to give III-c as pale yellow solid in 69% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.48 (s, 1H), 7.77-7.69 (m, 2H), 7.54 (d, J=2.1 Hz, 1H), 7.46 (dd, J=7.6, 0.9 Hz, 1H), 7.40 (dd, J=7.9, 1.0 Hz, 1H), 7.30 (t, J=7.9 Hz, 1H), 7.11 (d, J=8.3 Hz, 1H), 6.60 (dd, J=8.3, 2.5 Hz, 1H), 3.71 (s, 3H), 2.19 (s, 3H).
Synthesis of example 216: 1-{3-[2-(5-Methoxy-2-methyl-phenylamino)-thiazol-5-yl]-phenyl}-imidazolidin-2-one
[0259] In a sealed tube, to a solution of III-c (200 mg, 0.53 mmol) in dry dioxane (10 mL) were added successively 2-imidazolidinone (275 mg, 3.20 mmol), cesium carbonate (432 mg, 1.33 mmol), Pd 2 (dba) 3 (46 mg, 0.05 mmol), 4,5-Xantphos (61 mg, 0.11 mmol). The reaction mixture was stirred at 110° C. for 16 h. Water was added and the crude product was extracted with EtOAc (2 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 30% MeOH/EtOAc as eluent to give compound 216 as yellow solid in 41% yield. 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.36 (s, 1H), 7.75 (s, 1H), 7.63-7.56 (m, 2H), 7.37 (d, J=8.2 Hz, 1H), 7.29 (t, J=7.9 Hz, 1H), 7.15 (d, J=7.5 Hz, 1H), 7.11 (d, J=8.4 Hz, 1H), 7.01 (s, 1H), 6.59 (dd, J=8.3, 2.6 Hz, 1H), 3.93-3.83 (m, 2H), 3.72 (s, 3H), 3.44-3.37 (m, 2H), 2.20 (s, 3H).
Example 217
Synthetic Approach of Example 217
[0260]
Synthetic Approach of Intermediate IV-a
[0261]
Synthesis of intermediate IV-c: 1-Acetyl-3-(4-methyl-3-nitro-phenyl)-thiourea
[0262] To a solution of ammonium thiocyanate (1.05 g, 13.85 mmol) in acetone (21 mL) was added dropwise acetyl chloride (0.90 mL 12.70 mmol). The reaction mixture was stirred at 40° C. for 30 min. Then, a solution of 4-methyl-3-nitroaniline (1.76 g, 11.54 mmol) in acetone (7 mL) was added and the reaction mixture was stirred at room temperature for 4 h. The reaction mixture was poured into ice-water and the precipitate was filtered, washed with more water and cyclohexane to give compound IV-c as brown solid in 50% yield. (300 MHz, DMSO) δ 12.45 (s, 1H), 11.53 (s, 1H), 8.38 (d, J=2.0 Hz, 1H), 7.69 (dd, J=8.3, 2.0 Hz, 1H), 7.43 (d, J=8.3 Hz, 1H), 2.44 (s, 3H), 2.09 (s, 3H).
Synthesis of intermediate IV-d: (4-Methyl-3-nitro-phenyl)-thiourea
[0263] To a solution of IV-c (873 mg, 3.45 mmol) in methanol (5 mL) was added K 2 CO 3 (953 mg, 6.90 mmol). The reaction mixture was stirred at room temperature for 16 h. Then, the solvent was removed under reduce pressure, water was added and the crude product was extracted with EtOAc (twice), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 , and concentrated. The final product was purified by silica gel chromatography using 0 to 50% EtOAc/cyclohexane as eluent to give compound IV-d as yellow solid in 60% yield. (300 MHz, DMSO) δ 9.95 (s, 1H), 8.28 (d, J=2.1 Hz, 1H), 8.00-7.70 (m, 3H), 7.42 (d, J=8.3 Hz, 1H), 2.47 (s, 3H).
Synthesis of intermediate IV-e: (4-Methyl-3-nitro-phenyl)-thiazol-2-yl-amine
[0264] To a suspension of IV-d (377 mg, 1.79 mmol) in EtOH (7 mL) were added a solution of chloroacetaldehyde ((1.41 g, 17.93 mmol) in water (50% w/w) and KHCO 3 (539 mg, 5.37 mmol). The reaction mixture was stirred at 70° C. for 16 h. Then, the solvent was removed under reduce pressure, water was added and the crude product was extracted with EtOAc (3 times), the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 , and concentrated. The final product was purified by silica gel chromatography using 0 to 70% EtOAc/cyclohexane as eluent to give compound IV-e as yellow solid in 40% yield. (300 MHz, DMSO) δ 10.58 (s, 1H), 8.55 (d, J=2.4 Hz, 1H), 7.69 (dd, J=8.4, 2.4 Hz, 1H), 7.41 (d, J=8.5 Hz, 1H), 7.33 (d, J=3.7 Hz, 1H), 7.00 (d, J=3.7 Hz, 1H), 2.45 (s, 3H).
Synthesis of intermediate IV-f: 4-Methyl-N1-thiazol-2-yl-benzene-1,3-diamine
[0265] To a solution of IV-e (737 mg, 3.13 mmol) in EtOH/DCM: (30/13 mL) were added successively, SnCl 2 .2H 2 O (3.54 g, 15.65 mmol) and hydrochloric acid 37% (3 mL) dropwise. The reaction mixture was stirred at room temperature for 16 h. EtOH was removed under reduced pressure and to the resulting aqueous solution was added a solution of NaOH (10 N) until pH=6-7. Then, the crude product was extracted with DCM (twice) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 30% EtOAc/cyclohexane as eluent to give intermediate IV-f as yellow oil in 95% yield. (300 MHz, DMSO) δ 9.74 (s, 1H), 7.18 (d, J=3.7 Hz, 1H), 6.90 (d, J=2.0 Hz, 1H), 6.85-6.77 (m, 2H), 6.66 (dd, J=8.0, 2.0 Hz, 1H), 4.83 (brs, 2H), 1.99 (s, 3H).
Synthesis of intermediate IV-a: N-[5-(Acetyl-thiazol-2-yl-amino)-2-methyl-phenyl]-acetamide
[0266] To a solution of IV-f (610 mg, 2.97 mmol) and NaHCO 3 (2.50 g, 29.71 mmol) in dry DCE (10 mL), was added dropwise at 0° C. actyl chloride (0.634 mL, 8.91 mmol). The reaction mixture was stirred at 50° C. for 5 h. Then, water was added and the crude product was extracted with DCM (3 times) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 30% EtOAc/cyclohexane as eluent to give intermediate IV-a as yellow solid in 75% yield. (300 MHz, DMSO) δ 9.39 (s, 1H), 7.54 (d, J=1.7 Hz, 1H), 7.40-7.32 (m, 2H), 7.29 (d, J=3.6 Hz, 1H), 7.13 (dd, J=7.9, 1.9 Hz, 1H), 2.28 (s, 3H), 2.07 (s, 3H), 1.99 (s, 3H).
Synthesis of intermediate IV-b: N-{3-[5-(3-Bromo-5-isopropoxy-phenyl)-oxazol-2-ylamino]-4-methyl-phenyl}-N-thiazol-2-yl-acetamide
[0267] To a solution of NaH 60% dispersion in mineral oil (83 mg, 2.08 mmol) in dry DMF (3 mL) was added dropwise at 0° C. a solution of intermediate IV-a (300 mg, 1.04 mmol) in dry DMF (3 mL). The reaction mixture was stirred at room temperature for 1 h and a solution of intermediate I-d (328 mg, 1.04 mmol) in dry DMF (3 mL) was added dropwise at 0° C. The reaction mixture was stirred for 16 h at room temperature. Water was added and the crude product was extracted with EtOAc (twice), the organic layer was washed with a saturated solution of NaHCO 3 (3 times), then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 0 to 35% EtOAc/cyclohexane as eluent to give intermediate IV-b as beige solid in 46% yield. (300 MHz, DMSO) δ 9.63 (s, 1H), 8.08 (d, J=2.1 Hz, 1H), 7.65 (s, 1H), 7.47 (d, J=2.2 Hz, 1H), 7.45 (d, J=2.5 Hz, 1H), 7.42-7.38 (m, 2H), 7.19 (t, J=2.0 Hz, 1H), 7.15 (dd, J=7.9, 2.2 Hz, 1H), 7.11 (t, J=2.0 Hz, 1H), 4.78 (septuplet, J=5.8 Hz, 1H), 2.49 (s, 3H), 2.14 (s, 3H), 1.37 (d, J=6.0 Hz, 6H).
Synthesis of example 217: 1-(3-Isopropoxy-5-{2-[2-methyl-5-(thiazol-2-ylamino)-phenylamino]-oxazol-5-yl}-phenyl)-imidazolidin-2-one
[0268] In a sealed tube, to a solution of IV-b (219 mg, 0.42 mmol) in dry dioxane (5 mL) were added successively imidazolidin-2-one (286 mg, 3.36 mmol), cesium carbonate (162 mg, 0.50 mmol), Pd 2 (dba) 3 (11 mg, 0.01 mmol), and Xantphos (24 mg, 0.04 mmol). The reaction mixture was stirred at 110° C. for 16 h. Water was added, the crude product was extracted with EtOAc (twice) and the organic layer was washed with water, then with a saturated solution of NaCl, dried over MgSO 4 and concentrated. The final product was purified by silica gel chromatography using 50 to 100% EtOAc/cyclohexane as eluent to give compound 217 as beige solid in 49% yield. (300 MHz, DMSO) δ 10.12 (brs, 1H), 9.25 (s, 1H), 8.04 (d, J=2.1 Hz, 1H), 7.42 (s, 1H), 7.38 (dd, J=8.3, 2.1 Hz, 1H), 7.25 (brs, 1H), 7.19 (d, J=3.7 Hz, 1H), 7.15 (t, J=1.9 Hz, 1H), 7.10 (d, J=8.4 Hz, 1H), 7.01 (s, 1H), 6.85 (d, J=3.6 Hz, 1H), 6.81 (s, 1H), 4.61 (m, 1H), 3.84 (m, 2H), 3.38 (m, 2H), 2.23 (s, 3H), 1.27 (d, J=6.0 Hz, 6H).
[0269] (ESI+) m/z 491 (M+H) +
[0270] Retention time=3.13 min (method 2)
Example 218
Synthetic Approach of Example 218
[0271]
Synthetic Approach of Intermediate V-h
[0272]
Synthesis of intermediate V-a: 4-Methyl-pyridin-2-ol
[0273] Intermediate V-a was prepared using the method of Adger et al, in J. Chem. Soc. Perkin Trans. 1, 1988, p2791-2796. A 1L flask containing water (240 mL) was treated with conc. H 2 SO 4 (32 mL) and cooled to 0° C. then treated with the 2-amino-4-picoline in one portion (30 g, 277 mmol). A solution of NaNO 2 (20.6 g, 299 mmol) in water (40 mL) was added dropwise over 1 h such that the internal temperature never rose above 5° C. The reaction was stirred at 0° C. for 1 h then heated to 95° C. and after 15 min at this temperature cooled to room temperature. The solution was taken to pH 6-7 with 50% NaOH aq (exotherm) and extracted whilst hot with EtOAc (4×120 mL). The combined organics were dried (MgSO 4 ), filtered and evaporated to afford a beige crystalline solid (24.5 g, 81%) of intermediate V-a. 1 H NMR (300 MHz, DMSO-d 6 ) δ 11.31 (s, 1H), 7.23 (d, J=6.7 Hz, 1H), 6.10 (s, 1H), 6.00 (dd, J=6.7, 1.2 Hz, 1H), 2.10 (s, 3H).
Synthesis of intermediate V-b: 3-Bromo-4-methyl-pyridin-2-ol
[0274] A solution of 4-methyl-pyridin-2-ol V-a (25 g, 229 mmol) in glacial acetic acid (350 mL) and EtOAc (680 mL) was treated with NBS (37.4 g, 210 mmol) and stirred at room temperature for 30 min. The mixture was then taken to pH 8 with aqueous ammonia and extracted with EtOAc. The separated organics were washed with 1:1 H 2 O/brine then dried (MgSO 4 ), filtered and evaporated before purification by silica column chromatography (1-4% EtOH/DCM) to afford the desired product V-b as a white solid (8.66 g). 1 H NMR (300 MHz, DMSO) δ 11.90 (s, 1H), 7.32 (d, J=6.6 Hz, 1H), 6.19 (d, J=6.6 Hz, 1H), 2.25 (s, 3H).
Synthesis of intermediate V-c: 3-Bromo-2-methoxy-4-methyl-pyridine
[0275] A solution of 3-bromo-4-methyl-2-pyridone V-b (2.20 g, 11.7 mmol), in DCM (80 mL) was treated with MeI (7.29 mL, 117 mmol) and Ag 2 CO 3 (6.47 g, 23.5 mmol). The flask was stoppered and stirred under argon for 6 days. The mixture was filtered and purified by column chromatography (SiO 2 , 10% EtOAc in cyclohexane) to afford the desired product V-c as a clear mobile oil (1.83 g, 80%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (d, J=5.0 Hz, 1H), 6.77 (d, J=5.1 Hz, 1H), 4.00 (s, 3H), 2.39 (s, 3H).
Synthesis of intermediate V-d: 2-Methoxy-4-methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-pyridine
[0276] A dry sealed tube under argon was charged with 3-bromo-2-methoxy-4-methylpyridine V-c (813 mg, 4.02 mmol), bis(pinacolato)diboron (1.12 g, 4.41 mmol), PdCl 2 (dppf):DCM (146 mg, 0.20 mmol), KOAc (1.18 g, 12.0 mmol) and dry DMF (10 mL). After 1.5 h at 100° C., the mixture was cooled to room temperature and a further portion of catalyst (75 mg, 0.092 mmol) was added. The tube was sealed and the mixture stirred at 100° C. overnight. The mixture was cooled, the solvent evaporated and the mixture taken up in DCM before washing with water. The separated organics were dried (MgSO 4 ), filtered and evaporated before purification by column chromatography (SiO 2 , 10% to 20% EtOAc in cyclohexane) to afford the intermediate V-d as a mobile yellow oil (2.14 g, 51%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.00 (d, J=5.3 Hz, 1H), 6.65 (d, J=5.3 Hz, 1H), 3.89 (s, 3H), 2.33 (s, 3H), 1.40 (d, J=11.1 Hz, 12H).
Synthesis of intermediate V-e: 2′-Methoxy-4′-methyl-4-oxazol-5-yl-[2,3]bipyridinyl
[0277] An oven-dried flask under argon was charged with the 2-bromo-4-oxazol-5-yl-pyridine (Intermediate II-c, 461 mg, 2.07 mmol), 2-methoxy-4-methyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-pyridine V-d (510 mg, 2.07 mmol), K 3 PO 4 (2.82 g, 13.3 mmol), Pd(OAc) 2 (51 mg, 0.225 mmol), Davephos (89 mg, 0.225 mmol) in iPrOH (5 mL) and water (3 mL). After 40 min at 100° C., the mixture was cooled to room temperature, diluted with water and extracted with EtOAc then washed with brine. The organics were dried (MgSO 4 ), filtered and evaporated before purification by column chromatography (SiO 2 , 30% to 100% EtOAc in cyclohexane) to afford the desired product V-e as an off-white solid (240 mg, 43%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.78 (d, J=4.8 Hz, 1H), 8.10 (d, J=4.8 Hz, 1H), 8.01 (s, 1H), 7.59 (d, J=4.9 Hz, 2H), 7.51 (d, J=4.9 Hz, 1H), 6.86 (d, J=4.9 Hz, 1H), 3.88 (s, 3H), 2.16 (s, 3H).
Synthesis of intermediate V-f: 4-(2-Chloro-oxazol-5-yl)-4′-methyl-1′H-[2,3′]bipyridinyl-2′-one
[0278] 4-(2-Chloro-oxazol-5-yl)-4′-methyl-1′H-[2,3]bipyridinyl-2′-one V-f was prepared as for I-d above from 4′-methyl-4-oxazol-5-yl-1H-[2,3′]bipyridinyl-2′-one V-e (467 mg, 1.74 mmol) using LiHMDS (1M in THF, 2.62 mL, 2.62 mmol) and C 2 Cl 6 (496 mg, 2.10 mmol) in dry THF. The crude product was purified by column chromatography (SiO 2 ; eluting with 30% to 50% EtOAc in cyclohexane) to afford the intermediate V-f as white solid (261 mg, 50%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.76 (d, J=5.3 Hz, 1H), 8.12 (d, J=4.4 Hz, 2H), 7.70 (s, 1H), 7.64 (dd, J=5.2, 1.7 Hz, 1H), 7.00 (d, J=5.2 Hz, 1H), 3.78 (s, 3H), 2.06 (s, 3H).
Synthesis of intermediate V-h: 4-(3-Bromo-propoxy)-1-methyl-2-nitro-benzene
[0279] A solution of 4-methyl-3-nitrophenol (1.00 g, 6.53 mmol) in DMF (6 mL) was treated with K 2 CO 3 (0.903 g, 6.53 mmol) and 1,3-dibromopropane (6.63 mL, 65.3 mmol) and heated to 100° C. for 2.5 h. The cooled mixture was diluted with water and extracted with DCM. The combined organics were dried (MgSO 4 ), filtered and evaporated before purification by column chromatography (SiO 2 ; eluting with 20% EtOAc in cyclohexane) to afford the desired product V-h as a mobile yellow oil (1.05 g, 59%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.52 (d, J=2.7 Hz, 1H), 7.23 (d, J=8.5 Hz, 1H), 7.06 (dd, J=8.5, 2.7 Hz, 1H), 4.14 (t, J=5.8 Hz, 2H), 3.60 (t, J=6.4 Hz, 2H), 2.53 (s, 3H), 2.40-2.24 (m, 2H).
Synthesis of intermediate V-i: 4-[3-(4-Methyl-3-nitro-phenoxy)-propyl]-morpholine
[0280] A solution of the 4-(3-bromo-propoxy)-1-methyl-2-nitro-benzene V-h (500 mg, 1.82 mmol) in dry dioxane (30 mL) was treated with K 2 CO 3 (1.01 g, 7.28 mmol) and morpholine (319 μl, 3.65 mmol) and heated to 100° C. for 6 h. The cooled mixture was diluted with water and extracted with DCM. The combined organics were dried (MgSO 4 ), filtered and evaporated before purification by column chromatography (SiO 2 ; eluting with 2% EtOH in DCM) to afford the desired product as a yellow-orange oil V-i (356 mg, 70%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.51 (d, J=2.7 Hz, 1H), 7.21 (d, J=8.5 Hz, 1H), 7.05 (dd, J=8.5, 2.7 Hz, 1H), 4.06 (t, J=6.3 Hz, 2H), 3.79-3.66 (m, 4H), 2.49 (dt, J=9.0, 5.1 Hz, 9H), 2.07-1.88 (m, 2H).
Synthesis of intermediate V-g: 2-Methyl-5-(3-morpholin-4-yl-propoxy)-phenylamine
[0281] A solution of the 4-[3-(4-methyl-3-nitro-phenoxy)-propyl]-morpholine V-i (350 mg, 1.25 mmol) in 90% EtOH (15 mL) was treated with SnCl 2 .H 2 O (1.58 g, 6.24 mmol) and conc. HCl (1.04 mL, 12.5 mmol) and heated to reflux for 1 h. The cooled solution was concentrated under reduced pressure and taken to pH=8 with a saturated solution of NaHCO 3 then extracted with EtOAc. The combined organics were dried (MgSO 4 ), filtered and evaporated to the desired product V-g as a viscous yellow oil (306 mg, 98%). 1 H NMR (300 MHz, CDCl 3 ) δ 6.92 (d, J=8.8 Hz, 1H), 6.30-6.24 (m, 2H), 3.96 (t, J=6.3 Hz, 2H), 3.76-3.69 (m, 4H), 3.58 (s, 2H), 2.57-2.42 (m, 6H), 2.09 (s, 3H), 1.93 (dt, J=13.3, 6.5 Hz, 3H).
Synthesis of example 218: 4′-Methyl-4-{2-[2-methyl-5-(3-morpholin-4-yl-propoxy)-phenylamino]-oxazol-5-yl}-1′H-[2,3′]bipyridinyl-2′-one
[0282] A solution of 4-(2-chloro-oxazol-5-yl)-4′-methyl-1′H-[2,3]bipyridinyl-2′-one V-f (50 mg, 0.159 mmol) in iPrOH (4 mL) was treated with 2-methyl-5-(3-morpholin-4-yl-propoxy)-phenylamine V-g (48 mg, 0.191 mmol) and HCl (2M in ether, 120 μL, 0.240 mmol) and heated to reflux for 18 h. The solution was treated with a further 150 μL of HCl (2M in ether, 150 μL, 0.300 mmol) and heated for a further 2 h. The mixture was cooled to room temperature then the solvent was evaporated under reduced pressure. The residue was treated with ether and the white precipitate was filtered off to afford the compound 218 (31 mg, 39%). 1 H NMR (300 MHz, DMSO) δ 11.62 (s, 1H), 9.40 (s, 1H), 8.55 (d, J=5.3 Hz, 1H), 7.73 (s, 1H), 7.55-7.48 (m, 2H), 7.38 (dd, J=5.2, 1.7 Hz, 1H), 7.29 (d, J=6.7 Hz, 1H), 7.03 (d, J=8.8 Hz, 1H), 6.52 (dd, J=8.3, 2.5 Hz, 1H), 6.13 (d, J=6.7 Hz, 1H), 3.92 (t, J=6.4 Hz, 2H), 3.56-3.44 (m, 4H), 2.40-2.25 (m, 6H), 2.16 (s, 3H), 1.98 (s, 3H), 1.86-1.75 (m, 2H). ESI + MS m/z 502 (M+H) + . Retention time=1.76 min (method 1).
Example 219
Synthetic Approach of Example 219
[0283]
Synthesis of intermediate VI-a: 5-(3-Bromo-phenyl)-oxazole
[0284] 5-(3-Bromo-phenyl)-oxazole VI-a was prepared as described for intermediate I-c using 3-Bromo-benzaldehyde (10 g, 54 mmol), TosMIC (12.7 g, 65 mmol) and K 2 CO 3 (8.97 g) in MeOH to give the desired intermediate VI-a as a brownish solid (12.1 g, 100%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.92 (s, 1H), 7.80 (s, 1H), 7.57 (d, J=7.7 Hz, 1H), 7.46 (d, J=8.0 Hz, 1H), 7.37 (s, 1H), 7.29 (d, J=7.9 Hz, 1H).
Synthesis of intermediate VI-b: 2-Methoxy-3-(3-oxazol-5-yl-phenyl)-1,2-dihydro-pyridine
[0285] A mixture of 5-(3-bromo-phenyl)-oxazole VI-a (1.33 g, 5.94 mmol), 2-methoxy-3-pyridinylboronic acid (1.00 g, 6.53 mmol), Pd(PPh 3 ) 4 and K 2 CO 3 (1.81 g, 13.1 mmol) in THF (20 mL) and water (10 mL) was heated to reflux for 4 h. The mixture was cooled, then diluted with water and extracted with EtOAc. The combined organics were dried (MgSO 4 ), filtered and the residue purified by column chromatography (SiO 2 ; eluting with 30% EtOAc in cyclohexane) to afford the desired product VI-b as brown oil which crystallized on standing (1.37 g, 91%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.18 (dd, J=1.8, 5.0 Hz, 1H), 7.91 (s, 1H), 7.81 (s, 1H), 7.64 (d, J=6.9 Hz, 2H), 7.53-7.44 (m, 2H), 7.37 (s, 1H), 6.99 (dd, J=5.0, 7.2 Hz, 1H), 3.97 (s, 3H).
Synthesis of intermediate VI-c: 3-[3-(2-Chloro-oxazol-5-yl)-phenyl]-2-methoxy-1,2-dihydro-pyridine
[0286] 3-[3-(2-Chloro-oxazol-5-yl)-phenyl]-2-methoxy-pyridine VI-c was prepared as for intermediate I-d above from 2-methoxy-3-(3-oxazol-5-yl-phenyl)-pyridine (1.37 g, 5.43 mmol), LiHMDS (1M in THF, 5.97 mL, 5.97 mmol) and C 2 Cl 6 (1.54 g, 6.52 mmol) in dry THF (50 mL) to give the desired product VI-c as a white solid after purification by column chromatography (SiO 2 ; eluting with 10% to 30% EtOAc in cyclohexane) (1.24 g, 84%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.20 (dd, J=5.0, 1.9 Hz, 1H), 7.76 (t, J=1.6 Hz, 1H), 7.63 (dd, J=7.3, 2.0 Hz, 1H), 7.59-7.45 (m, 3H), 7.31 (s, 1H), 6.99 (dd, J=7.3, 5.0 Hz, 1H), 3.99 (s, 3H).
Synthesis of example 219: 3-{3-[2-(3,5-Dimethoxy-phenylamino)-oxazol-5-yl]-phenyl}-1H-pyridin-2-one
[0287] 3-{3-[2-(3,5-Dimethoxy-phenylamino)-oxazol-5-yl]-phenyl}-1H-pyridin-2-one 219 was prepared as for intermediate I-f above from 3-[3-(2-chloro-oxazol-5-yl)-phenyl]-2-methoxy-pyridine VI-c (40 mg, 0.150 mmol) with 3,5-dimethoxyaniline (29 mg, 0.190 mmol) and HCl (2M in ether, 120 μL, 0.23 mmol) in iPrOH (4 mL). The crude reaction mixture was evaporated under reduced pressure and the residue treated with a saturated solution of NaHCO 3 and EtOAc. A precipitate formed from the biphasic mixture and was filtered off and dried to give the compound 219 product as a beige solid (19 mg, 33%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 11.86 (s, 1H), 10.35 (s, 1H), 7.96 (s, 1H), 7.70 (dd, J=2.0, 6.9 Hz, 1H), 7.60-7.41 (m, 5H), 6.89 (d, J=2.0 Hz, 2H), 6.32 (t, J=6.7 Hz, 1H), 6.13 (s, 1H), 3.73 (s, 6H). ESI + MS m/z 390 (M+H) + . Retention time=3.45 min (method 1).
Example 220
Synthetic Approach of Example 220
[0288]
Synthesis of intermediate VII-a: 2-Fluoro-4-formyl-benzonitrile
[0289] A solution of 4-bromo-2-fluorobenzonitrile (5.00 g, 25 mmol) in dry THF (50 mL) at −10° C. under argon was treated with a solution of isopropylmagnesium chloride (2M in THF, 15.0 mL, 30.0 mmol) dropwise before stirring at this temperature for 3 h. A solution of N-formylpiperidine (3.89 g, 35.0 mmol) in dry THF (15 mL) was added dropwise and the mixture allowed to warm to room temperature before stirring for 1.5 h. The resultant solution was treated with 4M aq HCl (250 mL each) and the organics extracted with EtOAc. The combined organics were dried (MgSO 4 ), filtered and evaporated before purification of the residue by column chromatography (SiO 2 ; eluting with 30% to 50% EtOAc in cyclohexane) to afford 2-fluoro-4-formyl-benzonitrile VII-a as a pale yellow solid (2.73 g, 73%). 1 H NMR (300 MHz, CDCl 3 ) δ 10.07 (d, J=1.7 Hz, 1H), 7.90-7.79 (m, 2H), 7.74 (dd, J=8.5, 0.8 Hz, 1H).
Synthesis of intermediate VII-b: 2-Fluoro-4-oxazol-5-yl-benzonitrile
[0290] 5-(3-Bromo-phenyl)-oxazole VII-b was prepared as described for intermediate I-c using 2-Fluoro-4-formyl-benzonitrile VII-a (2 g, 13.43 mmol), TosMIC (2.85 g, 14.77 mmol) and K 2 CO 3 (2.41 g, 1.86 mmol) in MeOH (40 mL) to give the desired intermediate VII-b as a yellow solid (1.46 g, 58%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.94 (s, 1H), 7.62 (dd, J=8.0, 6.5 Hz, 1H), 7.52-7.37 (m, 3H).
Synthesis of intermediate VII-c: 2-(3-Methyl-2-oxo-2H-pyridin-1-yl)-4-oxazol-5-yl-benzonitrile
[0291] A solution of 3-methyl-1H-pyridin-2-one (1.43 g, 13.1 mmol) in absolute EtOH (100 mL) was treated with KOH (735 mg, 13.1 mmol) and heated to reflux with vigorous stirring for 2 h before cooling to room temperature and evaporation of the solvent under reduced pressure. The orange solid residue was taken up in dry DMF (100 mL) and treated with 2-fluoro-4-oxazol-5-yl-benzonitrile VII-b (2.24 g, 11.9 mmol) and stirred at 100° C. for 3 h. The solvent was evaporated under reduced pressure and the residue treated with a saturated solution of NaHCO 3 and extracted with DCM. The combined organics were dried (MgSO 4 ), filtered and evaporated and the residue purified by column chromatography (SiO 2 , eluting with 50% EtOAc in cyclohexane) to give the desired intermediate VII-c as an off-white solid (2.55 g, 77%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.62 (s, 1H), 8.15 (d, J=8.1 Hz, 1H), 8.04 (s, 2H), 7.99 (dd, J=8.1, 1.6 Hz, 1H), 7.62 (dd, J=6.9, 1.1 Hz, 1H), 7.49 (d, J=6.6 Hz, 1H), 6.34 (t, J=6.8 Hz, 1H), 2.07 (s, 3H).
Synthesis of intermediate VII-d: 4-(2-Chloro-oxazol-5-yl)-2-(3-methyl-2-oxo-2H-pyridin-1-yl)-benzonitrile
[0292] A solution of the 2-(3-methyl-2-oxo-2H-pyridin-1-yl)-4-oxazol-5-yl-benzonitrile VII-c (2.55 g, 9.19 mmol) in dry distilled THF (160 mL) at −78° C. under argon was treated dropwise with LiHMDS (1M in THF, 11.0 mL, 11.0 mmol) to give an opaque yellow slurry. After 1 h at this temperature, C 2 Cl 6 (3.26 g, 13.8 mmol) was added in one portion and the mixture was allowed to warm to room temperature. This mixture was treated with water and extracted with DCM. The combined organics were dried (MgSO 4 ), filtered and evaporated and the residue purified by column chromatography (SiO 2 ; eluting with 50% EtOAc in cyclohexane) to give the desired product VII-d as a pink solid (1.51 g, 52%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.16 (d, J=8.2 Hz, 1H), 8.10 (s, 1H), 8.02 (d, J=1.4 Hz, 1H), 7.96 (dd, J=8.1, 1.5 Hz, 1H), 7.61 (d, J=6.9 Hz, 1H), 7.49 (d, J=6.7 Hz, 1H), 6.35 (t, J=6.8 Hz, 1H), 2.07 (s, 3H).
Synthesis of intermediate VII-e: N-(5-ethoxymethyl-2-methyl-phenyl)-acetamide
[0293] N-(5-ethoxymethyl-2-methyl-phenyl)-acetamide VII-e was prepared as described for intermediate II-i using 5-ethoxymethyl-2-methyl-phenylamine I-e (5 g, 30.26 mmol), dry triethylamine (12.23 mL), DCM (60 mL) and AcCl (4.32 mL) to give the desired intermediate VII-e as a white solid (5.39 g, 86%). 1 H NMR (300 MHz, CDCl 3 ) δ 7.69 (s, 1H), 7.15 (d, J=7.7 Hz, 1H), 7.07 (d, J=8.2 Hz, 1H), 4.46 (s, 2H), 3.53 (q, J=7.0 Hz, 2H), 2.23 (s, 3H), 2.18 (s, 3H), 1.23 (t, J=7.0 Hz, 3H).
Synthesis of example 220: 4-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-2-(3-methyl-2-oxo-2H-pyridin-1-yl)-benzonitrile
[0294] A mixture of N-(5-ethoxymethyl-2-methyl-phenyl)-acetamide VII-e (74 mg, 0.361 mmol), dry THF (3 mL) and NaH (60% in oil, 29 mg 0.722 mmol) under argon was stirred at room temperature for 1 h. A suspension of 4-(2-chloro-oxazol-5-yl)-2-(3-methyl-2-oxo-2H-pyridin-1-yl)-benzonitrile VII-d (75 mg, 0.241 mmol) in dry THF (3 mL) was added dropwise at 0° C. before warming to room temperature over 2 h. The mixture was treated with water, and extracted with EtOAc. The combined organics were dried (MgSO 4 ), filtered and evaporated and the residue purified by column chromatography (SiO 2 ; eluting with 50% EtOAc in cyclohexane) to give the desired product 220 as a pink solid (61 mg, 56%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.55 (s, 1H), 8.05 (d, J=8.0 Hz, 1H), 7.83-7.68 (m, 4H), 7.61 (d, J=6.7 Hz, 1H), 7.48 (d, J=6.6 Hz, 1H), 7.18 (d, J=7.8 Hz, 1H), 6.97 (d, J=7.4 Hz, 1H), 6.33 (t, J=6.8 Hz, 1H), 4.41 (s, 2H), 3.46 (q, J=7.0 Hz, 2H), 2.27 (s, 3H), 2.06 (d, J=7.1 Hz, 3H), 1.12 (t, J=7.0 Hz, 3H).
Example 221
Synthetic Approach of Example 221
[0295]
Synthesis of intermediate VIII-a: 3-Bromo-5-oxazol-5-yl-pyridine
[0296] 5-(3-Bromo-phenyl)-oxazole VIII-a was prepared as described for intermediate I-c using 2-5-bromo-pyridine-3-carbaldehyde (0.260 g, 1.4 mmol), TosMIC (0.273 g, 1.54 mmol) and K 2 CO 3 (0.580 g, 4.2 mmol) in MeOH (15 mL) to give the desired intermediate VIII-a as a beige solid (0.16 g, 50%). 1 H NMR (300 MHz, DMSO) δ 8.95 (s, 1H), 8.70 (s, 1H), 8.59 (s, 1H), 8.43 (s, 1H), 7.95 (s, 1H).
Synthesis of intermediate VIII-b: 5′-Oxazol-5-yl-[1,3′]bipyridinyl-2-one
[0297] To an oven-dried sealed tube containing a solution of 3-bromo-5-oxazol-5-yl-pyridine VIII-a (1.00 g, 4.44 mol) in degassed 1,4-dioxane (20 mL) was added 2-hydroxypyridine (507 mg, 5.33 mmol), K 2 CO 3 (1.23 g, 1.78 mmol), Cut (169 mg, 0.899 mmol) and rac-trans-N,N′-dimethylcyclohexane diamine (280 μL, 1.78 mmol). The tube was flushed with argon and sealed then heated in an oil bath at 120° C. overnight. After cooling to RT, the mixture was filtered and the filter cake washed with 1,4-dioxane. The mixture was evaporated and the residue purified by column chromatography (2% to 5% EtOH in DCM) to give the desired product VIII-b as a beige solid (752 mg, 71%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.06 (s, 1H), 8.68 (s, 1H), 8.60 (s, 1H), 8.29 (s, 1H), 7.95 (s, 1H), 7.80 (dd, J=6.8, 1.6 Hz, 1H), 7.57 (ddd, J=8.8, 6.6, 1.9 Hz, 1H), 6.54 (d, J=9.2 Hz, 1H), 6.39 (t, J=6.7 Hz, 1H).
Synthesis of intermediate VIII-c: 5′-(2-Chloro-oxazol-5-yl)-[1,3]bipyridinyl-2-one
[0298] 5′-(2-Chloro-oxazol-5-yl)-[1,3′]bipyridinyl-2-one VIII-c was prepared as described for I-d above from 5′-oxazol-5-yl-[1,3′]bipyridinyl-2-one VIII-d (740 mg, 3.09 mmol) using LiHMDS (1M in THF, 4.64 mL, 4.64 mmol) and C 2 Cl 6 (1.10 g, 4.64 mmol) in dry THF. The crude product was purified by column chromatography (SiO 2 ; eluting with 2% to 5% EtOH in DCM) to afford the desired product VIII-c as a white solid (393 mg, 47%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.91 (s, 1H), 8.61 (s, 1H), 8.06 (t, J=2.2 Hz, 1H), 7.50-7.42 (m, 2H), 7.35 (dd, J=6.9, 1.9 Hz, 1H), 6.70 (d, J=9.3 Hz, 1H), 6.34 (td, J=6.8, 1.2 Hz, 1H).
Synthesis of example 221: 5′-[2-(5-Methoxy-2-methyl-phenylamino)-oxazol-5-yl]-[1,3]bipyridinyl-2-one
[0299] 5′-[2-(5-Methoxy-2-methyl-phenylamino)-oxazol-5-yl]-[1,3′]bipyridinyl-2-one 221 was prepared as described for I-f above from 5′-(2-Chloro-oxazol-5-yl)-[1,3′]bipyridinyl-2-one VIII-c (68 mg, 0.250 mmol), and 5-methoxy-2-methylaniline (35 mg, 0.250 mmol) in iPrOH (3 mL) to afford the title compound 221 after column chromatography (SiO 2 ; eluting with 2% to 5% EtOH in DCM) as an orange solid (28 mg, 30%). (300 MHz, CDCl 3 ) δ 8.83 (d, J=1.9 Hz, 1H), 8.45 (d, J=2.3 Hz, 1H), 7.93 (t, J=2.1 Hz, 1H), 7.73 (d, J=2.4 Hz, 1H), 7.41 (m, 1H), 7.34 (m, 1H), 7.30 (s, 1H), 7.07 (d, J=8.3 Hz, 1H), 6.78 (s, 1H), 6.68 (d, J=9.3 Hz, 1H), 6.55 (dd, J=8.3, 2.5 Hz, 1H), 6.30 (t, J=5.6 Hz, 1H), 3.81 (s, 3H), 2.25 (s, 3H). ESL MS m/z 375 (M+H) + . Retention time=2.99 min (method 1).
Example 222
Synthesis of example 222: 3-{3-[2-(3,5-Dimethoxy-phenylamino)-oxazol-5-yl]-phenyl}-1-(2-dimethylamino-ethyl)-1H-pyridin-2-one
[0300]
[0301] A mixture of 3-{3-[2-(3,5-Dimethoxy-phenylamino)-oxazol-5-yl]-phenyl}-1H-pyridin-2-one 219 (39 mg, 0.10 mmol), (2-chloro-ethyl)-dimethyl-amine hydrochloride (17.5 mg, 0.11 mmol), K 2 CO 3 (31 mg, 0.22 mmol) and potassium iodide (19 mg, 0.11 mmol) in DMF (4 mL) was heated at 50° C. for 16 h. After evaporation of DMF, the mixture was treated with water and extracted with EtOAc. The combined organics were dried (MgSO 4 ), filtered and evaporated and the residue purified by column chromatography (Al 2 O 3 ; eluting with 1% EtOH in DCM) to give the desired product 222 as a yellow solid (23 mg, 50%). 1 H NMR (300 MHz, DMSO) δ 10.32 (s, 1H), 7.95 (s, 1H), 7.72 (d, J=6.7 Hz, 1H), 7.66 (dd, J=6.9, 1.6 Hz, 1H), 7.58-7.31 (m, 4H), 6.90 (s, 1H), 6.89 (s, 1H), 6.35 (t, J=6.8 Hz, 1H), 6.13 (s, 1H), 4.07 (t, J=6.3 Hz, 2H), 3.73 (s, 6H), 2.55 (t, J=6.3 Hz, 2H), 2.20 (s, 6H). ESL MS m/z 461 (M+H) + . Retention time=2.90 min (method 1).
Example 223
Synthetic Approach of Example 223
[0302]
Synthesis of intermediate IX-a: 2-Bromo-4-(2-chloro-oxazol-5-yl)-pyridine
[0303] 2-Bromo-4-(2-chloro-oxazol-5-yl)-pyridine IX-a was prepared as for example I-d using 2-Bromo-4-oxazol-5-yl-pyridine (450 mg, 2 mmol), LiHMDS (2.2 mL, 2.2 mmol) and C 2 Cl 6 (568 mg, 2.4 mmol) in THF to give intermediate IX-a as a yellow-orange solid (465 mg, 90%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.43 (d, J=5.1 Hz, 1H), 7.68 (s, 1H), 7.53 (s, 1H), 7.46-7.36 (m, 1H).
Synthesis of intermediate IX-b: [5-(2-Bromo-pyridin-4-yl)-oxazol-2-yl]-(5-ethoxymethyl-2-methyl-phenyl)-amine
[0304] [5-(2-Bromo-pyridin-4-yl)-oxazol-2-yl]-(5-ethoxymethyl-2-methyl-phenyl)-amine IX-b was prepared as for example 220 using intermediate VII-e (169 mg, 0.65 mmol), N-(5-ethoxymethyl-2-methyl-phenyl)-acetamide (162 mg, 0.78 mmol) and NaH (65 mg, 1.6 mmol) in DMF to give intermediate IX-b as a yellow solid (162 mg, 64%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.32 (d, J=5.1 Hz, 1H), 7.94 (s, 1H), 7.56 (s, 1H), 7.42 (s, 1H), 7.32 (d, J=5.2 Hz, 1H), 7.21 (d, J=7.6 Hz, 1H), 7.06 (d, J=7.7 Hz, 1H), 6.91 (s, 1H), 4.54 (s, 2H), 3.58 (q, J=7.0 Hz, 2H), 2.34 (s, 3H), 1.27 (t, J=7.0 Hz, 3H).
Synthesis of example 223: 4′-[2-(5-Ethoxymethyl-2-methyl-phenylamino)-oxazol-5-yl]-3,4,5,6-tetrahydro-[1,2′]bipyridinyl-2-one
[0305] A mixture of intermediate IX-b (51 mg, 0.13 mmol), δ-valerolactam (16 mg, 0.16 mmol), cesium carbonate (60 mg, 0.18 mmol), Pd 2 (dba) 3 (4 mg, 0.004 mmol) and XantPhos (7 mg, 0.012 mmol) in dioxane (2.5 mL) was refluxed for 1 h, until no starting material remained (reaction monitored by TLC). The reaction mixture was then evaporated, and the crude oil was directly chromatographed (SiO 2 , eluting with 1 to 10% EtOH in DCM) to give example 223 as a yellow solid (22 mg, 42%). 1 H NMR (300 MHz, CDCl 3 ) δ 8.39 (d, J=5.3 Hz, 1H), 7.99 (s, 1H), 7.94 (s, 1H), 7.39 (s, 1H), 7.25-7.12 (m, 3H), 7.05 (d, J=7.6 Hz, 1H), 4.54 (s, 2H), 4.02-3.89 (m, 2H), 3.57 (q, J=6.9 Hz, 2H), 2.69-2.56 (m, 2H), 2.34 (s, 3H), 2.02-1.89 (m, 4H), 1.26 (t, J=7.0 Hz, 3H). ESL MS m/z 407 (M+H) + . Retention time=3.48 min (method 1).
Example 224
Synthesis of example 224: 1-{4-[2-((5-Ethoxymethyl)-2-methyl-phenylamino)-oxazol-5-yl]-pyridin-2-yl}-tetrahydro-pyrimidin-2-one
[0306]
[0307] A mixture of intermediate IX-b (50 mg, 0.13 mmol), N,N′-trimethyleneurea (130 mg, 1.3 mmol), cesium carbonate (46 mg, 0.14 mmol), Pd 2 (dba) 3 (4 mg, 0.004 mmol) and XantPhos (7 mg, 0.012 mmol) in dioxane (2.5 mL) was refluxed for 1 h30. The reaction mixture was then evaporated, dissolved in ethyl acetate, washed several times with water, dried over MgSO 4 , and concentrated. The crude oil was chromatographed (SiO 2 , eluting with 1 to 10% EtOH in DCM) to give example 224 as a yellow-orange solid (16 mg, 31%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.54 (s, 1H), 8.28 (d, J=5.2 Hz, 1H), 7.99 (s, 1H), 7.79 (s, 1H), 7.66 (s, 1H), 7.24-7.10 (m, 2H), 7.00-6.86 (m, 2H), 4.41 (s, 2H), 3.92-3.80 (m, 2H), 3.47 (q, J=6.9 Hz, 2H), 3.26-3.19 (m, 2H), 2.27 (s, 3H), 2.03-1.80 (m, 2H), 1.14 (t, J=7.0 Hz, 3H).
Example 225
Synthetic Approach of Example 225
[0308]
Synthesis of intermediate X-a: 5-(3-Nitro-phenyl)-oxazole
[0309] Intermediate X-a was prepared as for example I-c using 3-nitrobenzaldehyde (4 g, 26 mmol), TosMIC (5.7 g, 29 mmol) and K 2 CO 3 (4.4 g, 32 mmol) in MeOH to give intermediate X-a as a yellow solid (4.7 g, 93%). 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.56 (s, 1H), 8.50 (t, J=1.9 Hz, 1H), 8.21 (ddd, J=8.2, 2.3, 1.0 Hz, 1H), 8.17 (ddd, J=7.8, 1.6, 1.0 Hz, 1H), 7.99 (s, 1H), 7.78 (t, J=8.0 Hz, 1H).
Synthesis of intermediate X-b: 2-Chloro-5-(3-nitro-phenyl)-oxazole
[0310] Intermediate X-b was prepared as for example I-d using intermediate X-a (3.2 g, 17 mmol), LiHMDS (20.2 mL, 20 mmol) and C 2 Cl 6 (4.78 g, 20 mmol) in THF to give the desired intermediate X-b as a yellow solid (3.13 g, 82%). 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.48 (d, J=1.5 Hz, 1H), 8.24 (d, J=8.2 Hz, 1H), 8.14 (d, J=7.8 Hz, 1H), 8.09 (d, J=1.9 Hz, 1H), 7.80 (td, J=8.1, 1.9 Hz, 1H).
Synthesis of intermediate X-c: 4-Methyl-N3-[5-(3-nitro-phenyl)-oxazol-2-yl]-benzene-1,3-diamine
[0311] Intermediate X-c was prepared as for example 220 using intermediate X-b (448 mg, 2 mmol), N-(5-Amino-2-methyl-phenyl)-acetamide (394 mg, 2.4 mmol) and NaH (160 mg, 4 mmol) in THF to give intermediate X-c as an orange solid (236 mg, 64%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.17 (s, 1H), 8.32 (s, 1H), 8.07 (d, J=7.5 Hz, 1H), 8.00 (d, J=7.7 Hz, 1H), 7.72 (m, 2H), 7.11 (s, 1H), 6.82 (d, J=8.0 Hz, 1H), 6.24 (d, J=7.4 Hz, 1H), 4.91 (s, 2H), 2.11 (s, 3H).
Synthesis of intermediate X-d: N-{4-Methyl-3-[5-(3-nitro-phenyl)-oxazol-2-ylamino]-phenyl}-2-pyrrolidin-1-yl-acetamide
[0312] A mixture of intermediate X-c (226 mg, 0.72 mmol), 1-pyrrolidinyl acetic acid hydrochloride (158 mg, 0.94 mmol), 1-hydroxybenzotriazole hydrate (148 mg, 1.1 mmol), N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (252 mg, 1.3 mmol) and NEt 3 (360 μL, 2.6 mmol) in DMF (15 mL) was stirred at room temperature overnight. The reaction mixture was then evaporated, diluted with ethyl acetate, washed with water, dried over MgSO 4 , and concentrated to a minimum volume for allowing crystallisation. The title compound was then collected by filtration to afford intermediate X-d as a yellow solid (224 mg, 72%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.66 (s, 1H), 9.43 (s, 1H), 8.35 (s, 1H), 8.03 (d, J=7.3 Hz, 1H), 7.89 (d, J=7.9 Hz, 1H), 7.70 (m, 2H), 7.04 (s, 1H), 6.89 (d, J=8.1 Hz, 1H), 6.26 (d, J=7.5 Hz, 1H), 3.24 (s, 2H), 2.63-2.54 (m, 4H), 2.22 (s, 3H), 1.76-1.69 (m, 4H).
Synthesis of intermediate X-e: N-{3-[5-(3-Amino-phenyl)-oxazol-2-ylamino]-4-methyl-phenyl}-2-pyrrolidin-1-yl-acetamide
[0313] A mixture of intermediate X-d (220 mg, 0.52 mmol), SnCl 2 .2H 2 O (590 mg, 2.6 mmol) and concentrated hydrochloric acid (735 μL, 5.2 mmol) in a mixture ethanol/eau (9 mL/1 mL) was stirred at 40° C. for 4 h. The reaction mixture was then evaporated, diluted with ethyl acetate and aqueous NaOH. The aqueous layer was extracted twice with ethyl acetate, then the combined organic layers were washed with water, dried over MgSO 4 , and concentrated. The crude oil was chromatographed (Al 2 O 3 , eluting with 0.5% EtOH in DCM) to give intermediate X-e as a yellow-beige solid (147 mg, 72%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.68 (s, 1H), 9.40 (s, 1H), 8.21 (s, 1H), 7.95 (d, J=7.8 Hz, 1H), 7.88 (d, J=7.3 Hz, 1H), 7.56 (s, 1H), 7.32 (s, 1H), 7.05 (s, 1H), 6.91 (d, J=7.3 Hz, 1H), 6.19 (d, J=7.6 Hz, 1H), 4.85 (s, 2H), 3.28 (s, 2H), 2.67-2.56 (m, 4H), 2.23 (s, 3H), 1.78-1.68 (m, 4H).
Synthesis of example 225: N-(3-{5-[3-(2,6-Dioxo-piperidin-1-yl)-phenyl]-oxazol-2-ylamino}-4-methyl-phenyl)-2-pyrrolidin-1-yl-acetamide
[0314] To a solution of intermediate X-e (70 mg, 0.18 mmol) in anhydrous THF (4 mL) under argon at 0° C. was added glutaric anhydride (20 mg, 0.18 mmol) in several portions. The mixture was stirred at ambient temperature for 1 h, then refluxed overnight. The solid formed was collected by filtration, then washed with THF and diethyl ether, to give a white solid (52 mg), which was treated in anhydrous 1,2-dichloroethane (8 mL) with SOCl 2 (30 μL, 0.4 mmol) over a period of 10 min. The mixture was refluxed for at least 4 h, until no starting material remained, then diluted with DCM, washed with aqueous NaHCO 3 and water, dried over MgSO 4 , and concentrated. The residue was chromatographed (Al 2 O 3 , eluting with 0.5 to 1% EtOH in DCM) to give compound 225 as a beige solid (23 mg, 45%). 1 H NMR (300 MHz, DMSO-d 6 ) δ 9.96 (s, 1H), 9.64 (s, 1H), 9.27 (d, J=12.2 Hz, 1H), 8.03 (d, J=10.9 Hz, 1H), 7.94 (s, 1H), 7.54-7.46 (m, 1H), 7.35-7.27 (m, 3H), 7.10 (d, J=8.2 Hz, 1H), 3.23 (s, 2H), 2.69 (t, J=6.5 Hz, 4H), 2.63-2.56 (m, 4H), 2.23 (s, 3H), 2.12 (m, 2H), 1.74 (s, 4H).
[0315] In another embodiment, the invention relates to a pharmaceutical composition comprising a compound as depicted above.
[0316] Such a pharmaceutical composition can be adapted for oral administration, and can be formulated using pharmaceutically acceptable carriers well known in the art in suitable dosages. Such carriers enable the pharmaceutical compositions to be formulated as tablets, pills, dragees, capsules, liquids, gels, syrups, slurries, suspensions, and the like, for ingestion by the patient. In addition to the active ingredients, these pharmaceutical compositions may contain suitable pharmaceutically-acceptable carriers comprising excipients and auxiliaries which facilitate processing of the active compounds into preparations which can be used pharmaceutically. Further details on techniques for formulation and administration may be found in the latest edition of Remington's Pharmaceutical Sciences (Maack Publishing Co., Easton, Pa.).
[0317] The composition of the invention can also take the form of a pharmaceutical or cosmetic composition for topical administration.
[0318] Such compositions may be presented in the form of a gel, paste, ointment, cream, lotion, liquid suspension aqueous, aqueous-alcoholic or, oily solutions, or dispersions of the lotion or serum type, or anhydrous or lipophilic gels, or emulsions of liquid or semi-solid consistency of the milk type, obtained by dispersing a fatty phase in an aqueous phase or vice versa, or of suspensions or emulsions of soft, semi-solid consistency of the cream or gel type, or alternatively of microemulsions, of microcapsules, of microparticles or of vesicular dispersions to the ionic and/or nonionic type. These compositions are prepared according to standard methods.
[0319] The composition according to the invention comprises any ingredient commonly used in dermatology and cosmetic. It may comprise at least one ingredient selected from hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preservatives, emollients, viscosity enhancing polymers, humectants, surfactants, preservatives, antioxidants, solvents, and fillers, antioxidants, solvents, perfumes, fillers, screening agents, bactericides, odor absorbers and coloring matter.
[0320] As oils which can be used in the invention, mineral oils (liquid paraffin), vegetable oils (liquid fraction of shea butter, sunflower oil), animal oils, synthetic oils, silicone oils (cyclomethicone) and fluorinated oils may be mentioned. Fatty alcohols, fatty acids (stearic acid) and waxes (paraffin, carnauba, beeswax) may also be used as fatty substances.
[0321] As emulsifiers, glycerols, polysorbates, glycerides, and PEGs can be used in the invention.
[0322] As hydrophilic gelling agents, carboxyvinyl polymers (carbomer), acrylic copolymers such as acrylate/alkylacrylate copolymers, polyacrylamides, polysaccharides such as hydroxypropylcellulose, clays and natural gums may be mentioned, and as lipophilic gelling agents, modified clays such as bentones, metal salts of fatty acids such as aluminum stearates and hydrophobic silica, or alternatively ethylcellulose and polyethylene may be mentioned.
[0323] As hydrophilic active agents, proteins or protein hydrolysates, amino acids, polyols, urea, allantoin, sugars and sugar derivatives, vitamins, starch and plant extracts, in particular those of Aloe vera may be used.
[0324] As lipophilic active, agents, retinol (vitamin A) and its derivatives, tocopherol (vitamin E) and its derivatives, essential fatty acids, ceramides and essential oils may be used. These agents add extra moisturizing or skin softening features when utilized.
[0325] In addition, a surfactant can be included in the composition so as to provide deeper penetration of the compound capable of depleting mast cells, such as a tyrosine kinase inhibitor, preferably a c-kit inhibitor.
[0326] Among the contemplated ingredients, the invention embraces penetration enhancing agents selected for example from the group consisting of mineral oil, water, ethanol, triacetin, glycerin and propylene glycol; cohesion agents selected for example from the group consisting of polyisobutylene, polyvinyl acetate and polyvinyl alcohol, and thickening agents.
[0327] Chemical methods of enhancing topical absorption of drugs are well known in the art. For example, compounds with penetration enhancing properties include sodium lauryl sulfate (Dugard, P. H. and Sheuplein, R. J., “Effects of Ionic Surfactants on the Permeability of Human Epidermis An Electrometric Study,” J. West. Dermatol., V.60, pp. 263-69, 1973), lauryl amine oxide (Johnson et. al., U.S. Pat. No. 4,411,893), azone (Rajadhyaksha, U.S. Pat. Nos. 4,405,616 and 3,989,816) and decylmethyl sulfoxide (Sekura, D. L. and Scala, J., “The Percutaneous Absorption of Alkylmethyl Sulfides,” Pharmacology of the Skin, Advances In Biolocy of Skin, (Appleton-Century Craft) V. 12, pp. 257-69, 1972). It has been observed that increasing the polarity of the head group in amphoteric molecules increases their penetration-enhancing properties but at the expense of increasing their skin irritating properties (Cooper, E. R. and Berner, B., “Interaction of Surfactants with Epidermal Tissues: Physiochemical Aspects,” Surfactant Science Series, V. 16, Reiger, M. M. ed. (Marcel Dekker, Inc.) pp. 195-210, 1987).
[0328] A second class of chemical enhancers are generally referred to as co-solvents. These materials are absorbed topically relatively easily, and, by a variety of mechanisms, achieve permeation enhancement for some drugs. Ethanol (Gale et. al., U.S. Pat. No. 4,615,699 and Campbell et. al., U.S. Pat. Nos. 4,460,372 and 4,379,454), dimethyl sulfoxide (U.S. Pat. Nos. 3,740,420 and 3,743,727, and U.S. Pat. No. 4,575,515), and glycerine derivatives (U.S. Pat. No. 4,322,433) are a few examples of compounds which have shown an ability to enhance the absorption of various compounds.
[0329] The pharmaceutical compositions of the invention can also be intended for administration as an aerosolized formulation to target areas of a patient's respiratory tract.
[0330] Devices and methodologies for delivering aerosolized bursts of a formulation of a drug is disclosed in U.S. Pat. No. 5,906,202. Formulations are preferably solutions, e.g. aqueous solutions, ethanoic solutions, aqueous/ethanoic solutions, saline solutions, colloidal suspensions and microcrystalline suspensions. For example aerosolized particles comprise the active ingredient mentioned above and a carrier, (e.g., a pharmaceutically active respiratory drug and carrier) which are formed upon forcing the formulation through a nozzle which nozzle is preferably in the form of a flexible porous membrane. The particles have a size which is sufficiently small such that when the particles are formed they remain suspended in the air for a sufficient amount of time such that the patient can inhale the particles into the patient's lungs.
[0331] The invention encompasses the systems described in U.S. Pat. No. 5,556,611:
liquid gas systems (a liquefied gas is used as propellent gas (e.g. low-boiling FCHC or propane, butane) in a pressure container, suspension aerosol (the active substance particles are suspended in solid form in the liquid propellent phase), pressurized gas system (a compressed gas such as nitrogen, carbon dioxide, dinitrogen monoxide, air is used.
[0335] Thus, according to the invention the pharmaceutical preparation is made in that the active substance is dissolved or dispersed in a suitable nontoxic medium and said solution or dispersion atomized to an aerosol, i.e. distributed extremely finely in a carrier gas. This is technically possible for example in the form of aerosol propellent gas packs, pump aerosols or other devices known per se for liquid misting and solid atomizing which in particular permit an exact individual dosage.
[0336] Therefore, the invention is also directed to aerosol devices comprising the compound as defined above and such a formulation, preferably with metered dose valves.
[0337] The pharmaceutical compositions of the invention can also be intended for intranasal administration.
[0338] In this regard, pharmaceutically acceptable carriers for administering the compound to the nasal mucosal surfaces will be readily appreciated by the ordinary artisan. These carriers are described in the Remington's Pharmaceutical Sciences” 16th edition, 1980, Ed. By Arthur Osol, the disclosure of which is incorporated herein by reference.
[0339] The selection of appropriate carriers depends upon the particular type of administration that is contemplated. For administration via the upper respiratory tract, the composition can be formulated into a solution, e.g., water or isotonic saline, buffered or unbuffered, or as a suspension, for intranasal administration as drops or as a spray. Preferably, such solutions or suspensions are isotonic relative to nasal secretions and of about the same pH, ranging e.g., from about pH 4.0 to about pH 7.4 or, from pH 6.0 to pH 7.0. Buffers should be physiologically compatible and include, simply by way of example, phosphate buffers. For example, a representative nasal decongestant is described as being buffered to a pH of about 6.2 (Remington's, Id. at page 1445). Of course, the ordinary artisan can readily determine a suitable saline content and pH for an innocuous aqueous carrier for nasal and/or upper respiratory administration.
[0340] Common intranasal carriers include nasal gels, creams, pastes or ointments with a viscosity of, e.g., from about 10 to about 3000 cps, or from about 2500 to 6500 cps, or greater, may also be used to provide a more sustained contact with the nasal mucosal surfaces. Such carrier viscous formulations may be based upon, simply by way of example, alkylcelluloses and/or other biocompatible carriers of high viscosity well known to the art (see e.g., Remington's, cited supra. A preferred alkylcellulose is, e.g., methylcellulose in a concentration ranging from about 5 to about 1000 or more mg per 100 ml of carrier. A more preferred concentration of methyl cellulose is, simply by way of example, from about 25 to about mg per 100 ml of carrier.
[0341] Other ingredients, such as art known preservatives, colorants, lubricating or viscous mineral or vegetable oils, perfumes, natural or synthetic plant extracts such as aromatic oils, and humectants and viscosity enhancers such as, e.g., glycerol, can also be included to provide additional viscosity, moisture retention and a pleasant texture and odor for the formulation. For nasal administration of solutions or suspensions according to the invention, various devices are available in the art for the generation of drops, droplets and sprays.
[0342] A premeasured unit dosage dispenser including a dropper or spray device containing a solution or suspension for delivery as drops or as a spray is prepared containing one or more doses of the drug to be administered and is another object of the invention. The invention also includes a kit containing one or more unit dehydrated doses of the compound, together with any required salts and/or buffer agents, preservatives, colorants and the like, ready for preparation of a solution or suspension by the addition of a suitable amount of water.
[0343] Another aspect of the invention is directed to the use of said compound to manufacture a medicament. In other words, the invention embraces a method for treating a disease related to unregulated c-kit transduction comprising administering an effective amount of a compound as defined above to a mammal in need of such treatment.
[0344] More particularly, the invention is aimed at a method for treating a disease selected from autoimmune diseases, allergic diseases, bone loss, cancers such as leukemia and GIST, tumor angiogenesis, inflammatory diseases, inflammatory bowel diseases (IBD), interstitial cystitis, mastocytosis, infections diseases, metabolic disorders, fibrosis, diabetes and CNS disorders comprising administering an effective amount a compound depicted above to a mammal in need of such treatment.
[0345] The above described compounds are useful for manufacturing a medicament for the treatment of diseases related to unregulated c-kit transduction, including, but not limited to:
neoplastic diseases such as mastocytosis, canine mastocytoma, solid tumours, human gastrointestinal stromal tumor (“GIST”), small cell lung cancer, non-small cell lung cancer, acute myelocytic leukemia, acute lymphocytic leukemia, myelodysplastic syndrome, chronic myelogenous leukemia, colorectal carcinomas, gastric carcinomas, gastrointestinal stromal tumors, testicular cancers, glioblastomas, solid tumors and astrocytomas. tumor angiogenesis. metabolic diseases such as diabetes mellitus and its chronic complications; obesity; diabete type II; hyperlipidemias and dyslipidemias; atherosclerosis; hypertension; and cardiovascular disease. allergic diseases such as asthma, allergic rhinitis, allergic sinusitis, anaphylactic syndrome, urticaria, angioedema, atopic dermatitis, allergic contact dermatitis, erythema nodosum, erythema multiforme, cutaneous necrotizing venulitis and insect bite skin inflammation and blood sucking parasitic infestation. interstitial cystitis. bone loss (osteoporosis). inflammatory diseases such as rheumatoid arthritis, conjunctivitis, rheumatoid spondylitis, osteoarthritis, gouty arthritis and other arthritic conditions. autoimmune diseases such as multiple sclerosis, psoriasis, intestine inflammatory disease, ulcerative colitis, Crohn's disease, rheumatoid arthritis and polyarthritis, local and systemic scleroderma, systemic lupus erythematosus, discoid lupus erythematosus, cutaneous lupus, dermatomyositis, polymyositis, Sjogren's syndrome, nodular panarteritis, autoimmune enteropathy, as well as proliferative glomerulonephritis. graft-versus-host disease or graft rejection in any organ transplantation including kidney, pancreas, liver, heart, lung, and bone marrow. Other autoimmune diseases embraced by the invention active chronic hepatitis and chronic fatigue syndrome. subepidermal blistering disorders such as pemphigus. Vasculitis. HIV infection. melanocyte dysfunction associated diseases such as hypermelanosis resulting from melanocyte dysfunction and including lentigines, solar and senile lentigo, Dubreuilh melanosis, moles as well as malignant melanomas. In this regard, the invention embraces the use of the compounds defined above to manufacture a medicament or a cosmetic composition for whitening human skin. CNS disorders such as psychiatric disorders, migraine, pain, memory loss and nerve cells degeneracy. More particularly, the method according to the invention is useful for the treatment of the following disorders: Depression including dysthymic disorder, cyclothymic disorder, bipolar depression, severe or “melancholic” depression, atypical depression, refractory depression, seasonal depression, anorexia, bulimia, premenstrual syndrome, post-menopause syndrome, other syndromes such as mental slowing and loss of concentration, pessimistic worry, agitation, self-deprecation, decreased libido, pain including, acute pain, postoperative pain, chronic pain, nociceptive pain, cancer pain, neuropathic pain, psychogenic pain syndromes, anxiety disorders including anxiety associated with hyperventilation and cardiac arrhythmias, phobic disorders, obsessive-compulsive disorder, posttraumatic stress disorder, acute stress disorder, generalized anxiety disorder, psychiatric emergencies such as panic attacks, including psychosis, delusional disorders, conversion disorders, phobias, mania, delirium, dissociative episodes including dissociative amnesia, dissociative fugue and dissociative identity disorder, depersonalization, catatonia, seizures, severe psychiatric emergencies including suicidal behaviour, self-neglect, violent or aggressive behaviour, trauma, borderline personality, and acute psychosis, schizophrenia including paranoid schizophrenia, disorganized schizophrenia, catatonic schizophrenia, and undifferentiated schizophrenia, neurodegenerative diseases including Alzheimer's disease, Parkinson's disease, Huntington's disease, the prion diseases, Motor Neurone Disease (MND), and Amyotrophic Lateral Sclerosis (ALS). substance use disorders as referred herein include but are not limited to drug addiction, drug abuse, drug habituation, drug dependence, withdrawal syndrome and overdose. Cerebral ischemia. Fibrosis. Duchenne muscular dystrophy.
[0366] Regarding mastocytosis, the invention contemplates the use of the compounds as defined above for treating the different categories which can be classified as follows:
[0367] Category I is composed by two sub-categories (IA and IB). Category IA is made by diseases in which mast cell infiltration is strictly localized to the skin. This category represents the most frequent form of the disease and includes: i) urticaria pigmentosa, the most common form of cutaneous mastocytosis, particularly encountered in children, ii) diffuse cutaneous mastocytosis, iii) solitary mastocytoma and iv) some rare subtypes like bullous, erythrodermic and teleangiectatic mastocytosis. These forms are characterized by their excellent prognosis with spontaneous remissions in children and a very indolent course in adults. Long term survival of this form of disease is generally comparable to that of the normal population and the translation into another form of mastocytosis is rare. Category IB is represented by indolent systemic disease (SM) with or without cutaneous involvement. These forms are much more usual in adults than in children. The course of the disease is often indolent, but sometimes signs of aggressive or malignant mastocytosis can occur, leading to progressive impaired organ function.
[0368] Category II includes mastocytosis with an associated hematological disorder, such as a myeloproliferative or myelodysplastic syndrome, or acute leukemia. These malignant mastocytosis does not usually involve the skin. The progression of the disease depends generally on the type of associated hematological disorder that conditiones the prognosis.
[0369] Category III is represented by aggressive systemic mastocytosis in which massive infiltration of multiple organs by abnormal mast cells is common. In patients who pursue this kind of aggressive clinical course, peripheral blood features suggestive of a myeloproliferative disorder are more prominent. The progression of the disease can be very rapid, similar to acute leukemia, or some patients can show a longer survival time.
[0370] Finally, category IV of mastocytosis includes the mast cell leukemia, characterized by the presence of circulating mast cells and mast cell progenitors representing more than 10% of the white blood cells. This entity represents probably the rarest type of leukemia in humans, and has a very poor prognosis, similar to the rapidly progressing variant of malignant mastocytosis. Mast cell leukemia can occur either de novo or as the terminal phase of urticaria pigmentosa or systemic mastocytosis.
[0371] The invention also contemplates the method as depicted for the treatment of recurrent bacterial infections, resurging infections after asymptomatic periods such as bacterial cystitis. More particularly, the invention can be practiced for treating FimH expressing bacteria infections such as Gram-negative enterobacteria including E. coli, Klebsiella pneumoniae, Serratia marcescens, Citrobactor freudii and Salmonella typhimurium.
[0372] In this method for treating bacterial infection, separate, sequential or concomitant administration of at least one antibiotic selected bacitracin, the cephalosporins, the penicillins, the aminoglycosides, the tetracyclines, the streptomycins and the macrolide antibiotics such as erythromycin; the fluoroquinolones, actinomycin, the sulfonamides and trimethoprim, is of interest.
[0373] In one preferred embodiment, the invention is directed to a method for treating neoplastic diseases such as mastocytosis, canine mastocytoma, solid tumours, human gastrointestinal stromal tumor (“GIST”), small cell lung cancer, non-small cell lung cancer, acute myelocytic leukemia, acute lymphocytic leukemia, myelodysplastic syndrome, chronic myelogenous leukemia, colorectal carcinomas, gastric carcinomas, gastrointestinal stromal tumors, testicular cancers, glioblastomas, and astrocytomas comprising administering a compound as defined herein to a human or mammal, especially dogs and cats, in need of such treatment.
[0374] In one other preferred embodiment, the invention is directed to a method for treating allergic diseases such as asthma, allergic rhinitis, allergic sinusitis, anaphylactic syndrome, urticaria, angioedema, atopic dermatitis, allergic contact dermatitis, erythema nodosum, erythema multiforme, cutaneous necrotizing venulitis and insect bite skin inflammation and blood sucking parasitic infestation comprising administering a compound as defined herein to a human or mammal, especially dogs and cats, in need of such treatment.
[0375] In still another preferred embodiment, the invention is directed to a method for treating inflammatory diseases such as rheumatoid arthritis, conjunctivitis, rheumatoid spondylitis, osteoarthritis, gouty arthritis and other arthritic conditions comprising administering a compound as defined herein to a human in need of such treatment.
[0376] In still another preferred embodiment, the invention is directed to a method for treating autoimmune diseases such as multiple sclerosis, psoriasis, intestine inflammatory disease, ulcerative colitis, Crohn's disease, rheumatoid arthritis and polyarthritis, local and systemic scleroderma, systemic lupus erythematosus, discoid lupus erythematosus, cutaneous lupus, dermatomyositis, polymyositis, Sjogren's syndrome, nodular panarteritis, autoimmune enteropathy, as well as proliferative glomerulonephritis comprising administering a compound as defined herein to a human in need of such treatment.
[0377] In still another preferred embodiment, the invention is directed to a method for treating graft-versus-host disease or graft rejection in any organ transplantation including kidney, pancreas, liver, heart, lung, and bone marrow comprising administering a compound as defined herein to a human in need of such treatment.
[0378] In yet a further embodiment, the compounds of the invention or pharmaceutically acceptable salts thereof can be administered in combination with one or more other active pharmaceutical agents in amounts sufficient to provide a therapeutic effect. In one implementation, the co-administration of the compounds of the invention and the other agent(s) is simultaneous. In another implementation, the co-administration of the compounds of the invention and the other agent(s) is sequential. In a further implementation, the co-administration of the compounds of the invention and the other agent(s) is made over a period of time,
[0379] Examples of In Vitro TK Inhibition Assays
[0380] Procedures C-Kit WT and Mutated C-Kit (D816V) Assay
[0381] Proliferation Assays
[0382] Colorimetric cell proliferation and viability assay (reagent CellTiter-Blue purchased from Promega cat No G8081) was performed on BaF3 Kit WT or Kit D816 cell lines as well as on human and murine mastocytoma and mast leukemia cell lines.
[0383] A total of 2·10 4 cells/50 μl were seeded per well of a 96-wells plate. Treatment was initiated by addition of a 2× drug solution of ½ serial dilutions ranging from 0 to 10 μM. After incubating for 48 hours at 37° C., 10 μl of a ½ dilution of CellTiter-Blue reagent was added to each well and the plates were returned to the incubator for an additional 4 hours.
[0384] The fluorescence intensity from the CellTiter-Blue reagent is proportional to the number of viable cells and data were recorded (544 Ex /590 Em ) using a POLARstar OMEGA microplate reader (BMG LabteckSarl). A background control without cells was used as a blank. The positive control of the assay corresponds to the cell proliferation obtained in the absence of drug treatment (100% proliferation). Each sample was done in triplicate. The results were expressed as a percentage of the proliferation obtained in absence of treatment.
[0385] All drugs were prepared as 20 mM stock solutions in DMSO and conserved at −80° C. Drug dilutions were made fresh in medium before each experiment. A DMSO control was included in each experiment.
[0386] Cells
[0387] Human Kit WT and human Kit D816V are derived from the murine IL-3 dependent Ba/F3 proB lymphoid cells. While Ba/F3 Kit WT are stimulated with 250 ng/ml of recombinant murine SCF, cells expressing Kit D816V are independent of cytokines for their growth. The FMA3 and P815 cell lines are mastocytoma cells expressing endogenous mutated forms of Kit, i.e., frame deletion in the murine juxtamembrane coding region of the receptor-codons 573 to 579 (FMA3) and activating D814Y mutation in the kinase domain (P815). The human leukaemic MC line HMC-1 expresses two single point mutations in the c-Kit gene, V560G in the juxtamembrane domain and D816V in the kinase domain.
[0388] Immunoprecipitation Assays and Western Blotting Analysis:
[0389] For each assay, 5·10 6 Ba/F3 cells and Ba/F3-derived cells expressing various c-kit mutations were lysed and immunoprecipitated as described (Beslu et al., 1996). Briefly, cell lysates were immunoprecipitated using rabbit immunsera directed toward the cytoplasmic domain of either anti murine KIT (Rottapel et al., 1991) or anti human KIT (Santa Cruz). Western blot was hybridized with the 4G10 anti-phosphotyrosine antibody (UBI), the corresponding rabbit immunsera anti KIT or antibodies directed against signaling molecules. The membrane was then incubated either with HRP-conjugated goat anti mouse IgG antibody or with HRP-conjugated goat anti rabbit IgG antibody (Immunotech), Proteins of interest were then visualized by incubation with ECL reagent (Amersham).
EXPERIMENTAL RESULTS
[0390] The experimental results for various compounds according to the invention using the above-described protocols are set forth in Table 3:
[0000]
TABLE 3
in vitro inhibitions of various compounds
against c-kit WT and c-kit D816V
IC 50
Target
(microM)
Compounds
c-kit
IC 50 ≦ 1
001; 013; 014; 015; 016; 020; 021; 024; 025; 026;
WT
029; 031; 038; 041; 052; 054; 055; 056; 058; 059;
060; 061; 063; 064; 065; 066; 067; 068; 069; 070;
071; 072; 075; 076; 077; 079; 080; 081; 084; 086;
087; 092; 093; 094; 096; 097; 110; 122; 123; 126;
128; 135; 137; 138; 139; 140; 142; 145; 147; 168;
169; 171; 173; 177; 178; 181; 183; 186; 195; 199;
202; 212; 213; 214; 217; 218; 219; 222
c-kit
1 <
002; 003; 004; 005; 006; 007; 008; 009; 010; 011;
WT
IC 50 < 10
012; 017; 018; 019; 022; 023; 027; 028; 030; 032;
033; 034; 035; 036; 037; 039; 040; 042; 043; 044;
045; 046; 047; 048; 049; 050; 051; 053; 057; 062;
073; 074; 078; 082; 083; 085; 088; 089; 090; 091;
095; 099; 100; 101; 102; 103; 104; 105; 106; 107;
108; 109; 111; 112; 113; 114; 115; 116; 117; 118;
119; 120; 120; 124; 125; 127; 129; 130; 131; 132;
133; 134; 136; 141; 143; 144; 146; 148; 149; 150;
151; 152; 153; 154; 155; 156; 157; 158; 159; 160;
161; 162; 163; 164; 165; 166; 167; 170; 172; 174;
175; 176; 179; 180; 182; 184; 185; 187; 188; 189;
190; 191; 192; 193; 194; 196; 197; 198; 200; 204;
205; 206; 207; 208; 210; 211; 215; 216; 220; 221;
223; 224; 225
c-kit
IC 50 ≦ 1
001; 002; 007; 008; 009; 010; 014; 016; 020; 021;
D816V
022; 024; 025; 026; 027; 028; 029; 030; 031; 032;
033; 034; 035; 036; 038; 040; 042; 043; 044; 048;
049; 051; 052; 053; 054; 055; 056; 057; 058; 059;
060; 061; 062; 063; 064; 065; 066; 067; 068; 069;
070; 071; 072; 073; 074; 075; 076; 077; 078; 079;
081; 082; 083; 084; 085; 086; 087; 088; 089; 090;
091; 092; 093; 094; 095; 096; 097; 098; 099; 100;
103; 107; 110; 111; 114; 116; 119; 122; 123; 126;
127; 128; 130; 131; 132; 133; 135; 136; 137; 138;
139; 140; 142; 143; 144; 145; 146; 147; 148; 153;
154; 155; 156; 160; 161; 168; 169; 170; 171; 173;
177; 178; 179; 180; 182; 183; 184; 186; 188; 189;
192; 193; 194; 195; 196; 199; 200; 202; 206; 207;
208; 210; 212; 213; 214; 215; 216; 217; 218; 219;
220; 222
c-kit
1 <
003; 004; 005; 006; 011; 012; 013; 015; 017; 018;
D816V
IC 50 < 10
019; 023; 037; 039; 041; 045; 046; 047; 050; 080;
101; 102; 104; 105; 106; 108; 109; 112; 113; 115;
117; 118; 120; 121; 124; 125; 129; 134; 141; 149;
150; 151; 152; 157; 158; 159; 162; 163; 164; 165;
166; 167; 172; 174; 175; 176; 181; 185; 187; 190;
191; 197; 198; 201; 203; 204; 205; 209; 211; 221;
223; 224; 225
[0391] The inventors observed a very effective inhibition of a protein kinase and more particularly of native and/or mutant c-kit by the class of compounds of formula I of the invention. The listed compounds in Table 3 are well representing the class of compounds of formula I.
|
The present invention relates to compounds of formula I or pharmaceutically acceptable salts thereof:
wherein R 1 , R 2 , R 3 , A, Q, W and X are as defined in the description.
These compounds selectively modulate, regulate, and/or inhibit signal transduction mediated by certain native and/or mutant protein kinases implicated in a variety of human and animal diseases such as cell proliferative, metabolic, allergic, and degenerative disorders. More particularly, these compounds are potent and selective native and/or mutant c-kit inhibitors.
| 2
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of U.S. application Ser. No. 10/894,628, filed Jul. 20, 2004 now U.S. Pat. No. 7,478,426.
BACKGROUND OF THE INVENTION
FIG. 1 depicts conventional networks 10 and 20 which may be connected to the Internet 30 . Each network 10 and 20 includes host 12 , 14 and 16 and 22 and 24 , respectively. Each network 10 and 20 also includes a switch 18 and 26 , respectively, and may include one or more servers such as the servers 17 , 19 and 28 , respectively. In addition, each network 10 and 20 may include one or more gateways 13 and 25 , respectively, to the Internet 30 . Not explicitly shown are routers and other portions of the networks 10 and 20 which may also control traffic through the networks 10 and 20 and which will be considered to be inherently depicted by the switches 18 and 26 , respectively, and the networks 10 and 20 in general.
In order to manage communications in a network, such as the network 10 or 20 , filter rules are used to enforce a plurality of networking rules for multi-field classification searches of the network. Filter rules are typically employed by switches of the network. Exemplary rules include filtering, quality of service, traffic engineering and traffic redirection rules. A filter rule may test packets entering the network from an outside source to ensure that attempts to break into the network can be thwarted. For example, traffic from the Internet 30 entering the network 10 may be tested in order to ensure that packets from unauthorized sources are denied entrance. Similarly, packets from one portion of a network may be prevented from accessing another portion of the network. For example, a packet from some of the hosts 12 , 14 or 16 may be prevented access to either the server 17 or the server 19 . The fact that the host attempted to contact the server may also be recorded so that appropriate action can be taken by the owner of the network. Filter rules may also be used to transmit traffic based on the priorities of packets. For example, packets from a particular host, such as the host 12 , may be transmitted because the packets have higher priority even when packets from the hosts 14 or 16 may be dropped. Filter rules may also be used to ensure that new sessions are not permitted to be started when congestion is high even though traffic from established sessions is transmitted.
Filter rules generally test a packet “key” in order to determine whether the filter rule will operate on a particular packet. The key that is typically used is the Internet Protocol (IP) “five-tuple” of the packet. The IP five-tuple typically contains five fields of interest: the source address, the destination address, the source port, the destination port and the protocol. These fields are typically thirty-two bits, thirty-two bits, sixteen bits, sixteen bits and eight bits, respectively. Thus, the part of IP five-tuple of interest is typically one hundred and four bits in length. Filter rules typically utilize these one hundred and four bits, and possible more bits, in order to perform their functions. For example, based on the source and destination addresses, the filter rule may determine whether a packet from a particular host is allowed to reach a particular destination address.
Filter rules can also interact, based on the priority for the filter rule. For example, a first filter rule may be a default filter rule, which treats most cases. A second filter rule can be an exception the first filter rule. The second filter rule would typically have a higher priority than the first filter rule to ensure that where a packet matches both the first and the second filter rule, the second filter rule will control.
One well known structure for organizing and applying a plurality of filter rules is a “Patricia tree”, wherein Patricia refers to the acronym PATRICIA: Practical Algorithm to Retrieve Information Coded in Alphanumeric. A Patricia tree is a decision tree structure, wherein a “yes” or “no” decision from the application of a first “node” filter rule leads to the responsive selection of one of two sub-tree “branch” filter rules, each of which may serve as a node of two more sub-tree branch filter rule applications, each of which may also serve as another sub-node. One reference for Patricia trees is D. R. Morrison, “PATRICIA—Practical Algorithm to Retrieve Information Coded in Alphanumeric”, Jrnl. of the ACM, 15(4) pp 514-534, October 1968.
With respect to Patricia tree applications in network filter rule management it is known that a balanced tree structure is desired in order to minimize the depth of the tree, and thus minimize search times. U.S. Pat. No. 6,473,763 to Corl, Jr. et al for “System, Method and Computer Program for Filtering Multi-Action Rule Set” issued Oct. 29, 2002 (the “'763 patent”) describes a method of resolving a Multi-field search key to an associated network management rule (such as, for example filtering, QOS, and redirection rules). The '763 patent teaches a “choice bit” algorithm for optimally select distinguishing bits while building a tree structure with an optimum balance, thus minimizing the number of chained pointers (i.e. “depth” of the tree) that must be traversed to resolve a search. The entire tree is rebuilt in a network control plane each time an update is required, the new tree is downloaded to a network data plane, and the data plane is then switched to the new tree while obsolescing the old tree.
This approach works reasonably well for applications requiring infrequent rule changes, for example where a network administrator specifically alters rules to account for an office move. However, processor cycle and bandwidth limits between the control plane and the data plane limit the usefulness of this method when rule changes are more frequent.
What is needed is an improved method and system for handling network filter rule changes that efficiently supports frequent incremental updates to the network filter rules without requiring responsively large network resource commitments, processor cycles and bandwidth.
SUMMARY OF THE INVENTION
The present invention relates to a method and computer system device for applying a plurality of rules to data packets within a network computer system. A filter rule decision tree is updated by adding or deleting a rule. If deleting a filter rule then the decision tree is provided to a network data plane processor with an incremental delete of the filter rule. If adding a filter rule then either providing an incremental insertion of the filter rule to the decision tree or rebuilding the first decision tree into a second decision tree responsive to comparing a parameter to a threshold. In one embodiment the parameter and thresholds relate to depth values of the tree filter rule chained branches. In another the parameter and thresholds relate to a total count of rule additions since a building of the relevant tree.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a conventional computer network system.
FIG. 2 is a block diagram of a computer network system appropriate to the present invention.
FIG. 3 is a flow chart diagram of a decision tree rebuild decision process according to the present invention.
FIG. 4 is a flow chart diagram of an algorithm for rule change according to the present invention.
FIG. 5 is a flow chart diagram of another algorithm for rule change according to the present invention.
FIG. 6 is an article of manufacture comprising a computer usable medium having a computer readable program according to the present invention embodied in said medium.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides an improved method and system for handling rule changes that efficiently supports frequent incremental updates. The method and system are based on the fact that a slightly sub-optimal tree structure can be tolerated with very little impact to search latency. The present invention thus responds to each individual rule insertion or deletion according to the same procedures used in a Fixed Match (FM) Tree. FM trees are more fully described in commonly-assigned U.S. Pat. No. 6,675,163, issued Jan. 6, 2004 to Bass et al. for “Full match (FM) search algorithm implementation for a network processor”, which is hereby incorporated by reference into this description as fully as if here represented in full. What is new in the present invention is a system and method for supplementing prior art procedures to determine whether or not the insertion of a new rule can be made without rebuilding the table.
In a preferred implementation, the deletion of a rule will never require rebuilding the table, since it can only make a tree branch shorter. Alternatively, the insertion of a new rule will make a tree branch longer by adding one new node at the end of the closest matching branch. This insertion point is determined by identifying the last node visited while doing a search for the entry. Note that the search will be unsuccessful, since the entry hasn't been added yet. It will follow a linked list of pointers in the Patricia tree structure ending at a table entry that causes a “miscompare.” It is conventional for network hardware to remember the last node in the Patricia tree (the one pointing to the table entry that caused miscompare). However, if the insertion doesn't impact the previously longest branch of the tree, it will not increase the worst-case latency. Accordingly, in one embodiment of the present invention a test is applied whenever a rule is inserted to determine the number of chained pointers required to solve a search to the new rule. If the resulting tree depth is greater than the tolerable worst-case tree depth, the tree is rebuilt by the control point. An important advantage of the present invention is that the test insertion and rule check may be done in the control point, and the decision made about rebuilding the table can be made without disrupting the data plane.
According to the present invention a “tolerable worst case” tree depth is determined each time the tree is rebuilt, and is preferably set responsive to the longest chain of pointers in the current tree. In some embodiments the worst case tree depth is set equivalent to the length of the current longest chain of pointers: thus if the new rule is added to a smaller chain in the current chain no rebuild is indicated. Alternatively, worst case tree depth may also be set to a growth factor “N” links longer than the current longest chain to increase the number of updates that can be handled without rebuilding the table. The growth factor N may be fixed (exemplary values include 1 or 6) or it may be responsive to table size, preferably made smaller as a table gets larger, since a smaller table is more likely to insert on the longest branch and also requires more room to grow than a larger table. The worst case tree depth may also be set to a minimum value MV independent of the current longest chain value, in order to ensure room for growth.
In an alternative embodiment of the present invention rebuilding the table may be indicated once for every M insertions, where M may be a constant or may be a function of the table size. What is important is that in the present invention the number of times a table must be rebuilt is significantly reduced, over potentially several orders of magnitude, compared to prior art systems, and thus it is practical to support highly dynamic rule changes while still maintaining control over worst-case search latencies with the system and method of the present invention.
Referring now to FIG. 2 , according to the present invention a network administrator 212 inputs rule changes to the Control Plane Processor (“Control Point”) 214 of the network processing system 10 , and the Control Point 214 responsively coordinates any required updates to one or more tables 230 , the tables 230 accessible by one or more data plane processors 242 defining a data plane 240 , wherein the data plane is interfaced with one or more network ports 250 in the gateway 13 . The Control Point 214 responsively sets up appropriate tables or other appropriate search structures, enabling the data plane processors 242 to independently apply the responsively updated or changed rules to each packet forwarded by the data plane 240 .
FIG. 3 is a flow chart diagram representation of the determination of a decision tree rebuild responsive to a rule change according to the present invention. When a rule change request 102 is received by the control point, a type determination 104 is made as to whether an old rule is being removed or a new rule is being added. If an old rule is being removed, then an incremental delete command is passed directly to the data plane at step 106 , and an appropriate data plane resource removes the corresponding rule from the active table; the algorithm 100 then ends at step 108 .
However, if a new rule is being added into the search structure as determined at step 104 , the control point responsively increments a parameter at step 110 . The control point then compares the incremented parameter to a previously established threshold at step 112 . If the parameter is lower than or equal to the threshold, then an incremental insert command is passed directly to the data plane at step 114 , and an appropriate data plane resource inserts the corresponding rule in the active table. Alternatively, if the determination is made that the new pointer chain length is greater than the threshold, then the entire rule table is rebuilt at step 120 . The new table/tree is then transferred to the data plane table memory at step 122 .
It is preferred, although not required, that the threshold is set responsive to the current table. Accordingly, it is preferred that when the new tree structure is constructed in step 120 that the threshold is also recalculated responsive to at least one characteristic of the rebuilt tree, and the recalculated threshold utilized in the next iteration of step 112 .
FIG. 4 illustrates one rule update procedure algorithm 300 according to the present invention carried out by a control point 214 in response to requests from a network administrator or other controlling entity. It is important to note that the desire to support fast incremental updates may be partially driven by applications requiring automated control of rule changes rather than being driven by human interaction. According to the present embodiment, when a rule change request 302 is received by the control point, a type determination 304 is made as to whether an old rule is being removed or a new rule is being added. If an old rule is being removed, then an incremental delete command is passed directly to the data plane at step 306 , and an appropriate data plane resource removes the corresponding rule from the active table; the algorithm 300 then ends at step 308 . Note that this action will always result in a shorter chain of pointers to all remaining rules downstream from the deletion point, and will not affect the length of the pointer chain (depth of tree) for all other rules. Thus, if the search latency was acceptable for achieving a specific performance level before the delete action; the search latency will also be acceptable after the delete action, since it will be less than or equal to the previous search latency.
Alternatively, if a new rule is being added into the search structure, according to the present embodiment 300 search latency to resolve the new rule may be longer than a previous worst case latency, but search latency for previously existing rules, except for the one rule at the insertion point, is not affected since the rule is always inserted at the end of a tree branch.
To prevent search latency from growing without bounds, it is preferred that a threshold is established at the time the table is built to limit the allowable tree depth. Thus if a new rule is being added into the search structure as determined at step 304 , the control point computes the length of the pointer chain responsive to the new rule at step 310 . The control point then compares the pointer length to the previously established threshold at step 312 . If the new pointer chain length (tree depth) is lower than or equal to the threshold, then an incremental insert command is passed directly to the data plane at step 314 , and an appropriate data plane resource inserts the corresponding rule in the active table. Alternatively, if the determination is made that the new pointer chain length is greater than the threshold, then the entire rule table is rebuilt at step 320 to attempt to better balance the tree depth.
Once the new tree structure has been constructed, the longest tree branch is identified. The tree depth threshold is then updated in step 322 , preferably set responsive to the longest chain of pointers in the new tree. In one embodiment the tree depth threshold is set to be N links greater than the number of links in the longest branch path of the new tree. N may be set to zero, 1, or to a greater predetermined maximum value such as 6, although other desirable values may be readily apparent to one skilled in the art. Setting N to a larger value this will ensure room for growth and thus reduce the likelihood that the table will be rebuilt responsive to subsequent determination steps 312 . The worst case tree depth may also be set to a minimum value MV independent of the current longest chain value: this may be desirable to give more room to grow for a small table, yet apply a tighter control to a larger table as it approaches a critical search latency. If insertions are well distributed, the larger table will be able to support more incremental insertions, even with a smaller allowable change in tree depth. Thus tighter control probably doesn't mean that the table must be rebuilt more often.
Alternatively, the growth factor N may be responsive to table size. It is preferable that N be made smaller as a table gets larger, since a smaller table is more likely to insert on the longest branch and also requires more room to grow than a larger table. For example N may be set to 6 links greater than the number of links in the longest branch path of the new tree when a small table is built (e.g. longest branch path has just 3 or 4 links). Then, each time the number of links in the longest branch increases, N is increased by a fraction of the increase in the longest branch. For example, if the longest branch increased by 2, N might be increased by 1, and further adjusted to insure N continues to be greater than the number of branches in the longest branch. Note that in any case, N should be at least equal to one greater than the number of links in the longest branch.
Once the new table has been built by the control point at step 320 , the entire new table is transferred to the data plane table memory at step 322 . Initially, the new table is in standby mode, and the old table continues to be used by the data plane for packet forwarding in order to avoid disruption of data plane packet forwarding. Once the new table is in place (as determined by down-load bandwidth of the system), it is placed in active state and the old table is switched to standby. Storage used by the old table can then be made available to support the next complete table swap.
FIG. 5 illustrates another algorithm embodiment 400 of the present invention. When a rule change request 402 is received by the control point, a type determination 404 is made as to whether an old rule is being removed or a new rule is being added. If an old rule is being removed, then an incremental delete command is passed directly to the data plane at step 406 , and an appropriate data plane resource removes the corresponding rule from the active table; the algorithm 400 then ends at step 408 .
Alternatively, if a new rule is being added into the search structure as determined at step 404 , then a rule update count is incremented in step 410 to determine a total number of rule insertions since a last table rebuild in step 420 . If the new rule change in step 402 results in a total rule change count that exceeds a maximum value M, then a step 420 table rebuild is indicated. The table is rebuilt and the update count is accordingly reset to zero in step 420 , the new table is sent to the control plane in step 422 , and the process ends for this iteration in step 408 .
M may be a predetermined fixed value. In some embodiments M may be dependent upon the table size: for example M may be set to equal 25% of the number of entries in the table since the last time the table was rebuilt. Where M is dependent upon table size, then M is also updated in step 420 responsive to the size of the new table built: thus each time the table is rebuilt, M is set to a value responsive to the number of total entries in the newly built table. It will be readily apparent to one skilled in the art that other percentage values may be chosen for M, or other table attributes may be selected to drive a function selecting the value of M, and the present invention is not to be construed as restricted to the embodiments described thus far.
The embodiment of the invention described above may be tangibly embodied in a computer program residing on a computer-readable medium or carrier 490 shown in FIG. 6 . The medium 490 may comprise one or more of a fixed and/or removable data storage device such as a floppy disk or a CD-ROM, or it may consist of some other type of data storage or data communications device. The computer program may be loaded into memory to configure a computer processor for execution. The computer program comprises instructions which, when read and executed by a processor causes the processor to perform the steps necessary to execute the steps or elements of the present invention.
While preferred embodiments of the invention have been described herein, variations in the design may be made, and such variations may be apparent to those skilled in the art of computer network design and management, as well as to those skilled in other arts. The embodiments of the present invention identified above are by no means the only embodiments suitable for carrying out the present invention, and alternative embodiments will be readily apparent to one skilled in the art. The scope of the invention, therefore, is only to be limited by the following claims.
|
The present invention relates to a method and computer system device for applying a plurality of rules to data packets within a network computer system. A filter rule decision tree is updated by adding or deleting a rule. If deleting a filter rule then the decision tree is provided to a network data plane processor with an incremental delete of the filter rule. If adding a filter rule then either providing an incremental insertion of the filter rule to the decision tree or rebuilding the first decision tree into a second decision tree responsive to comparing a parameter to a threshold. In one embodiment the parameter and thresholds relate to depth values of the tree filter rule chained branches. In another the parameter and thresholds relate to a total count of rule additions since a building of the relevant tree.
| 7
|
This Application is a Divisional Application of a patent application Ser. No. 09/480,915 filed by the Applicant of this invention on Jan. 11, 2000, now U.S. Pat. No. 6,377,484.
BACKGROUND OF THE INVENTION
The present invention relates to electrically programmable read only memory (EPROM) device, and more particularly to embedded EPROM devices manufactured by existing integrated circuit (IC) technologies.
Current art EPROM devices are manufactured by special technologies that are optimized only for stand-along EPROM products. It is not practical to put other types of integrated circuits, such as DRAM or high performance logic circuits, on the same wafer with current art EPROM devices. On the other hand, it is strongly desirable to have programmable devices for DRAM or logic circuits. DRAM devices are typically high density devices; each individual DRAM device contains millions or even billions of memory cells. It is very difficult to manufacture such a large device without any local failures. DRAM devices are therefore equipped with programmable redundancy circuits. The redundancy circuits repair partial failures on individual devices. Such redundancy circuits improve DRAM yield dramatically and therefore reduce the cost of DRAM products significantly. The redundancy circuits must be programmable to fix failures at different locations. Ideally, we would like to program those redundancy circuits using EPROM. When the device can be programmed electrically, the required testing costs can be reduced significantly. The problem is that no current art EPROM devices can be manufactured using current art DRAM manufacture technologies. Current art DRAM redundancy circuits usually use fuses to support its programmable functions. Those fuses occupy relatively large areas. Sophisticated wafer level testing equipment equipped with LASER is required to burn those fuses in order to configure the redundant circuits. The process is destructive and cumbersome. It is therefore strongly desirable to use EPROM devices, instead of fuses, to support DRAM redundancy circuits.
Besides redundancy circuits, EPROM devices are very useful for other applications. For example, we can implement programmable firmware on logic circuits so that the same product can be programmed to support different applications. Each individual product can have its own identification (ID) number for security purpose if it is equipped with EPROM devices. The problem is, again, current art EPROM devices can not be manufactured by standard logic technologies. Currently, special embedded EPROM technologies are available to build conventional EPROM devices and logic circuits on the same wafer. Such special technologies require many more manufacturing steps than standard logic technologies so that the cost is significantly higher. Another major problem is that conventional EPROM devices require high voltages to support programming and erase operations. The requirement for high voltages further complicates the manufacture technology. It is therefore strongly desirable to have EPROM devices that can be manufactured by standard logic technologies.
SUMMARY OF THE INVENTION
The primary objective of this invention is, therefore, to providing practical methods to build embedded EPROM devices using existing IC manufacture technologies. One objective of the present invention is to provide EPROM device for DRAM redundancy circuits using existing DRAM technology. Another objective of the present invention is to provide EPROM devices manufactured by standard logic technologies. It is also desirable that such devices do not require high voltages for its operations.
These and other objectives are accomplished by novel device structures that utilize existing circuit elements to build EPROM devices without complicating existing manufacture technologies. For example, DRAM storage capacitors are used as the coupling capacitors to build floating gate EPROM devices. Another example is to utilize transistor properties changed under stress conditions to support EPROM operations.
While the novel features of the invention are set forth with particularly in the appended claims, the invention, both as to organization and content, will be better understood and appreciated, along with other objects and features thereof, from the following detailed descriptions taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is the cross section diagram for a current art DRAM memory cell;
FIGS. 2 ( a-d ) are cross section diagrams illustrating the manufacture procedures for current art DRAM;
FIGS. 3 ( a-c ) are cross section diagrams illustrating the manufacture procedures for an EPROM device of the present invention;
FIG. 4 ( a ) is the schematic diagram for the DRAM memory cells in FIG. 1;
FIG. 4 ( b ) is the schematic diagram for the EPROM memory cells in FIG. 3 ( c ).
FIG. 5 shows the current-voltage (I-V) relationship for a metal-oxide-siliconn (MOS) transistor before and after hot electron stress; and
FIGS. 6 ( a-d ) are the symbolic block diagram of the supporting circuit for stress EPROM devices of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The physical structure of a DRAM memory device is illustrated by the simplified cross-section diagram in FIG. 1 . Each DRAM memory cell ( 101 ) contains one select transistor ( 103 ) and one storage capacitor ( 107 ). The gate ( 105 ) of the select transistor is connected to memory word line (WL). This gate ( 105 ) is typically made of polycrystalline silicon (poly) thin film. The gate is separated from the substrate by a thin film gate oxide, but the gate oxide is too thin to be shown in the diagram. The source ( 106 ) of the select transistor is connected to the bottom electrode ( 108 ) of the storage capacitor ( 107 ). This storage capacitor ( 107 ) contains two electrodes. The top electrode ( 109 ) is usually called the “plate” electrode in current art DRAM technology. The plate is usually shared by a plural of memory cells, and it is usually connected to a stable voltage source. The bottom electrode ( 108 ) of the storage capacitor ( 107 ) is unique for each memory cell, and it is used to store data. There is a thin insulating layer between the two electrodes of the storage capacitor, which is too thin to be shown in our figures. A contact plug ( 102 ) is usually used to connect the bottom electrode ( 108 ) of the storage capacitor to the source ( 106 ) of the select transistor, which is separated from the source of nearby transistor (not shown) by filed oxide ( 112 ). The drain ( 104 ) of the select transistor is connected to the memory bit line (not shown). To reduce bit line loading, the drain ( 104 ) electrode is typically shared by the select transistor ( 113 ) of a nearby memory cell. In FIG. 1, this drain ( 104 ) area is represented by dashed lines because it is usually not on the same cross-section plan as the storage capacitor ( 107 ).
The manufacture procedures for the DRAM storage capacitor ( 107 ) are illustrated by the simplified cross-section diagrams in FIGS. 2 ( a-d ). FIG. 2 ( a ) shows the structure just before the beginning of the storage capacitor manufacture procedures. At this time, the select transistor ( 103 ) is fully manufactured, while the location for the storage capacitor is covered with insulator layers ( 201 ). The next step is to dig a deep DRAM contact hole ( 221 ) through the insulator ( 201 ) to the silicon substrate at the source ( 106 ) of the select transistor ( 103 ), as illustrated by the cross section diagram in FIG. 2 ( b ). Plasma etching is usually needed for this manufacture step. Typically, a plug ( 211 ) is placed into the bottom of the contact hole ( 221 ) before the bottom electrode ( 223 ) of the storage capacitor is formed around the contact hole ( 221 ) as illustrated by FIG. 2 ( c ). The top electrode ( 231 ) of the storage capacitor and the insulator between those two electrodes are formed in the contact hole ( 221 ) by a series of complex manufacture procedures, and the resulting structures are illustrated in FIG. 2 ( d ). The storage capacitor manufacture processes are very complex, and they can be different for technologies developed by different companies. For example, the contact plugs ( 211 ) usually are manufactured by separated processing steps. We do not intend to cover details of those manufacture procedures because the present invention is not dependent on such manufacture details.
The manufacture procedures for an EPROM memory cell of the present invention are illustrated by the cross section diagrams in FIGS. 3 ( a-c ). FIG. 2 ( a ) shows the structure just before the beginning of the EPROM coupling capacitor is manufactured. At this time, the EPROM transistor ( 303 ) is fully manufactured, and its structure is very similar to the structure shown in FIG. 2 ( a ) except that the cross-section is taken away from the transistor at a nearby field oxide layer ( 312 ). The source ( 306 ) and drain ( 304 ) of the EPROM transistor ( 303 ) are represented by dashed lines because they are typically not on the same cross-section plan as the couple capacitor. The area on tope of those transistors is covered with insulator layers ( 315 ). The gate ( 305 ) of this EPROM transistor ( 303 ) is not connected to a word line; it is isolated from other EPROM memory cells to be served as the floating gate of the EPROM memory cell. The next step is to dig an EPROM contact hole ( 321 ) as illustrated by FIG. 3 ( b ). The EPROM contact holes ( 321 ) and the DRAM contact holes ( 211 ) are manufactured simultaneously with identical manufacture procedures. The difference is that an EPROM contact hole ( 321 ) is placed on top of the poly gate ( 305 ) electrode instead of the source ( 306 ) of the EPROM select transistor ( 303 ). The physical structure of an EPROM contact hole ( 321 ) is nearly identical to a DRAM contact hole ( 221 ). The floating gate ( 305 ) is made of polycrystalline silicon thin film that is of similar etching rate as the silicon substrate at the source ( 106 ) of a DRAM select transistor ( 103 ). It is therefore possible to manufactured both the DRAM contact holes ( 221 ) and the EPROM contact holes ( 321 ) simultaneously while using identical etching procedures. After the EPROM contact holes ( 321 ) are opened, coupling capacitors ( 307 ) that has nearly identical structures as the DRAM storage capacitors ( 107 ) are manufactured at the locations of EPROM contact holes ( 321 ). The EPROM coupling capacitors ( 307 ) and the DRAM storage capacitors ( 107 ) are manufactured with identical procedures simultaneously.
The cross section diagram in FIG. 2 ( c ) illustrated the final structures of a DRAM based EPROM ( 301 ) memory cell of the present invention. The top electrode ( 309 ) of the coupling capacitor ( 307 ) serves as the control gate (CG) of the EPROM memory cell. This control gate is manufactured with identical procedures and identical materials as the plate electrode ( 109 ) of the DRAM memory cell. The bottom electrode ( 308 ) of the coupling capacitor ( 307 ) is connected to the gate ( 305 ) of the EPROM select transistor ( 303 ), and serves as the floating gate (FG) of the EPROM memory cell ( 301 ). The drain ( 304 ) of the EPROM transistor ( 303 ) is connected to ERPROM bit lines (EBL).
FIGS. 4 ( a, b ) are schematic diagrams showing the connections of the above DRAM and EPROM devices. Each DRAM memory cell ( 401 ) contains one select transistor ( 403 ) and one storage capacitor ( 407 ) as shown in FIG. 4 ( a ). The gate of the select transistor ( 403 ) is connected to word line (WL), its drain is connected to bit line (BL), and its source is connected to one terminal of its storage capacitor; the other terminal of the storage capacitor is connected to the plate electrode (PL). Each EPROM memory cell ( 411 ) contains one transistor ( 413 ) and one coupling capacitor ( 417 ). The drain of the EPROM transistor is connected to bit line (EBL), its source is connected to ground, and its gate is a floating gate (FG) connected to one electrode of the coupling capacitor; the other terminal of the coupling capacitor is connected to the control gate (CG). For an EPROM device of the present invention, the EPROM coupling capacitor ( 417 ) is manufactured in the same way as the DRAM storage capacitor ( 407 ). For most cases, the EPROM transistor ( 413 ) is also manufactured in the same way as the DRAM select transistor ( 403 ). It is therefore possible to have both DRAM and EPROM devices on the same wafer without adding cost to the manufacture procedures.
The operation principles of the above EPROM memory cell of the present invention are the same as that of prior art EPROM memory cells. During a programming operation, the source ( 306 ) of the EPROM transistor ( 303 ) is connected to ground, the control gate (CG) is connected to a first voltage, and the drain ( 304 ) is connected to a second voltage. Electrons are injected into the floating gate (FG) of the EPROM cell by hot electron injection mechanism. Another method to program the EPROM cell is to apply a high positive voltage to the control gate (CG) so that electrons are injected into the floating gate (FG) by tunneling mechanism. To erase the EPROM cell, a high positive voltage is applied on the drain ( 304 ) and/or the source ( 306 ) of the EPROM transistor ( 303 ) while the control gate (CG) is connected to ground. Electrons are pulled out of the floating gate (FG) by tunneling mechanism during such erase operation. Another way to erase the cell is to apply ultra violet (UV) light to the EPROM memory cells so that electrons can leak out of the floating gate (FG). During a read operation, a voltage is applied on the control gate (CG), and the source ( 306 ) is connected to ground. External sense amplifiers (not shown) detects the current flowing out of the drain ( 304 ) into the EPROM bit line (EBL) to determine the data stored in the EPROM cell.
While specific embodiments of the invention have been illustrated and described herein, it is realized that other modifications and changes will occur to those skilled in the art. It should be understood that the above particular examples are for demonstration only and are not intended as limitation on the present invention. Near every semiconductor manufacturer has specific methods in building the storage capacitors for DRAM memory cells. Key element of the above EPROM device of the present invention is to use DRAM storage capacitor as the coupling capacitor of EPROM memory cell. An EPROM device of the present invention utilizes the same manufacture procedures as the DRAM manufacturing procedures. Therefore, its detailed structures will vary as the details for the DRAM memory cell vary while the functions of the EPROM devices of the present invention are independent of those detailed variations. The scope of the present invention should not be limited by detailed structures of its coupling capacitors. Other modifications to the structures of the EPROM devices of the present invention will also become obvious upon disclosure of the present invention.
The above EPROM devices of the present invention have the following advantages:
The major advantage is the capability to manufacture EPROM devices using existing DRAM manufacture technologies. It is therefore possible to have EPROM memory devices and DRAM memory devices on the same wafer without introducing additional manufacture cost.
The coupling capacitors ( 417 ) of the EPROM devices of the present invention are by far larger than those of current art EPROM memory devices.
Since the capacitance of a DRAM storage capacitor is typically more than 20 times higher than the capacitance of a transistor of equivalent area, the gate coupling ratio (GCR) of an EPROM device of the present invention is almost always higher than 0.95. The GCR for a current art EPROM device is typically around 0.5. That means the operation voltages needed to support the EPROM devices of the present invention can be reduced by nearly 50%. The programming and erase voltages requires to support EPROM devices of the present invention is therefore by far lower than that of current art EPROM memory devices. Lowering the supporting voltages dramatically simplifies the requirements on supporting circuits.
The most obvious application of the present invention is to build programmable redundancy circuits on DRAM devices. Current art DRAM devices use fuses to program its on chip redundancy circuits. That repair mechanism is destructive, and the fuses occupy large areas. The programming method also requires sophisticated wafer level tester that increases testing costs. When a repair circuit uses EPROM devices of the present invention, it can be reprogrammed multiple times using simple electrical procedures. The repair also can be done in the field in case a device is damaged after installation. The repair circuits will have much smaller area while operating at much higher performance.
Comparing to current art EPROM devices, one potential disadvantage of the above EPROM devices of the present invention is the durability of the gate oxide. Current art EPROM devices use special treatments on the gate oxide so that they can tolerate more than 100,000 program-erase (PE) cycles. When the EPROM devices of the present invention uses the same gate oxide as DRAM transistors, the gate oxide may not be able to tolerate such a large number of PE cycles. That is usually not a problem because most applications do not require many PE cycles. For applications that require high PE cycles, we need to use the gate oxide for conventional EPROM while we still can use DRAM storage capacitor as the EPROM gate coupling capacitor. In this way, we need to pay additional complexity in manufacturing two types of gate oxides. The resulting increase in price is still by far less than the condition to make DRAM and EPROM separately.
Current art EPROM devices and the above EPROM devices of the present invention store data by putting electrical charges into floating gates (FG). Another way to build embedded EPROM device using existing manufacture technologies is to build EPROM devices without using floating gate devices. Such EPROM devices of the present invention use the damages caused by electrical stresses on common transistors. By comparing the electrical properties of transistors with different levels of damages, we are able to build novel EPROM devices that are extremely convenient for embedded applications.
for example, we can utilize the hot carrier effects to build EPROM devices using common transistors. When an MOS transistor is operating at high drain-to-source voltage (Vds) while the gate-to-source voltage (Vgs) is slightly higher than its threshold voltage (Vt), there is a strong electrical field build up near its drain area. Such operation conditions are called “hot carrier stress” conditions. Under this stress condition, high energy electrons or holes (called hot carriers) generated by the strong electrical field cause damages to the transistor. The damages, called hot carrier effects, cause changes in transistor electrical properties. Typically, the threshold voltage (Vt) of an n-channel transistor increases after it is damaged by hot carrier effect as illustrated in FIG. 5 . The drain to source current under the same bias voltages is also lower after hot carrier damages. On the other words, the current driving capability of n-channel transistors decrease by hot carrier effects. P-channel transistors usually behave in the opposite way; their current driving capabilities increase after hot carrier stress.
The damaging rate of hot carrier effect is significant only when the transistor is under hot carrier stress conditions. At other conditions the hot carrier damage rate is negligible. For example, when Vgs is much higher than Vt or when Vgs is lower than Vt, the transistor won't have a high electrical field near its drain so that there would be no hot carrier damage. Similarly, when Vds is small, the hot carrier effect is negligible. The knowledge allow us to operate a transistor under conditions that will not cause hot carrier damages.
Another type of well-known transistor damage is the gate voltage (Vg) stress damage. Put a high voltage on the gate of a transistor, and permanent damages can be done to the transistor. For most n-channel transistors, Vg stress results in reduced current driving capability.
The hot carrier effect and the Vg stress effect are well-known to the IC industry. They are usually major limiting factors for the development of new IC technologies. Special cares are taken to improve the tolerance in those effects. Special structures such as the lightly doped drain (LDD) structures are implemented to improve tolerances in hot carrier effects. These effects are therefore always fully studied and well-documented for all IC technologies.
The hot carrier damages and Vg stress damages are permanent. Once a transistor is damaged, the effects remain for its lifetime. Under certain conditions (for example, thermal annealing) a damaged transistor can partially recover, but the damages can never fully recover. It is therefore possible to use these effects to store data and to build EPROM devices using common transistors. These types of EPROM devices of the present invention are named “stress effect programmable read only memory” (SEPROM) devices by the present inventor.
Other types of active devices, such as bipolar transistors or diodes, also experience changes in properties after different types of electrical stresses. We can build SEPROM devices using bipolar transistors or diodes as building blocks following the same principles.
FIG. 6 ( a ) is a symbolic block diagram illustrating the general operations of SEPROM devices. A stress circuit ( 602 ) applies proper electrical stresses to one or more data devices ( 600 ) and a reference device ( 601 ). Data are represented by the property differences between the data devices and the reference device. Sometimes the reference device can be another data device. A sense circuit ( 604 ) senses the differences in device properties between them in order to read the data.
FIG. 6 ( b ) shows the schematic diagram for one practical example of a SEPROM device. A SEPROM memory block ( 610 ) comprises a two dimensional (M by N) array of transistors. At the n'th row of the memory block, the gates for data transistors (M nl , . . . , M nm , . . . , M nM ) , and the gate for a reference transistor (M nr ) are connected together to a word line (WL n ) as shown in FIG. 6 ( b ). At the m'th column of the memory block, the drains for transistors M lm , . . . , M nm , . . . , M Nm are connected together to a bit line (BL m ). The drains for reference transistors M lr , . . . , M nr , . . . , M Nr are connected together to the reference bit line (BL r ). The sources of all those transistors are connected to ground. Each word line (WL n ) is connected to the output of a word line decoder ( 612 ). Each bit line (BL m ) is connected to the input of a bit line sensor ( 614 ) and the output of a bit line stress circuit ( 616 ). The reference bit line (BL r ) is connected to a reference signal generator ( 618 ) that generates a reference signal (Sr) to bit line sensors ( 614 ).
During a write operation (also called “programming” operation in current art), one of the word line decoder ( 612 ) pulls the voltage on the selected word line (WL n ) to a voltage optimized for maximum stress rate (Vgst). All the other word lines remain at low voltages. The bit line stress circuits ( 616 ) provide bit line stress voltages to the bit lines (BL m ) according to the data values to be written to each transistor (M nl , . . . , M nm , . . . M nM , M nr ) on the selected row; to store a digital data ‘1’, the corresponding bit line voltage should be high, and the corresponding selected transistor will experience hot carrier stress; to store a digital data ‘0’, the corresponding bit line voltage should be zero, and the corresponding selected transistor will not be stressed; the reference bit line voltage usually remains low. The digital data certainly can be stored in opposite ways. Hot carrier effect damages transistors when the transistors are (1) on the selected word line and (2) on a bit line that is pulled high. In this way, data can be written into the memory block selectively. The selected word line voltage Vgst, should be controlled to have maximum hot carrier damage rate.
During a read operation, one of the word line decoder ( 612 ) pulls the voltage on the selected word line (WL n ) to a high voltage. All the other word lines remain at zero. The voltage on the selected word line (WL n ) during a read operation should be high enough and the voltage on the bit lines should be low enough that the selected transistors (M nl , . . . , M nm , . . . , M nM , M nr ) will not experience hot carrier effects during this operation. All the bit line stress circuits ( 616 ) should be off during this read operation. Each selected transistor (M nl , . . . , M nm , . . . , M nM , M nr ) drives a current I nl , . . . , I nm , . . . , I nM , I nr ) through its corresponding bit line to corresponding bit line sensors ( 614 ); for a transistor that has been stressed in previous write operation, its bit line current should be smaller than the reference current (I nr ); for a transistor that has not been stressed in previous write operation, its bit line current should be about the same as or larger than the reference current (I nr ). The bit line sensor circuits ( 614 ) sense the amplitudes of those bit line currents to determine corresponding data values. If p-channel transistors, instead of n-channel transistors, are used in the memory block ( 610 ), then current differences may behave in opposite ways.
It is a common practice to execute a read operation after a write operation in order to make sure correct data pattern has been written properly. Multiple write/read operations maybe necessary to assure correct data are written. During an erase operation, one of the word line decoder ( 612 ) pulls the voltage on the selected word line (WL n ) to a voltage optimized for maximum stress rate (Vgst). All the other word lines remain at zero. The bit line stress circuits ( 616 ) should drive zero to all bit lines except to the reference bit line. The reference bit line voltage should be high so that the selected reference transistor (M nr ) is under hot carrier stress. The reference transistor should be stressed as hard as all the other stressed transistors on the same word line so that new data can be written into the data transistors by another write operation. It is usually necessary to do a read operation following an erase operation in order to make sure enough stress has been done to the reference transistor. Multiple erase/read operations maybe necessary to assure the erase operation is properly done.
While specific embodiments of the invention have been illustrated and described herein, it is realized that other modifications and changes will occur to those skilled in the art. It should be understood that the above particular examples are for demonstration only and are not intended as limitation on the present invention. For example, the bit line sensor circuits in FIG. 6 ( b ) senses the difference in transistor currents between two transistors experienced different levels of hot carrier damages. For a designer skilled in the art, there are infinite ways in designing the sensor circuits. The sensor can sense current, threshold voltage, transconductance, . . . etc. Each bit line sensor circuit can have a multiplexer so that only a sub-set of the bit line currents are sensed. We also can have multiple levels of bit line sensor/amplifier circuits for a large SEPROM device. To achieve optimum reliability, we can have one reference transistor for every one data transistor. The size of the reference transistor can be different from the data transistors. There are also infinite ways in designing the stress circuits. There are infinite ways in the configuration of the SEPROM memory blocks. We also can have multiple levels of memory blocks for large SEPROM devices. Hot carrier effects are used in the above example, while one can use Vg stress or other types of electrical stresses to alter the properties of transistors to achieve the same purpose. In the above example we use MOS transistors as the stressed devices. We also can use other types of devices. FIG. 6 ( c ) shows an example when bipolar transistors are used in the memory block, and FIG. 6 ( d ) shows an example when diodes are used.
The SEPROM devices of the present invention have the following advantages:
The major advantage is that SEPROM can be manufactured by any IC technologies. They are ideal for embedded applications. Each data point is memorized by one transistor; it is therefore possible to store large number of data at very low cost. The data stored in SEPROM devices are not detectable by any physical analysis, and the devices appear identical to any other transistors; it is therefore ideal for security applications.
One potential disadvantage of SEPROM is that writing data to SEPROM can take longer time than writing to floating gate devices. This problem can be solved by many methods. For example, we can set the stress condition at maximum stress rate determined by existing data. Increasing stress voltages usually increase the stress rate exponentially. We also can reduce the channel length of the transistors to increase stress rate. Removing LDD will increase hot carrier effects significantly.
Another disadvantage is that SEPROM devices can not be re-programmed for many times because the stress damage is usually accumulative.
The stress damage can partially recover after initial programming. That is not a problem when the supporting sense circuit has enough margins. We also can refresh the data by writing the same data back into the SEPROM periodically.
Above all, SEPROM devices provide the possibility to support a wide variety of novel applications.
While specific embodiments of the invention have been illustrated and described herein, it is realized that other modifications and changes will occur to those skilled in the art. It is therefore to be understood that the appended claims are intended to cover all modifications and changes as fall within the true spirit and scope of the invention.
|
The present invention teaches novel electrically programmable read only memory (EPROM) devices for embedded applications. EPROM devices of the present invention utilize existing circuit elements without complicating existing manufacture technologies. They can be manufactured by dynamic random access memory (DRAM) technologies, standard logic technologies, or any type of IC manufacture technologies. Unlike conventional EPROM devices, these novel devices do not require high voltage circuits to support their programming operation. EPROM devices of the present invention are ideal for embedded applications. Typical applications including the redundancy circuits for DRAM, the programmable firmware for logic products, and the security identification circuits for IC products.
| 7
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. Utility application Ser. No. 11/482,356, entitled “METHOD AND PROCESS OF COLLECTING, PACKAGING AND PROCESSING RECYCLABLE WASTE,” filed on Jul. 7, 2006, which is a continuation of U.S. Utility application Ser. No. 11/299,442, entitled “METHOD AND PROCESS OF COLLECTING AND PROCESSING RECYCLABLE WASTE,” filed on Dec. 12, 2005, which is a continuation of U.S. Utility application Ser. No. 11/166,516, entitled: “METHOD AND PROCESS OF COLLECTING AND PROCESSING RECYCLABLE WASTE,” filed on Jun. 24, 2005, each of which are incorporated herein by reference in their entireties. This application also claims the benefit of U.S. Provisional Application No. 60/617,971, filed Oct. 11, 2004, which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. The Field of the Invention
[0003] The present invention relates to the field of recycling. More particularly, the present invention relates to systems, methods, and devices for collecting and processing recyclable waste byproducts through the formation of bales including the recyclable waste.
[0004] 2. The Relevant Technology
[0005] As the consuming public demands increased convenience when shopping for products and services, retail and wholesale distribution centers are following the “super-center” trend and carrying not only greater quantities and varieties of products, but are also offering services which have previously required consumers to visit a separate store. With the increased quantity and variety of products and services, the amount of waste generated at such retail and wholesale centers has also increased. As a result, recycling is increasingly important to control the costs associated with this increased amount of waste.
[0006] By way of example, retail and wholesale centers are now common which merge the traditional department stores carrying clothing with a grocery store. As a result, customers can visit a single store to obtain most of the items the customer may need, whether it be groceries or clothing. Moreover, many of these stores offer an even greater one-stop-shopping experience by combining even more types of products and services into a single establishment.
[0007] For instance, a single store may now offer not only clothing and grocery items, but also furniture, electronics, office supplies, automobile parts, sporting goods, and the like. Some retail and wholesale distribution centers have expanded even further and provide auto servicing centers, business centers, beauty salons, restaurants and vending areas, photography studios, and the like all under the same roof.
[0008] Each type of product or service potentially brings with it various types of recyclable and non-recyclable waste which must be dealt with by the retail or wholesale center. For example, the use of plastic wrap and plastic film bags is increasingly permeating more and more aspects of retail sales as well as the shipping and packaging industry. For example, plastic shopping bags are well known to the general public as they are a predominant method for consumers to carry groceries and other purchased goods from a store. An even greater volume of plastic film, however, is generated for product packaging and distribution. For example, palates of goods are frequently wrapped with large sheets of shrink wrap plastic film to keep the contents of the pallet from shifting or falling during transit. Groceries may, for example, be loaded by a distributor onto the pallet and then wrapped with shrink wrap in this manner.
[0009] Another example is in clothing distribution in which each garment is typically transported wrapped in its own plastic sleeve and/or included with a plastic clothing hanger used by the retailer to store and display the item. Some estimates are that plastic bags on apparel can account for over sixty percent of plastic waste at retail department stores.
[0010] Restaurants and vending areas may also receive food items and food containers which are similarly packaged and wrapped in shrink wrap that must be disposed of by the store. In addition, recyclable products such as aluminum beverage cans or drink bottles made of polyethylene terephthalate (PET) or another plastic may collect in such areas and, if not recycled, are also discarded by the store. Business centers and auto servicing centers similarly produce still other waste byproducts. For example, an auto servicing center may provide various servicing options such as oil changes and fluid exchange services. As a result, the auto servicing center may produce and discard large numbers of gallon bottles used to store window washing fluid or antifreeze/coolant or quart bottles used to store motor oil. In some cases, such bottles are made of high density polyethylene (HDPE) or another recyclable plastic. Business centers, in which consumers may make photocopies or access computers to print documents or images, may also produce large amounts of discarded paper and shredded paper. Such paper, coupled with the paper and shredded office paper produced by the store's managing office, is often a large quantity of recyclable waste.
[0011] With this vast amount of plastic and other recyclable waste byproducts used in the packaging and shipping industries, and in the everyday operations of a retail or wholesale distribution center, there is a need to recover this material out of the waste stream in an efficient and effective manner. Stores that aggressively collect and recycle waste byproducts separate from other garbage frequently save hundreds of dollars per month in the cost of trash hauling. Still, the storage, baling, shipping, and processing of plastic and other recyclable waste byproducts is extremely inefficient under current methods.
[0012] At stores and distribution centers, for example, one conventional method of collecting plastic waste film for recycling is to stuff the plastic into other large plastic bags and toss them somewhere in the facility in a haphazard fashion (e.g., on top of other bales or bins). For transportation, the bags are thrown into the back of a truck for transportation. Similar methods are often used for collecting other recyclable waste byproducts such as beverage containers, plastic bottles, shredded paper, and plastic hangers. These methods are, however, extremely inefficient uses of space.
[0013] Because of these challenges, much of otherwise recyclable waste is disposed of as garbage. Not only does this add to pollution and more quickly fill landfills, but the recyclable waste byproducts fill on-site trash receptacles very quickly. Because waste is typically paid for by volume, i.e. the number of waste containers hauled off, the large volume of recyclable waste that is disposed of in on-site trash receptacles represents a significant cost. In addition, such waste has a recycling value that is unrealized when the recyclable waste is disposed of as garbage.
[0014] Despite the challenges in collecting recyclable waste byproducts, uses for recycled waste are quickly expanding. For example, recycled plastic is now used in plastic garbage can liners, landfill liners, agricultural film, and composite lumber products for picnic tables, park benches, porches, and walkways where rot-resistant wood-like products are desired. Shipping containers, carpet materials, and hard plastic containers are also more and more frequently made with recycled plastics. This increased demand for products made from recycled materials is fueling an increased demand for the collection of recyclable plastic and other waste.
[0015] In addition, recent increases in the cost of raw petroleum have led to a dramatic increase in the cost of plastics for plastic products. As a result, the per pound value of collected recyclable plastic has also increased dramatically. This adds to the demand for the collection of recyclable plastic.
[0016] Nevertheless, the volume of plastic and other waste that is collected for recycling remains considerably lower than is feasible. One key limitation on the use of recyclable waste is that the waste is often difficult and costly to collect. For example, consumers using small plastic bags rarely return them to a source whereby they can be recycled. In addition, at department stores shrink wrap plastic, garment bags, plastic clothing hangers, plastic bottles, metal cans, and the like are often discarded rather than collected. In particular, at department stores and warehouse stores recyclable materials, such as shrink wrap plastic, garment bags, plastic clothing hangers, plastic bottles, metal cans, and the like, are often discarded because the volume of space required to store all the recyclable materials accumulated within the store becomes too expensive to dedicate to that purpose. Although there are feasible methods for collecting such waste products, such as dedicated compacters and balers for each type of waster product, these devices are too expensive and the volume of space that must be dedicated to storing pre-compacted recyclable waste is usually impractical for most businesses. For instance, the amount of plastic film or garment bags necessary to form an entire bale of only plastic may take weeks or months to accumulate. The same holds true for plastic bottles, metal cans, and the like
[0017] By analogy, efforts at recycling cardboard have been much more successful. Cardboard recycling is performed at retailers, for example, by using large cardboard balers to compact waste cardboard and form the waste cardboard into bales for storage and transportation to cardboard recycling facilities. Cardboard balers are generally not used for recycling other types of recyclable materials, however, because they are often too large for the volume of specific types recyclable materials that are dealt with. Cardboard balers are typically designed to form forty-eight inch tall bales. The amount of individual types of recyclable material, such as plastic film, plastic bottles, metal cans, and the like, it would take to form a forty-eight inch tall bale typically cannot be stored by most, if not all, retailers. As a result, unlike cardboard, for which there is an efficient recycling infrastructure, there is currently no effective method for collecting large volumes of other types of recyclable materials.
[0018] In addition, cardboard cannot be mixed with plastic or other recyclable waste products during recycling. This is because they are completely different materials that are recycled by very different chemical and mechanical processes. There are also no efficient methods to separate such waste byproducts from cardboard since the value of either material does not justify the labor. For this reason, it is well known that the presence of plastic film, for example, in a cardboard bale leads to rejection of the entire bale such that it is discarded rather than recycled.
[0019] Accordingly, it would represent an advance in the art to provide systems and methods to more efficiently and less expensively collect and process recyclable waste byproducts for use in downstream recycling processes.
BRIEF SUMMARY OF THE INVENTION
[0020] The present invention relates to the collection of recyclable waste in bulk form. As noted above, the disposal or collection of recyclable waste from large retail stores, discount warehouses, and distribution centers has heretofore presented a significant cost to companies that made it inefficient or impractical. This difficulty in recovering recyclable waste results in the waste of a significant amount of otherwise recyclable materials and reduces profits for those that do not collect and recycle these byproducts.
[0021] These problems are overcome by the herein disclosed methods for the collection of recyclable waste within composite bales formed through novel methods of using balers such as conventional cardboard balers. In general, a composite bale is formed of multiple types of recyclable materials. For instance, a layer of recyclable cardboard can be combined with one or more layers of a different type of recyclable waste byproduct to form a composite bale. Similarly, one or more layers of a first type of recyclable waste byproduct, such as plastic film, can be combined with one or more layers of a second type of recyclable waste byproduct, such as metal cans, to form a composite bale. Still further, different recyclable waste byproducts, such as plastic film, plastic bottles, and shrink wrap, can be combined, either in layers or randomly, to form a composite bale. Thus, an amount of a type of waste insufficient to form a bale by itself can be combined with one or more different types of waste and compacted in a composite bale. As a result of these improved methods, a locale can use a cardboard baler not only to form cardboard bales, but also to form composite bales having any number of different recyclable materials therein.
[0022] Accordingly, a first embodiment of the invention is a composite bale formed of recyclable waste. The bale generally includes a layer of plastic that has a generally uniform thickness. The layer of plastic can include, for example, plastic bags, plastic film, or shrink wrap. The bale also includes a layer of recyclable waste on top of and in contact with the layer of plastic. The recyclable waste layer can also have a substantially uniform thickness. In addition, the recyclable waste layer itself may include multiple types of recyclable waste byproducts. For instance, by way of example, the layer may include used plastic bags, plastic film, aluminum cans, plastic bottles, plastic hangers, shredded paper, additional cardboard, and the like. The layer of plastic and the layer of recyclable waste are compactly bound together to facilitate transportation and storage of said bale
[0023] Another embodiment of the invention is a method for using a baler to collect recyclable waste. The method generally includes forming a composite bale of multiple recyclable materials by forming a layer of plastic and forming a layer of recyclable waste on top of the layer of plastic. The layer of recyclable waste can include multiple types of recyclable waste byproducts. The layer of plastic and the layer of recyclable waste are then compacted together with the baler. The compacted layers are bound together to maintain the bale in its compacted form.
[0024] Yet another embodiment of the invention is composite bale formed of recyclable waste. The composite bale includes a layer of recyclable waste. The layer of recyclable waste includes a plurality of types of recyclable waste products. At least a portion of the recyclable waste products are packaged in one or more compressible containers. Each of the one or more compressible containers can be dedicated to a single type of the plurality of types of recyclable waste products. Plastic bags or plastic film can further be sandwiched between the compressible containers of recyclable waste, either with or without a container of its own, to bond the containers of waste together and maintain the structural integrity of the bale during stacking, storage and/or transport. The layer of recyclable waste is compactly bound together to facilitate transportation and storage of the bale.
[0025] These and other objects and features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] To further clarify the above and other advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
[0027] FIG. 1 illustrates a cardboard bale according to the prior art;
[0028] FIG. 2 illustrates a plastic/cardboard composite bale according to one embodiment of the invention;
[0029] FIG. 3 illustrates a plastic/cardboard composite bale according to another embodiment of the invention;
[0030] FIG. 4 illustrates a composite bale having two layers of different types of recyclable waste according to yet another embodiment of the invention;
[0031] FIG. 5 illustrates a composite bale having three layers of differing types of recyclable waste according to an embodiment of the invention;
[0032] FIG. 6 illustrates another embodiment of a three layer composite bale according to the invention;
[0033] FIG. 7 illustrates a composite bale according to yet another embodiment of the invention, the bale having multiple types of recyclable waste randomly grouped within the bale;
[0034] FIG. 8 illustrates the composite bale of FIG. 7 wrapped in shrink wrap;
[0035] FIG. 9 illustrates the insertion of recyclable waste byproducts into a cardboard baler for forming a composite bale according to embodiments of the invention;
[0036] FIG. 10 illustrates a composite bale formed in a cardboard baler according to embodiments of the invention;
[0037] FIG. 11 illustrates a bin for storing recyclable waste prior to its compacting into a composite bale according to another embodiment of the invention; and
[0038] FIG. 12 illustrates another bin for storing recyclable waste prior to its compacting in a composite bale according to another embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] Reference will now be made to the figures wherein like structures will be provided with like reference designations. It is understood that the drawings are diagrammatic and schematic representations of presently preferred embodiments of the invention, and are not limiting of the present invention nor are they necessarily drawn to scale.
[0040] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be obvious, however, to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known aspects of cardboard balers and recyclable waste byproducts have not been described in particular detail in order to avoid unnecessarily obscuring the present invention.
[0041] Referring now to FIG. 1 , a conventionally formed cardboard bale 100 includes a compacted single layer 102 of cardboard. As depicted, the compacted cardboard bale 100 is bound together by bands 104 to keep the cardboard bale 100 in a compacted state. Cardboard bale 100 can be formed by a cardboard baler as generally depicted in FIG. 9 or any other suitable baler or device used to compact cardboard. Typically, the majority of the individual pieces of cardboard that form cardboard bale 100 come from the same product distribution activities that generate most recyclable plastic film.
[0042] As previously noted, it has been conventionally held that cardboard cannot be mixed with plastic film or other types of recyclable waste byproducts in collecting the materials for recycling. More particularly, the chemical and mechanical processes for recycling cardboard cannot work if plastics, metals, or other recyclable materials are also present. It has therefore been axiomatic that cardboard bales, such as bale 100 , cannot contain any plastic film or other recyclable waste byproducts, or the whole bale must be discarded. This is not only because the materials cannot be mixed in recycling processes, but the cost of separating other recyclable waste from the cardboard is too high for cost-effective recycling. The same holds true for mixing other types of recyclable materials. Specifically, the cost of separating and the differing recycling processes for plastics, metals, papers, etc. have prevented these types of materials from being mixed together in a single bale. As a result, mixed bales of recyclable material, including materials such as cardboard, plastic, metal, glass, and other types of recyclable waste have heretofore been discarded as waste.
[0043] Contrary to this conventional thinking, however, it has been surprisingly found that various types of recyclable waste can be effectively combined to form a combined, composite bale. As generally depicted in FIG. 2 , one embodiment of such a combined composite bale 200 having a thickness 202 incorporates a first layer 204 of cardboard and a second layer 206 of plastic, such as plastic film and/or used plastic bags. In the illustrated embodiment, the plastic layer 206 is positioned on top of cardboard layer 204 . Bale 200 can be formed in the reverse order with cardboard layer 204 on top of plastic layer 206 . In either configuration, the compacted plastic/cardboard bale 200 is bound together by bands 208 .
[0044] It can be readily seen in FIG. 2 how a significant amount of plastic film has been compacted to a relatively small space in the composite plastic/cardboard bale. In addition, it is also apparent that a significantly less amount of plastic is used in this plastic/cardboard bale than if the entire bale were formed of only plastic film. Thus, because a smaller amount of plastic film can be compacted in a single bale, the plastic can be disposed of in a timely fashion from a single location. In contrast, if the plastic were required to fill the entire bale, it may require many days, weeks, or even months to fill a single bale, requiring great expense to store a significant amount of un-compacted plastic.
[0045] Now referring to FIG. 3 , an additional embodiment of an exemplary composite bale 250 is illustrated. As generally depicted in FIG. 3 , composite bale 250 having a thickness 252 incorporates a first layer 254 of plastic, a cardboard layer 256 , and a second layer 258 of plastic. The cardboard layer 256 is in effect sandwiched between the two plastic layers 254 , 258 . The compacted composite bale is bound together by bands 260 . Thus, as depicted in FIG. 3 , composite bales can be formed with multiple layers of different types of recyclable waste. While FIG. 3 is illustrated has having a single cardboard layer sandwiched between two plastic layers, it will be appreciated that the bale could be formed with a single plastic layer sandwiched between two cardboard layers. Similarly, as discussed in greater detail below, the composite bale can also be formed with a plurality of layers and multiple types of recyclable waste, and the recyclable waste can be arranged in almost any configuration.
[0046] For example, FIG. 4 illustrates an additional embodiment of an exemplary composite bale 300 . As generally depicted in FIG. 4 , composite bale 300 has a thickness 302 and incorporates a plastic layer 304 and a recyclable waste layer 306 of multiple types of recyclable waste byproducts. The compacted composite bale is bound together by bands 308 .
[0047] Composite bale 300 acts as a complete packaging system in which a retail or wholesale distribution center—or any other location in which recyclable waste is produced—can package one or more types of recyclable waste byproducts into a single bale for shipment and delivery to a processing and/or recycling center. In the illustrated embodiment, for example, recyclable waste layer 306 includes a plurality recyclable portions 310 a - g which include one or more types of recyclable waste. For example, each recyclable portion 310 a - g may include one or more types of recyclable waste produced by a retail or wholesale distribution center. For instance, recyclable portions 310 a - g may include plastic hangers, shredded paper, plastic or aluminum beverage containers, plastic fluid containers, shrink wrap, used plastic bags, and the like.
[0048] As will be appreciated, particularly in light of the disclosure herein, recyclable portions 310 a - g may be of varying sizes, shapes and configurations within recyclable layer 306 . In some cases, this variation results from the type of recyclable waste byproduct packaged in composite bale 300 . More particularly, some recyclable waste products are highly compressible, such that when compacted in a baler, the volume the recyclable waste occupies in the bale can be significantly reduced. For instance, used plastic bags and plastic shrink wrap are pliable and also highly compressible. Similarly, plastic beverage containers, plastic fluid containers, and even aluminum beverage cans may contain a significant amount of air when discarded, and when compacted, the air can be discharged and the volume of the recyclable waste reduced.
[0049] Other recyclable waste, however, may be less compressible. For instance, plastic hangers do not capture a significant amount of air and are not pliable. Accordingly, when a volume of plastic hangers is compressed in a baler, the hangers maintain much of their original shape, thereby resulting in compression that can be much less significant than the compression of the same volume of, for example, plastic film or plastic beverage containers.
[0050] Accordingly, and as illustrated in FIG. 4 , when recyclable portions 310 a - g are compressed and baled, the shapes, sizes and configurations of each portion can vary. For instance, a recyclable portion with plastic hangers (e.g., portion 310 d ) will result in a greater thickness within composite bale 300 than a recyclable portion of the same volume that is filled with a more compressible material (e.g., portion 310 g ).
[0051] As discussed in greater detail herein, different recyclable waste byproducts can be packaged separately within composite bale 300 . For instance, recyclable portions 310 a - g can each be packaged within a compressible container such as, for example, a plastic bag made of a plastic film material. Separating materials into containers is desirable for a variety of reasons. For example, waste byproducts may be generated at different locales within a retail or wholesale distribution center such that it is more convenient for each different locale to package its recyclable waste byproducts separately. In addition, as discussed in more detail hereafter, such separation may facilitate handling of the byproducts at a processing or recycling center.
[0052] In one embodiment, the compressible container is a deformable plastic bag container. For instance, in one embodiment, the various recyclable waste products can be enclosed within a used shopping bag or clothing bag, such that the recyclable waste is enclosed within other types of recyclable waste byproducts. In other embodiments, it however, the compressible container is not a waste byproduct. For instance, a plastic bag may be obtained for the purpose of packaging of the recyclable waste and not generated by the day-to-day operations of a retail, wholesale or distribution center.
[0053] With continued reference to FIG. 4 , it will be seen that in some embodiments, a composite bale which packages multiple types of recyclable waste byproducts and/or waste byproducts which are not highly compressible, may further be configured to maintain its structural integrity during storage and shipment of the composite bale. For instance, composite bale 30 is adapted to maintain its structural integrity where a potential weak point otherwise exists in the bale.
[0054] In particular, when different portions 310 a - g of recyclable waste byproducts are compressed together, they may become rigid and/or not conform to the shape of an adjacent portion. Consequently, when the bale is created, the different portions can shift position during storage and/or transport, thereby weakening the bale. To reduce the effect of such weak points, composite bale 300 optionally includes bonding agents 312 between some or all of recyclable portions 310 a - g . Optionally, bonding agents 312 can be placed in recyclable layer portion 306 between recyclable portions 310 a - g and plastic layer 304 .
[0055] The bonding agent acts to stabilize the position of recyclable portions 310 a - g relative to an adjacent recyclable portion and/or plastic layer 304 . In one embodiment, for example, bonding agent 312 includes a compressible material that is sandwiched between two or more of recyclable portions 310 a - g . As a result, when a baler compresses bonding agent 312 and recyclable portions 310 a - g , the compressible bonding agent 312 can conform to the shape of the adjacent recyclable portions, thereby eliminating or reducing the space between portions and further increasing the structural integrity of the bale.
[0056] Bonding agent 312 may comprise any suitable material. For instance, in one embodiment, bonding agent 312 include compressible, recyclable waste byproducts generated by a retail, wholesale or distribution center that packages its recyclable waste into composite bale 300 . For instance, byproducts such as plastic film or used plastic bags can be placed between different containers of other recyclable waste products to bond them together and increase the bale strength. Such recyclable waste may be directly placed between recyclable portions 310 a - g or, in other embodiments, may be placed within a container such as a plastic bag, and the plastic bag then sandwiched between different recyclable portions.
[0057] Illustrated in FIG. 5 is another exemplary embodiment of a composite bale that can be formed according to the present invention. More specifically, FIG. 5 illustrates a composite bale 350 that has a total thickness 352 . Bale 350 is formed of three layers of recyclable waste. The first layer is a plastic layer 354 , the second layer is a recyclable waste layer 356 of multiple types of recyclable waste byproducts, and the third layer is another plastic layer 358 . The recyclable waste layer 356 is effectively sandwiched between the two plastic layers 354 , 356 . The compacted composite bale is bound together by bands 360 .
[0058] Similar to the recyclable waste layer 306 of bale 300 , recyclable waster layer 356 of bale 350 also includes a plurality of recyclable portions 362 a - g . The plurality of recyclable portions 362 a - g can include one or more types of recyclable waste. For example, each recycling portion 362 a - g may include plastic hangers, shredded paper, plastic or aluminum beverage containers, plastic fluid containers, shrink wrap, used plastic bags, and the like.
[0059] Additionally, recyclable waste layer 356 can also include a bonding agent 364 , which is similar to bonding agent 312 discussed above. More particularly, a bonding agent 364 , such as plastic film or used plastic bags, can be placed between recycling portions 362 a - g to bond them together and increase the strength of the bale as described above with regard to bale 300 .
[0060] FIG. 6 illustrates yet another embodiment of a composite bale formed according to the present invention. There is illustrated a composite bale 400 that has a total thickness 402 . Bale 400 has a similar makeup as bale 350 , except the layers of recyclable material are reversed. Specifically, bale 400 has a single plastic layer 406 sandwiched between two recyclable waste layers 404 , 408 . The compacted composite bale 400 is bound together with bands 410 .
[0061] Each of the recyclable waste layers 404 , 408 of bale 400 can include a plurality of recyclable portions, each having one or more types of recyclable waste such as plastic hangers, shredded paper, plastic or aluminum beverage containers, plastic fluid containers, shrink wrap, used plastic bags, and the like. Furthermore, each of the recyclable waste layers can also include a bonding agent, such as plastic film or used plastic bags, placed between the recycling portions to bond them together and increase the strength of the bale as described elsewhere herein.
[0062] FIG. 7 illustrates still a further embodiment of a composite bale 450 formed according to the present invention. Bale 450 differs from the previously described bails formed according to the present invention in that bail 450 does not comprise multiple layers of different types of recyclable waste. Rather, bail 450 comprises a single recyclable waste layer 452 . As with the recyclable waste layers described above, recyclable waste layer 452 includes a plurality of recyclable waste portions 454 a - o . Each of the recyclable waste portions 454 a - o can include one or more types of recyclable waste. For example, recyclable waste portions 454 a - o may include plastic hangers, shredded paper, plastic or aluminum beverage containers, plastic fluid containers, shrink wrap, used plastic bags, and the like.
[0063] Furthermore, when bail 450 is formed of differing materials that may not conform to the shape of adjacent materials, bonding agent 456 can be included in bail 450 . As described above, the inclusion of a bonding agent, such as plastic film or used plastic bags, between the recyclable waste portions 454 a - o can increase the structural integrity of bale 450 by acting to stabilize the position of recyclable portions 454 a - o relative to one another.
[0064] As noted herein, a composite bale may have any number of layers. For example, a bale may have a one layer of recyclable waste ( FIG. 7 ), two layers of different types of recyclable waste ( FIGS. 2 and 4 ), or three layers of recyclable waste ( FIGS. 3 , 5 , and 6 ). Additionally, a composite bale may have more than three layers of recyclable waste. For example, a composite bale may have three layers of plastic interposed between four layers of another type of recyclable waste. Thus, it will be appreciated, in view of the disclosure herein, that a composite bale with any number of layers of recyclable waste, with any number of intermediate layers of recyclable waste or cardboard, and which include any of various types of recyclable waste can be formed according to the present invention. The limiting factor is that the thickness of each layer of recyclable waste, and the number of such layers must be cost effective. This use of numerous layers may be preferable in locations where there is little storage space for loose or collected recyclable waste or cardboard, and so it is desirable to frequently compact the on hand loose and collected waste and cardboard in multiple layers. It may also be useful where, for example, different departments or service centers deliver their waste to the a baler at different times, so as to allow compaction of the various types of recyclable waste from a department or service center upon delivery of the waste to the baler.
[0065] Attention is now directed to FIG. 8 , in which the bale 450 from FIG. 7 is illustrated with shrink wrap 475 wrapped around the sides and ends thereof. Wrapping a compacted composite bale with shrink wrap can provide multiple benefits. For example, during transportation of the composite bale, the bale may be subjected to forces that can harm the structural integrity of the bail. Such forces can be forces normally encountered during transportation, including lifting, stacking, and dropping of the bale. Additionally, bales are often transported on flatbed transport vehicles. The high winds experienced by the bale during transportation on such a vehicle can cause some of the recyclable material in the bale to become dislodged and blow away from the bale.
[0066] In order to increase the structural integrity of the bale and prevent materials from falling or blowing out of the bale, the bale can be wrapped in shrink wrap as illustrated in FIG. 8 . Wrapping a bale in shrink wrap is an easy, quick, and convenient way to increase the bales structural integrity and enclose any loose materials within the bale. Thus, after the bale has been formed as described herein, an employ of the retail, wholesale or other facility or the transport personnel can simply wrap the bale in shrink wrap prior to transportation.
[0067] With reference now to FIG. 9 , a conventional cardboard baler 500 is used to form composite bales according to embodiments of the invention. Using conventional cardboard balers greatly reduces the cost to retailers and distributors that already have the balers on-site in that they do not have to acquire another machine nor do they have to store two or more machines, one for cardboard and one for each type of recyclable waste byproduct. The construction and operation of conventional cardboard balers, such as for example cardboard baler 500 , is well known in the art and will not be described in great detail herein. Most conventional balers are designed to form 48 inch, 60 inch, or 72 inch bales. While the discussion of FIGS. 9 and 10 refer to a bale formed of a plastic layer and a recyclable waster layer, it will be appreciated, that similar process steps can be followed to form any type of composite bale as described herein.
[0068] Generally, it can be seen that cardboard, plastic, and other types of recyclable waste byproducts can each be inserted through a top opening 502 while a gate 504 is in the open position. In the illustration, a series of bags 510 a - d containing recyclable waste have been inserted into baler 500 . Although not visible in FIG. 9 , a layer of compacted plastic is already formed below uncompacted bags 510 a - d in the bottom portion 506 of baler 500 , as can be seen in FIG. 10 . After gate 504 is closed, baler 500 can then be operated to compact bags 510 a - d into a compacted recyclable waste layer over the previously compacted plastic layer. It some embodiments, and with some types of recyclable waste, is preferable to load and compact several cycles of recyclable waste, for example eight to twelve cycles, to form an ideally sized recyclable waste layer.
[0069] In some embodiments, such as that illustrated in FIG. 9 , bags 510 a - d may include one or more air release holes 512 . Release holes 512 are, in this embodiment formed near the neck of bags 510 a - d and are configured to allow air to be easily released from bags 510 a - d when bags 510 a - d are compacted by baler 500 . One feature of holes 510 a - d is that as bags 510 a - d are compressed, air can easily flow through bags 510 a - d , thereby preventing breakage or rupture of bags 510 a - d that could otherwise occur were air to be trapped inside the bags. Should rupture to occur, the recyclable waste enclosed within bags 510 a - d could become separated from the bale and/or create voids within the bale. In either case, a weak point in the bale structure may be created, such that prevention of such facilitates maintenance of the structural integrity of the compacted composite bale.
[0070] While four release holes 512 are illustrated near the neck of each of bags 510 a - d , it will be appreciated that this is exemplary only and that any number and placement of holes 512 is contemplated. For example, holes 512 may be positioned at the bottom of bags 510 a - d , along the length of bags 510 a - d , or any combination thereof. In other embodiments, bags 510 a - d are made of a breathable material such that air can be expelled sufficiently through the surface of the bag.
[0071] Bags 510 a - d may further be made of a pliable material that stretches to prevent rupture or breakage before or during compression of the bag by baler 500 . This feature may be particularly desirable for some types of recyclable waste byproducts that are rigid, have sharp edges, or which are not highly compressible. For example, plastic clothing hangers may be placed in a flexible bag when they are discarded. To maximize the number of hangers in the bag, the hangers may be manually compressed into the bag, thereby causing the hangers to push against the interior surface of the bag, causing it to tear. By using a bag that stretches, however, the bag may have sufficient give to allow the contents of the bag to shift, and the bag stretches without rupturing. Similarly, when such materials are compacted by cardboard baler 500 , the contents of each bag can shift, thereby pushing against the bag and causing it to tear or stretch.
[0072] In some embodiments where bags 510 a - d are plastic and flexible, bags 510 a - d are made of a linear molecular plastic that stretches to prevent popping, tearing, or splitting of the bag. For example, the bags may be made of a non-porous linear low density polyethylene (LLDPE), although other types of bags are contemplated. For example, in other embodiments, the bag is not stretchable, is porous, and/or is not made of a plastic or polymer material.
[0073] After the recyclable waste layer is formed, an operator can insert one or more additional layers of recyclable material, such as another plastic layer, a recyclable waste layer having one or more different types of recyclable materials, a cardboard layer, or the like. After any additionally layers have been inserted into baler 500 , the operator can then operate baler 500 to compress the additional layer(s) over the recyclable waste layer. Once all the desired layers have been inserted and compressed, the finished bale is bound, preferably with wire in contrast to conventional plastic bands, so as to keep the bale compacted, after which it is then ejected from the baler 500 . Preferably the bales have two wires at each end to further bind the bales.
[0074] FIG. 10 illustrates a completed and bound composite bale 300 seated within bottom portion 506 of baler 500 . Alternatively, as previously discussed and illustrated in FIGS. 2 , 3 , and 5 - 7 , bales having one or more layers of different types of recyclable waste can be formed within a single bale.
[0075] One example process of implementing the invention involves first gathering recyclable waste to a single location. Such waste may include plastic, paper, metal, or other recyclable materials generated or produced on-site. For example, plastic shrink wrap used to package shipped products, plastic garment bags or clothing hangers removed from clothing prior to or at the time of sale, shredded paper, aluminum beverage cans, plastic beverage bottles, blow molded plastic one gallon or one quart containers, and the like. Such waste byproducts may also be gathered from other locations. For example, a collection location may have a collection program wherein consumers can return their aluminum cans, beverage bottles, or small plastic grocery or shopping bags for recycling. In addition, such items can be collected throughout a community, such as at local schools, to promote recycling and thereby provide the double effect of providing a revenue stream for the store (sales of recyclable waste) and by generating community goodwill.
[0076] The gathered waste may then be stored for a brief period of time until sufficient waste is collected to form a bale. Storing recyclable waste according to one embodiment of the invention includes providing a specially designed collection area. As seen in FIGS. 11 and 12 , such a collection area may be for example a tall narrow ball bin 600 , 650 similar to those currently used to store large rubber balls and the like. Within a ball bin 600 , 650 a plurality of bags 510 , such as a garbage bags, or other suitable bags or containers such as those described herein, are filled with the accumulated recyclable waste materials. The bags 510 are preferably themselves recyclable plastic film bags, although it will be appreciated that this is not necessarily a limiting feature of the present invention.
[0077] A ball bin 600 , 650 can be conveniently located near a cardboard baler so that bags 510 of recyclable waste can be stored vertically to minimize occupied floor space. Optionally, each locale at which recyclable waste is located has its own one or more collection bins. Accordingly, and by way of example, grocery and clothing departments may have their own bins, an auto servicing area may have its own bin, a vending/restaurant area may have a separate bin, an office center may have yet another bin, and so forth. The ball bins can also be formed or placed on a pallet 602 or wheeled dolly so it can be moved as desired. In the embodiment of FIG. 11 , the ball bin 600 can have a lightweight frame 604 , for example formed of PVC or some other hollow tubing. The depicted ball bin has a funneled top opening 606 and plurality of bungee cords or ropes 608 that keep bags 510 from falling out. For storage, bags 510 can be either tossed in through the funneled top opening or pushed between the movable bungee retainer cords 608 . The bags can then be removed for compacting by pulling them through the movable bungee retainer cords 608 . In the example embodiment depicted of FIG. 12 , the ball bin 650 may also be a metal cage having top and bottom openings where the plastic bags 510 can be tossed in and removed.
[0078] The bags of recyclable waste are preferably stored in a ball bin until it is completely full. That volume of recyclable waste is then loaded into the baler over a series of compacting cycles to make a composite bale. It has been determined, for example, that one bin of approximately four feet in width, four feet in depth, and ten feet in height can hold the plastic generated over two to three days by a typical large retail store or discount warehouse.
[0079] Upon formation of a composite bale, such as for example composite bales 200 , 250 , 300 , 350 , 400 , 450 , the composite bale can then be stored on-site until it is shipped to a processing center, optionally via other distribution locales such as return centers. Because, the recyclable waste has been compacted in the composite bales, it takes up the less space in a trailer or other transportation vehicle as a similar weight of loosely gathered recyclable waste.
[0080] At the downstream processing center the bale is separated into its constituent parts. For example, with reference to FIG. 4 , plastic layer 304 is separated from recyclable waste layer 306 , and the bags within recyclable waste layer 306 are further separated. With respect to FIG. 5 , first and second plastic layers 354 , 358 of bale 350 are separated from recyclable waste layer 356 , and the bags within recyclable waste layer 356 are further separated. Because each of the layers of recyclable material in the composite bale is contiguous, the compacted layers can be easily and readily removed and isolated for recycling. Moreover, where each bag within a recyclable waste layer contains only one type of recyclable waste product, the various types of waste products do not contaminate each other nor the other layers of recyclable material within the bale. A similar separating process can be followed for processing any composite bale formed of recyclable material, including bales similar to bales 200 , 250 , 400 , 450 described herein.
[0081] Various approaches can be used to track the weight of recyclable waste that is pressed into each composite bale. One efficient manner of keeping track of the volume of recyclable waste that is compacted in each bale is simply to measure the thickness of each layer of a distinct type of recyclable material and multiply that thickness times other known constants such as the dimensions of the bale to determine an approximate volume. This number is particularly helpful for use in determining the value of the recyclable plastic film that has been recovered.
[0082] For example, it is currently known that every three inches of compacted plastic film in a bale measuring sixty inches by forty-eight inches by thirty inches weighs about fifty pounds. A seventy-two inch by forty-eight inch by thirty inch bale, in turn weighs about sixty-five pounds. Thus, upon the formation of the bale the thickness of a layer of plastic film can be approximately measured in inches and a weight estimate can be made.
[0083] Alternatively, the thickness of a recyclable waste layer can be estimated as a fraction of the bale thickness. Regardless, the entire bale can also be weighed so that the correct fractional portion of the load is assigned to the recyclable waste.
[0084] In yet another alternative, past measurements of the various types of recyclable waste byproducts included in the composite bales can be used. For instance, for a particular size of bag, historical averages for the various types of recyclable waste can be calculated and used to approximate the weight of each type of waste material in the bale. Accordingly, upon creation of the bale, the retailer or other person can indicate on the bale, or on the shipping documents, the number of bags of each type recyclable waste byproduct that are in the bale. In this manner, when the bale is received by the processing center, the processing center can calculate the approximate weight of each recyclable material even without separating the bale. Of course, the processing or recycling center can also separate the bale and count the bags of each type of product to, for example, verify the retailer's count and/or to update historical average data.
[0085] In other embodiments, the historical weight averages may be used even without an indication by the retailer of the number of each type of product in the bale. For instance, the processing center may merely separate the bale and count each type of bag. To facilitate such counting, each bag may contain only one type of recyclable waste byproduct. In such cases, when a bale is created, recyclable waste such as plastic film, used plastic bags, HDPE bottles, PET bottles, aluminum cans, plastic hangers, shredded paper, and the like may not be combined into a single bag, but each packaged separately in one or more bags. Further, each type of byproduct may be enclosed in a different color bag such that the byproduct therein can easily be identified by the processing center even without opening the bag. In alternative embodiments, indicia may be provided on the container enclosing the byproduct (e.g., a description or picture of the byproduct) to facilitate identification, or the bags may not include any indicia or other method for distinguishing between types of content.
[0086] If a more accurate measurement of the recovered waste products is desired, then the whole bales can be again weighed at the processing or recycling center. Thereafter, after the bales are broken open and the various types of recyclable waste are separated from one another, each bag or each type of byproduct can once more be weighed to get a final accurate measurement of the recovered amount. Of course, not all of these measurements may be necessary depending upon the accuracy and tracking that is desired.
[0087] After sorting the various types of recyclable byproducts from each bale, each of the various types of byproducts can be baled separately and/or shipped either on truck or rail car to paper, metal and plastic manufacturers and recyclers throughout the country.
[0088] The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
|
Recyclable waste byproducts are efficiently collected for recycling at stores or other locations by compacting the recyclable waste as layers in a composite bale. The composite bales can be formed using existing cardboard balers that retailers or other stores typically already have for baling recyclable cardboard. In one embodiment, the composite bales are formed by binding together a layer of one type of recyclable waste and a layer of recyclable waste that includes one or more types of recyclable waste byproducts. The layered structure can be modified to omit one of the layers or to add additional waste byproduct layers.
| 1
|
This application is a continuation-in-part of application Ser. No. 830,701 filed Sept. 6, 1977, now abandoned.
FIELD OF THE INVENTION
This invention relates to a displacement measuring device and, more particularly, relates to an improved device for measuring and indicating the displacement of a movable member relative to a fixed member.
BACKGROUND OF THE INVENTION
It is oftentimes desirable to measure the displacement of a movable element relative to a related fixed element and to remotely indicate such displacement. Such can be the case, for example, where it is desirable to measure the displacement of a piston rod relative to the cylinder of a power actuator which can be utilized, again by way of example, on earth working implements such as plows or the like carried by a tractor carried by a road grader or the like.
Indicating devices have been heretofore suggested for indicating displacement of movable elements, including indicating displacement of a piston rod relative to the cylinder of a power actuator. Among such devices have been mechanical devices such as shown, by way of example, in U.S. Pat. Nos. 1,746,133; 3,077,179; 3,132,627; 3,275,174; 3,443,705; 2,704,047; 3,796,335; 3,883,021; and 3,900,073. In addition, stroke control of a piston is shown in U.S. Pat. No. 2,851,014.
Sensing of displacement of a movable element such as a piston has also been heretofore suggested in driven vehicles and such sensing has included, for example, the use of differential transformers or magnetic sensing (see, for example, U.S. Pat. Nos. 3,456,132; 3,956,973; 3,649,450; and 3,217,307).
In addition, sensing of movement of a movable element such as a piston, has also been sensed by mechanical means such as through the use of a ratchet and suitable other gearing (see, for example, U.S. Pat. Nos. 2,839,031 and 2,915,034) with the use of a ratchet and other gearing also having been heretofore suggested in conjunction with electrical circuitry for position indicating in U.S. Pat. Nos. 3,227,863 and 2,582,146, the latter of which also suggests the use of a variable resistance means in measuring water power.
Earth moving, or working, implements have heretofore been suggested having electro-mechanical indicating means for indicating the positioning of a blade or the like. Examples of such devices are shown in U.S. Pat. Nos. 3,512,589 and 2,972,194, the former of which includes switch controlled indicating lights and the latter of which includes a variable resistor the effective resistance of which is varied depending upon the blade cutting angle. In addition, earth working implements have also been heretofore suggested with indicating means that include a variable resistor the effective resistance of which is varied depending upon piston rod displacement of a power actuator (see, for example, U.S. Pat. No. 3,540,028).
Thus, while the prior art has suggested various types of electro-mechanical sensing devices including the use of variable resistors and associated circuitry for remotely indicating displacement of a piston rod relative to a cylinder of a power actuator, improvements in such electro-mechanical sensing devices are felt to be still possible.
SUMMARY OF THE INVENTION
This invention provides an improved electro-mechanical measuring device for measuring the displacement of a movable member relative to a fixed member and is particularly well suited for measuring piston rod displacement relative to the cylinder of a power actuator on an earth working implement.
According to the inventor:
"An Indiana farmer using a tractor and a pull type plow found that he spent as much time looking backward adjusting the plow as he did looking forward driving the tractor. It was obvious that as the hydraulic ram was extended or retracted, the plow was accordingly adjusted, and by placing an indicator on the tractor instrument panel, he would not need to look back as often. With the increase in size and length, implements have become increasingly hard to control. This is further aggravated by the fact that most tractors have a cab enclosure which restricts visibility. By using the subject invention, the operator or driver can make precise adjustments and have unlimited control of the implements he is using even though he cannot see them. The accessory assembly of the subject invention can be readily installed to hydraulic cylinders or units already owned.
The subject invention is used to indicate the position of a hydraulic ram and structures operable thereby. It converts the linear motion of the ram into an electrical signal with a corresponding read out on the instrument panel. When used on farm equipment, it provides a precise depth control monitor means.
The invention has a broad range of application. In fact, it need not be used with a hydraulic cylinder of actuator type assembly. It can be attached to any relatively movable objects where an indication of position is useful or meaningful; i.e., the travel of a rod or shaft in relation to a fixed member. A few of the suggested applications are: as an indicator of grain elevator chute door positions; to show the depth of cut on the blade of large earth moving equipment; to show the elevation of a dump truck bed as it is raised. Another application where this device can be used is to set the stroke limiting rods on a bolt bending machine even though a ram is not used.
Summarizing the objectives and advantages, it will be manifest that the invention promotes safe driving conditions for the driver as well as provides the remote control of tools or implements connected to or drawn by the tractor. The accessory allows the operator to have unlimited control of his equipment and the ability to make precise adjustment without leaving the operator's position. The unit is easily attachable to existing cylinders or actuators."
It is therefore an object of this invention to provide an improved electro-mechanical measuring device.
It is another object of this invention to provide an improved electro-mechanical measuring device for measuring the displacement of a movable member relative to a fixed member.
It is yet another object of this invention to provide an improved measuring device for measuring the displacement of a piston rod relative to the cylinder of a power actuator on an earth working implement.
It is still another object of this invention to provide an improved measuring device wherein one of a variable resistance means and a gearless actuating means is aligned with and extends along a movable member for a substantial distance in accomplishing the desired end.
In view of the foregoing a very important object of the subject invention is to provide an accessory assembly having a housing which is readily attachable to a hydraulic unit, means connecting a rear part of a tractor to a front part of an implement supporting frame whereby a driver can ascertain the position of the frame and/or implement by reading an instrument or indicator forwardly of or adjacent to the driver without the necessity of his looking backwardly to determine its trailing elevation, thereby promoting the safety of the driver and efficient operation of the tractor, since the hydraulic unit in at least some installations currently in use are substantially concealed from view or are not readily visible and thereby requires a driver to lean rearwardly or sideways in precarious or dangerous positions to determine the position of the unit and/or a frame in accord with at least those installations presently known to the inventor which are currently available on the market.
Another significant objective of the invention is to provide a durable accessory assembly for the purpose described above in which certain mechanical and electrical components of the system in the housing are responsive to the operation of a hydraulic unit and that a wiring harness or insulated conductors afford a unique setup whereby these electrical components and the instrument can be readily operatively connected to a source of electrical energy. The housing serves to substantially protect the components therein and means are provided whereby to facilitate attachment of the housing to a cylinder of a hydraulic unit.
Attention is directed to the important fact that the complete accessory assembly is located externally of a hydraulic unit and is comprised of relatively few components or parts.
Attention is further directed to the important fact that the subject invention has proven to be very practical under all conditions of use and particularly so since a driver by merely observing the instrument can operate the hydraulic unit to obtain a correct positioning of the frame and/or implement to obtain uniformity in the work to be performed by the implement carried by the frame. This factor is particularly advantageous where, for example, the depth that an implement is to till or condition soil can be predetermined to obtain uniformity in the conditioning process.
Summarizing the objectives and advantages it will be manifest that the invention promotes safe driving conditions for a driver or operator of a tractor; improves uniformity in conditioning of soil; the disposition of certain relatively simple durable and reliable responsive components in a housing or box which is readily detachably connectible to the upper side of a rear extremity of a cylinder to facilitate installation and access to the components, as distinguished from any intricate or complicated controls which are concealed in a cylinder of a hydraulic unit and difficult to correctly assemble and disassemble.
With these and other objects in view, which will become apparent to one skilled in the art as the description proceeds, this invention resides in the novel construction, combination, and arrangement of parts substantially as hereinafter described, and more particularly defined by the appended claims, it being understood that such changes in the precise embodiments of the herein disclosed invention are meant to be included as come within the scope of the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings illustrate complete embodiments of the invention according to the best mode so far devised for the practical application of the principles thereof, and in which:
FIG. 1 is a perspective view showing the device of this invention mounted on a tractor with a remotely positioned indicator;
FIG. 2 is a side view of the preferred embodiment of the displacement measuring device of this invention;
FIG. 3 is a side view of an alternate embodiment of this invention utilizing engageable arms and fingers;
FIG. 4 is a side view of another alternate embodiment of this invention showing a linear resistance element mounted on the cylinder;
FIG. 5 is a side view of still another alternate embodiment of this invention showing a linear resistance element mounted in the piston rod;
FIGS. 6 through 10 are directed to disclosures substantially constituting structure or system in addition to that depicted in FIGS. 1 through 5:
More particularly, FIG. 6 is a diagramatic or pictorial view showing the accessory as applied to a hydraulic cylinder;
FIG. 7 is a transverse section taken substantially on line 7--7 of FIG. 6;
FIG. 8 is a perspective view illustrating the operative relationship or certain components of the accessory;
FIG. 9 is view showing means for facilitating attachment of the accessory assembly to power unit; and
FIG. 10 is a schematic wiring diagram as utilized in the operation of the structure embodying the attributes of the subject invention.
DESCRIPTION OF THE INVENTION
Referring now to the drawings, the numeral 7 refers generally to the measuring device as accessory assembly of this invention, shown in FIG. 1 mounted on a conventional tractor 9 to measure the displacement of piston rod 11.
As is well known, earth working implements (such as a tractor or road grader or the like), often have mounted thereon, one or more power actuators 13 to position a frame 15 for supporting working elements or implements (such as those shown in FIG. 1).
Such power actuators 13 conventionally include a cylinder 17 having a piston 19 therein that is movable in opposite axial directions within the cylinder by introduction of fluids (gas or liquid) into the cylinder under pressure through the desired one of the fluid inlets 21 and 22.
Piston 19 has piston rod 11 connected therewith so that the rod, or ram, is movable in opposite directions into and out of the cylinder depending upon piston movement within the cylinder, as is well known. Cylinder 17 has a clevis or means 24 at the end opposite to piston rod 11 for mounting the cylinder on tractor 9 in conventional fashion but at a lower rear part thereof. The other or rear end of rod 11 likewise has a clevis or means 26 thereon for mounting the rod to the structure to be positioned (ie, the frame 15, for example), again in conventional fashion.
The measuring device or accessory assembly of this invention is mounted between the fixed member (cylinder) and movable member (piston rod) to measure the displacement of the movable member relative to the fixed member. In the preferred embodiment shown in FIG. 2, a variable resistor 30 is mounted exteriorly on the upper side of a rear extremity of cylinder 17 by detachable connecting means such as a conventional clamp, or collar, 32. As is conventional, variable resistor 30 includes resistive element 34 and a wiper arm 36 which engages the resistance element with the positioning of the wiper arm determining the effective resistance of the resistor, as is well known. Wiper arm 36 is mounted on control shaft 38 so as to be rotatable therewith with shaft 38 extending from resistor 30 normal to the central axis of the cylinder (and hence normal to the opposite axial directions of movement of piston 11).
Control shaft 38 has a pulley 40 mounted thereon outwardly of the resistor and is provided with a retraction spring 42 biasing the shaft an pulley to rotative movement in one direction.
A cable or flexible element 44 is wound about pulley 40 in a direction so that the cable tends to wind about the pulley (rather than being biased for unwinding) and the outer end of cable 44 is fastened to means such as a collar 46 mounted on piston rod 11 outwardly of the cylinder and preferably near the means or clevis 26.
Electrical leads 50 and 51 are connected between connecting ears 53 and 54 on variable resistor 30 and indicator 56 which is remotely mounted and preferably mounted for easy viewing by the tractor operator. Indicator 56 may be conventional and indicates displacement depending upon the effective resistance of variable resistor 30 electrically connected therewith.
In operation, as piston rod 11 is moved, or displaced,relative to the cylinder by withdrawing the rod from the cylinder, cable 44 is pulled outwardly from the variable resistor to unwind the cable from pulley 40. This causes the control shaft 38 of the variable resistor to move wiper arm 36 in one rotative direction and thus changes the effective resistance of the resistor (for example, to increase the effective resistance). When the piston rod is moved in the opposite direction, ie, into cylinder 17, the cable is caused to be rewound on pulley 40 by retraction spring 42. This causes the control shaft 38 of the resistor to be rotated in the opposite direction and moves the wiper arm in the opposite direction to change the effective resistance of the resistor (for example, to decrease the effective resistance if movement in the first direction increased the effective resistance). Sensing of the effective resistance is then utilized in the indicator to indicate displacement by simple preadjustment of the dial and suitable calibration as would be obvious to one skilled in the art.
In FIG. 3, the first alternate embodiment 107 of the measuring device is shown. In this embodiment, an arm 144 extends rearwardly from a collar 146 on piston rod 11 (and is preferably pivoted thereon) along and above piston rod 11 and cylinder 17 with an arm 144 extending outside the cylinder. A second arm 160 is mounted for pivotal movement in a substantially vertical path above cylinder 17 by a collar 162. As can be seen in FIG. 3, arm 160 is pivoted upwardly when arm 144 is moved rearwardly above the cylinder by retraction of piston rod 11 into cylinder 17, and allowed to pivot downwardly under the force of gravity when arm 144 is moved forwardly due to withdrawal of piston rod 11 from cylinder 17. If desired, a conventional shoulder 164 can be positioned on the underside of arm 160 to govern the rate of elevation or pivotal movement to be imparted to arm 160 due to movement of arm 144.
As shown in FIG. 3, variable resistor 30 is mounted above cylinder 17 and the control shaft 138 has a first finger 166 extending radially from control shaft 138 so as to be intregal with a finger 168 also mounted above cylinder 17 so as to be slidably connected with arm 160 and be pivoted thereby when arm 160 is pivoted upwardly. Finger 168 is contoured, as shown, so that the upward movement of arm 160 pivots finger 168 to move a finger 166 then engaging finer 168 and this rotates control shaft 138 a predetermined distance. This, of course, changes the effective resistance of resistor 30.
A second alternate embodiment 207 of the measuring device is shown in FIG. 4. In this embodiment, an arm 244 is mounted on a collar 246 (mounted on piston rod 11) with arm 244 extending rearwardly from collar 246 along and above piston rod 11 and cylinder 17. A linear, or straight line, resistive element 234 is mounted above cylider 17, as by collars 262, with the element extending along the cylinder so as to be engageable with a wiper arm 236 mounted on the rearwardly extending end portion of arm 244. As piston rod 11 is moved, the wiper arm 236 will engage a different portion of the resistive element so that the effective resistance that the resistor reflects on leads 250 and 251 will vary depending upon the positioning of the piston rod.
A third alternate embodiment of the measuring device 301 is shown in FIG. 5. In this embodiment, a resistive element 334 is mounted in the piston rod 11 and extends rearwardly into cylinder 17. Wiper arm 336 is mounted in the front edge of the cylinder so as to engage the resistive element, the portion of the element then being engaged depending upon the positioning of the piston rod relative to the cylinder. The effective resistance of the variable resistor is thus directly determined by piston rod displacement relative to the cylinder and is indicated by coupling to the indicator through electrical leads 350 and 351.
As can be seen from the foregoing, this invention provides an improved measuring device for measuring the displacement of a movable element relative to a fixed element.
The following description is presented to supplement and/or amplify that which has been set forth above with respect to FIGS. 1 through 5 and is directed particularly to the disclosures in FIGS. 6, 7, 8, 9 and 10. In order to promote continuity in the description new numerals are employed to designate the majority of components illustrated.
Referring specifically to FIG. 6 there is illustrated an accessory assembly comprisng a housing or box generally designated 400 containing the mechanical and electrical components shown in FIGS. 7 and 8. The accessory also preferably includes a cable 401 containing conductors attached to a female plug 402, a male plug 403 connectible to the female plug and a cable 404 containing conductors 405 and 406 attachable to a source of electrical energy and to ground and conductors 407 and 408 connectible with an instrument 409 the latter of which is adapted for mounting at a remote location such as at the front of a driver for readily ascertaining the position of the implement supporting frame 15. The conductors and plugs may be considered to constitute a wiring harness and a fitting 402' is provided to assist in the installation of the accessory wherever desired. Obviously, the lengths of the cables 401 and 404 and conductors therein can be modified to suit different installation requirements.
The housing comprises a base plate 410, front and back opposed walls 411 and 412, a pair of side walls 413, and a top or cover 414. The front and back walls are respectively provided with openings 415 and 416 for respectively receiving the cable 401 and a flexible element 417. The terms front, back and side walls are merely relative and applicable only to their position with respect to a tractor. The lower portions of the aforesaid walls are preferably flanged as indicated at 418 in FIG. 7 and are secured to the base plate by any suitable means such as by rivets 419. The top 414 is preferably an integral portion of the housing or it can be a separate member sealably connected whereby to facilitate access to internal components in the housing. In any event access to the components in the housing can be obtained more readily as compared to certain prior art structures in which complicated electrical and mechanical components are intricately mounted in a hydraulic cylinder of a power unit. The housing may be mounted wherever desired but is preferably detachably connected externally to an upper side of a rear extremity of a power unit in an out of way position by any means suitable for the purpose but a pair of crossed flexible straps or members are preferably secured to the underside of the base plate whereby to facilitate a durable detachable wrap connection about a cylinder. Obviously, means other than a pair of straps with bolts or screws or the use of a single strap 420 as shown may be utilized.
Support means preferably in the form of upstanding substantially planar supports 421, 422 and 423 are fixedly connected by any suitable fastening means, such as rivets 424 to the base 410 to locate the supports in the housing and position them in a predetermined spaced parallel relationship to provide a pair of spaced formations 425 and 426. The supports 422 and 423 are joined together by a bottom wall 427 and provides the formation 425 and the support 421 in combination with the intermediate support 422 provide the formation 426. These supports are respectively provided with aligned apertures through which a control shaft 428 is rotatably mounted.
A pulley or member 429 is fixedly secured to the shaft 428 for rotation therewith in the formation 425 provided by the supports 422 and 423. The flexible element 417 extends through the opening 416 in the rear wall 412 of the housing and has an inner end connected to the pulley and an outer end connected to the outer rear end of a piston rod 430 of a cylinder 430' by a clamp 431 or other suitable means. The rear end of this rod is connectible with the implement supporting frame 15 and the fore end of the cylinder to the tractor 9 as described above or the cylinder can be mounted wherever desired contemplated by the invention. A stationary means preferably in the form of a pin or bridge member 432 is secured to the supports 421 and 422 of the support means and biasing means preferably in the form of a helical spring 433 is disposed in the formation 426 formed by the supports 421 and 422, with the inner and outer ends of the spring being respectively fixedly connected to the shaft 428 and to the pin 432 in a manner whereby when the piston rod 430 is extended the pulley 429 will be rotated and cause the flexible element 417 to unwrap from the pulley and rewrap itself on the pulley whenever the rod is retracted. Bearing means 428' is carried by the support 423 for rotatably supporting the shaft 428.
The accessory assembly also includes electrical means confined in the housing 400. The electrical means preferably comprises a potentiometer generally designated 434, a combined trimmer 435 and a junction block 436, and a voltage regulator 437. These components are operatively connected and are responsive to the rotation of the pulley or operation of the mechanical components described above.
The potentiometer 434 as depicted in FIGS. 7 and 8 preferably includes a casing 438 fixedly secured to the outside surface of the support 423 and contains a resistance coil 439 and is provided with three terminals 440, 441 and 442. An arm or contact 443 is fixed for movement with the shaft 428 and an outer end of the arm serves to frictionally engage the coil 439 in a conventional manner.
The trimmer 435 is of a conventional character, mounted on the base plate 410 and has three conductors 444, 445 and 446 extending therefrom and the junction block 436 is preferably supported in an upstanding position in relation to the trimmer and provided with three terminals 447, 448 and 449.
The voltage regulator 437 is of a conventional character and is preferably mounted on the support 423 and provided with three terminals 450, 451 and 452.
The conductor 444 extending from the trimmer is connected to the terminal 450 of the voltage regulator 437, the conductor 445 to the terminal 440 of the potentiometer 434 and conductor 446 to terminal 448 of the junction block 436. A conductor 453 connects the terminal 452 of the regulator with terminal 449 of the block, a conductor 454 connects the terminal 451 of the regulator and terminal 442 of the potentiometer and block, and a conductor 456 connects terminals 442 and 448 of the potentiometer and block, all of which is depicted in FIG. 8.
The cable 401 extending through the front opening 415 in the housing contains three conductors 457, 458 and 459 which are respectively connected to terminals 447, 448 and 449 of the junction block 436. As depicted in FIG. 10 a fuse 460 is interposed in conductor 406 which is not shown in FIG. 6.
Referring to the schematic drawing of the electrical system as depicted in FIG. 10 of the drawing, the electrical means defined in certain of the claims includes the potentiometer 434 of a 10K character, the voltage regulator 437 as alluded to above and an adjustable 10K resistor or tirmmer 435. These components are operatively connected and preferably mounted within the confines of the housing 400 indicated by the dotted lines. The electrical means is also operatively connected to a source of electricity such as a battery 461 and to the instrument or volt meter 409, the latter of which is preferably located an appreciable remote distance from the housing and is provided with suitable indicia or dial as shown to indicate the position of the reciprocable member 430 which is operable by the power unit or cylinder 430'. The source or battery may offer a voltage within a range of 8 to 30 volts DC. The schematic drawing is presented for clarity and a better understanding of the system and it does not include all of the terminals and conductors above referred to with respect to FIGS. 7 and 8.
The male and female connectors 403 and 402, above referred to, serve to provide a quick detachable connection between the components in the housing and the wiring harness which is connected to the battery 461 and instrument 409 in order to facilitate installation of the accessory assembly. The fuse 460 in the conductor 406 obviously serves to protect the electrical system.
The female plug 402 is provided with three terminals 462, 463 and 464 and the male plug with three terminals 465, 466 and 467 which respectively engage the terminals of the female plug. The conductor 406 from a positive side of the battery is connected to the terminal 465 and a conductor 405 from the negative side of the battery is connected to the conductor 407, the latter of which extends from the instrument 409 and is connected to the terminal 467 of the male plug. The other conductor 408 extending from the instrument is connected to the terminal 466. The conductors 407 and 405 are grounded as indicated at 469.
The wiring harness also includes three conductors 459, 457 and 458 which are respectively connected to the terminals 462, 463 and 464 of the female plug 402. A conductor 446 extends from one end of the coil 439 of the potentiometer and is connected to the conductors 454 and 458 and to ground 474. The conductor 457 is connected to the arm 443 of the potentiometer which is rotatable with the shaft 428 and responsive to the operation of the member 430. The voltage regulator 437 is interposed between lines 454 and 459. One part of the adjustable resistor or trimmer 435 is connected to the voltage regulator by a conductor or line 444 and another part to an opposite end of the coil 439 of the potentiometer by a conductor 445.
As to the operation the inventor states that:
"The source of electrical energy or the battery 461 provides a voltage anywhere from 8 to 30 volts DC. The in-line-fuse 460 serves to protect the electrical circuitry. The voltage regulator provides an output of 6 volts regulated DC voltage. This voltage is fed through the 10K Ohm adjustable resistor 435 where 5 volts DC are picked off and fed to the 10K Ohm potentiometer 434. In other words, the resistor controls and adjusts the amount of energy flowing to the potentiometer. When the potentiometer is operated by movement of the arm 443 which is actuated by the shaft 428 through the agency of the flexible element 417 and reciprocable member 430 of the power unit the resistance is changed or varied and this affects a change across the potentiometer (0-5 volts DC). The voltage change is fed to the instrument of position indicator 409 which is a 0-5 volt DC voltage meter which is preferably located in front of a driver for readability to determine how the power unit 430' should be operated to raise or lower the implement supporting frame."
It should be manifest that the operation of the potentiometer is responsive to the actuation of the reciprocable member 430; that the voltage regulator controls the amount of energy flowing to the resistor 435 and that the resistor controls and adjusts the voltage to the potentiometer and that the latter transmits its message to the instrument 409.
The foregoing system has proven to be very reliable, efficient and durable when subjected to all normal conditions of use, at least with respect to farm implements as described above, and does not involve the use of a multitude of intricate or complicated components or parts when compared with the electrical and mechanical systems disclosed in certain of the prior art patents related to remote indication.
Having thus described my invention, it is obvious that various modifications may be made in the same without departing from the spirit of the invention, and therefore, I do not wish to be understood as limiting myself to the exact forms, constructions, arrangements, and combinations of the parts herein shown and described.
|
A displacement measuring device is disclosed that is particularly useful for measuring and remotely indicating the displacement of a piston rod relative to the cylinder of a power actuator of an earth working implement. The device includes a variable resistor controlled by a gearless actuator connected with the piston rod so that the effective resistance of the resistor is varied depending upon the axial displacement of the piston rod relative to the cylinder. An indicator is connected by electrical circuitry with the variable resistor to display the amount of piston rod displacement relative to the cylinder. A plurality of embodiments of the device are disclosed with one disclosed embodiment including a cable wound about a pulley mounted on the rotatable control shaft of the variable resistor with the cable having one end fastened to the piston rod and a retraction spring to maintain the cable taut regardless of piston displacement in either axial direction. The other disclosed embodiments include a linear resistant element mounted on either the cylinder or the piston rod with a wiper arm engaging the resistance element so that the effective resistance is varied depending upon the amount of piston rod displacement relative to the cylinder and a cylinder mounted pivotable first rod pivoted by a second rod mounted on the piston rod so that pivoting of the first rod in one direction causes a finger to be pivoted to rotate the control shaft of a variable resistor to thus vary the effective resistance of the resistor.
| 5
|
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 13/038,381, filed Mar. 1, 2011, which is a continuation of U.S. application Ser. No. 12/229,736, filed Aug. 25, 2008, which claims the benefit of U.S. Provisional Application No. 60/966,012 filed Aug. 25, 2007, the entire contents of which are incorporated by reference in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates generally to cleaning wipes, and more particularly has reference to a textured cleaning wipe for cleaning cell phones or other electronic devices.
BACKGROUND OF THE INVENTION
[0003] In the past decade cell phones have penetrated nearly 50% of the global population. It is estimated that about 4 billion people currently have a cell phone or other mobile electronic communication device such as a smartphone. Cell phone usage has also exploded during this time. As calling plans are more affordable, people are more accustomed and dependent on mobile communication, and cell phones do much more than just make calls, with many models providing web-surfing, email and gaming functions, in addition to organizer-like functions such as calendars and notepads, as well as video and image recording and playback. All this has physically resulted in a significant majority of the population, of all ages, constantly carrying around and often holding or using some type of small electronic gadget such as a cell phone, smartphone, mp3 player, digital camera, or other electronic device. These electronic devices typically have numerous buttons, slots, crevices, keys, screens and other uneven surfaces from which germs and bacteria accumulated from continuous use cannot be easily reached and cleaned with an ordinary wipe or cloth.
[0004] As a result, some scientists and microbiologists have concluded through lab tests and other studies that an average cell phone may be dirtier than a toilet seat. Even without these scientific studies, it is common sense that cell phones accumulate and harbor germs from constant use with hands, and from being pressed against the side of the face during a phone call. Women for example, suffer especially because they often get makeup on their cell phones. A need exists for a consumer cleaning article that will effectively clean the hard to reach spaces on various cell phone devices and other electronics such as game controllers, computer mice, mp3 players, etc. The present invention satisfies that need.
SUMMARY OF THE INVENTION
[0005] The present invention relates to cleaning wipes for electronic devices made from non-woven fabrics having a textured surface on one or both sides and their use as a wipe to clean and/or disinfect surfaces and crevices of electronic devices such as cell phones, keyboards, and digital cameras. In one embodiment, a cleaner and/or disinfectant solution is absorbed into the fabric. In another embodiment the cloth will have a plurality of projections that will extend across one length of the cloth without breakage. In another embodiment a plurality of projections will have triangular cross-sections and in another embodiment, a plurality of projections will have rectangular cross-sections. In one embodiment a plurality projections will be in form of pyramids, with breakage horizontally and vertically across the length and width of the cloth and will have triangular cross sections.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a simplified plan view illustration of a cleaning wipe embodying the novel features of the present invention, and showing a pattern of cone-shaped projections rising from the surface of a non-woven fabric.
[0007] FIG. 2 is a side elevational view of the cleaning wipe shown in FIG. 1 .
[0008] FIG. 3 is an enlarged, fragmentary, cross-sectional view, taken substantially along the line 3 - 3 , of FIG. 1 .
[0009] FIG. 4 is a simplified perspective view illustration of an alternative embodiment of the invention, showing a pattern of long triangular ridges extending across the surface of a non-woven fabric.
[0010] FIG. 5 is a simplified plain view illustration of yet another embodiment of the invention, showing a zig zag pattern of ridges extending across the surface of a non-woven fabric.
[0011] FIG. 6 is a simplified plan view illustration of yet another embodiment of the invention, showing a pattern of undulating ridges extending across the surface of a non-woven fabric.
[0012] FIG. 7 is a simplified plan view illustration of yet another embodiment of the invention, showing a pattern of pyramid-shaped projections rising from the surface of a non-woven fabric.
[0013] FIG. 8 is a perspective view of the wipe shown in FIG. 7 .
[0014] FIG. 9 is a simplified plan view illustration of yet another embodiment of the invention, showing another pattern of long triangular ridges extending across the surface of a non-woven fabric.
[0015] FIG. 10 is a perspective view of the wipe shown in FIG. 9 .
[0016] FIG. 11 is a cross-sectional view, taken substantially along the line 11 - 11 , of FIG. 9 .
[0017] FIG. 12 is a fragmentary, side elevational view of a roller die used to form projections on the surface of a cleaning wipe of the present invention.
[0018] FIG. 13 is an enlarged, fragmentary view of another embodiment of the invention, showing a cross-sectional view of long rectangular ridges extending across the surface of a non-woven fabric.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention relates to a cleaning wipe for electronic devices made up of a non-woven fabric having a textured surface on one or both sides of the baric especially designed to clean and disinfect the surfaces of electronic devices such as cell phones, keyboards, and digital cameras.
1. Definitions
[0020] The following terms are utilized throughout this application:
[0021] Projection or texture refer to any raised or lowered portions of a fabric with respect to the horizontal plane of the fabric. Thus, the term “projection” or “texture” includes, without limitation, a raised or depressed portion of the fabric that is surrounded by flat areas of the fabric (hereinafter “isolated projection”) and long continuous raised or depressed portions of the fabric that runs across the surface of the fabric (hereinafter “ridge”).
[0022] Triangular refers to a shape that resembles a geometric two-dimensional triangle. Triangular may cover shapes that do not have perfectly angled tips or flat surfaces of a triangle. The term triangular may include, without limitation, shapes which are wide at the base but narrows when approaching the apex.
[0023] Triangular cross section refers to the resultant triangular shape of a cross section through the middle of a projection.
[0024] Rectangular refers to a shape that resembles a geometric two-dimensional rectangle. Rectangular may cover shapes that do not have perfectly angled corners or flat surfaces of a rectangle. Rectangular may include, without limitation, shapes which are wide at the base and similarly wide at the top.
[0025] Rectangular Cross section refers to the resultant rectangular shape of a cross section through the middle of a projection.
[0026] The invention of the present application may be described by, but not necessarily limited to, the exemplary embodiments provided.
[0027] As is shown in the drawings for purposes of illustration, the invention embodies a textured cleaning wipe specially adapted for cleaning cell phones or other electronic devices. Preferably, the wipe is made of non-woven fabric that has projections on the surface of the fabric. In another embodiment, projections have a triangular or rectangular cross section.
[0028] A desirable feature of projections having a triangular cross-sectional shape is that they are adapted to effectively clean crevices and other small areas on the surface of electronic devices. The variable width from the base to the apex of a projection with a triangular cross section provides greater surface area to contact crevices and other small areas on the surface of electronic devices. This configuration allows projections to reach a plurality of hard to reach spaces on the surfaces of key pads, cell phones, or other electronic device. Projections with a triangular cross-sectional shape include, but are not limited to, conical projections, pyramidal projections, and ridges with a triangular cross section.
[0029] In a preferred embodiment, the projections have a triangular cross section as best shown in FIGS. 2-3 . The projections 2 rise from the surface 4 of a non-woven fabric 6 and have a triangular cross-section with a pointed tip 8 and wider base 10 , no matter what shape or pattern they create on the surface of the wipe (i.e. zig-zags, straight lines, S-curves, etc.)
[0030] Specific examples of suitable textures include an array of cones ( FIGS. 1-3 ) or pyramid-shaped projections ( FIGS. 7-8 ) arranged on the surface of the wipe in a series of rows and columns which forms a rectangular grid pattern, with each cone or projection being spaced from the adjacent cone or projection and being surrounded by flat areas of the surface.
[0031] Alternatively, the projections can be provided as a series of spaced-apart elongated ridges ( FIGS. 4-6 ) which run parallel to each other and extend across the surface of the wipe. The ridges can be straight ( FIG. 4 ), curved ( FIG. 6 ), or have a zigzag pattern ( FIG. 5 ). Preferably, each projection is relatively wide in cross-section as compared to its height.
[0032] The projections can be hollow (as shown), or more preferably, solid and filled with the same fabric material as the underlying substrate.
[0033] These projections with triangular cross sections can have a variety of different sizes and shapes. For example, the projections can have the shape of pyramids or cones, with square or round bases, respectively. The heights can vary from about 0.2-5.0 mm, and more preferably 0.5-2.5 mm. In a typical example, the bases (or diameters for cones) will be about 3 mm wide, and spaced about 2-4 mm apart horizontally and vertically across the surface of the non-woven fabric in a rectangular or non-rectangular grid pattern of discrete, spaced-apart projections.
[0034] Other embodiments feature long triangular ridges 12 or continuous elevations that run one length of the non-woven fabric, as best shown in FIG. 4 . One embodiment of the present invention involves utilizing triangular ridge projections between 0.5-2.5 mm in height, with a base width of about 1.0-5.0 mm spaced preferably 1.0-5.0 mm apart and having a length which is equal or substantially equal to the length of the fabric.
[0035] Other embodiments feature long rectangular ridges, 15 or continuous elevations that run one length of the non-woven fabric, as shown in a cross-sectional view in FIG. 13 . One embodiment of the present invention involves utilizing rectangular ridge projections between 0.3-2.5 mm in height, with a base width of about 1.0-5.0 mm spaced preferably 1.0-5.0 mm apart and having length which is equal or substantially equal to the length of the fabric.
[0036] Yet other embodiments modify the above ridges design by introducing vertical spaces or separations along the length-long ridges, resulting in a pattern such as the pyramid design described above, or the zig-zag pattern shown in FIG. 5 .
[0037] Yet other embodiments feature ridges that run across the wipe in zig-zag patterns ( FIG. 5 ), or S-shaped patterns ( FIG. 6 ). These produce a randomized cleaning angle, which is good for cleaning surfaces with a variety of differing sizes and shapes of crevices. Still other embodiments (not shown) feature ridges representing a mark or other figure or image, while maintaining the disclosed triangular or rectangular cross-section.
[0038] The non-woven fabric may be formed from a variety of different fiber blends and compositions. 100% split microfiber, 20-80% Polyester and 80-20% Nylon is presently preferred.
[0039] Alternatively, the fiber composition may consist of Eighty Percent (80%) Polyester and Twenty Percent (20%) Nylon. Additional, either Polyester or Nylon may be replaced with Rayon or other synthetic fiber or natural fiber. Other embodiments may be 25-95% split microfiber and 75-5% combination of synthetic or natural fibers less than 1 denier but preferably not split-able and not bi-combinant fibers. A particular fiber blend suitable for use with the present invention is One-Hundred and Fifty (150) gram fabric, 50% split microfiber (80/20% polyester/nylon blend) and 50% viscose (which gives it better body, folding ability and moisture absorption/release). Preferably, the resulting fabric is scratch-free. Examples of other fiber blends for the present invention include Microfiber 16 segmented PIR shaped rolls of fabric with central round core, star-like projections and triangular segments between each star shaped projection. In one embodiment of the present invention such fabric shall contain a Polyester core where triangles in between are Nylon, can be made with Nylon Core and protuberances and Polyester triangular segments in between. One method uses the bicombinant, drawn yarn; drawn through spinnerets however making the product with staple can be done and used if desired. Staple fiber is when the filament fiber is cut into pieces, then spun, drawn or by other method, made into a finished yarn which is then made into the non-woven substrate.
[0040] It is desirable for the projections to be sufficiently stiff or firm to resist axial compression when subjected to the range of pressures typically exerted by a person wiping a surface with a cloth. Various production methods can be used for making the non-woven fabric and the stiff projections with triangular or rectangular cross sections on the surface of the fabric.
[0041] The surface texturing can be formed in a variety of different ways, including calendaring, embossing, or embroidering, from a single piece of material. Alternatively, if desired, the projections can be formed separately from the same or different material, and attached to the wipe by adhesive or other suitable bonding methods.
[0042] For example, the non-woven webs may be created using a number of production methods common in the trade, including without limitation, needlepunch, spunlace, hydrojet or lattice methods.
[0043] The triangular or rectangular ( FIG. 13 ) ridges, cones or other projections created can be made using a heat roller with die on one or both sides and the fabric passing through the custom die(s) where with pressure and heat the projections are formed into the non-woven fabric. Examples of suitable devices include a metal, ultrasonic heated roller die 14 ( FIG. 12 ) or a hard rubber roller die with electrical coils (non shown).
[0044] A variety of different methods can be used to keep the projections firm. Thus, for example, in a production method using die, heat and pressure to create the triangular projections, the heat and pressure are also used to cause the projections created and its surrounding fabric to be pressed down, compressed using, for example, 10-1000 psi and heat of 100-225 degrees F., depending upon the fiber materials being used. The firmness also can be affected by the weight of the base fabric (e.g., 50 grams/square meter) and the fiber blend (e.g., 50% polyester/50% viscose).
[0045] In some embodiments of the present invention, a liquid solution is absorbed into the wipe. Dry fabrics generally do not remove oil and germs effectively.
[0046] In some embodiments of the present invention, a cleaning or disinfecting solution is absorbed into the wipe. Some cleaning or disinfecting solutions to be absorbed into a non-woven fabric include, but are not limited to, ethyl alcohol, Benzethonium Chloride, Alkyl, and Dimethyl Benzyl Ammonium Chloride. A variety of different cleaning or disinfecting solutions can be used. One cleaning solution is a quick-drying, alcohol-based cleaning solution to minimize the potential hazard of shorting electronic equipment. A calibrated amount of solution is used to moisten but not over saturate the non-woven fabric to minimize the potential hazard of shorting electronic equipment, while still providing effective cleaning power. Thus, for example, in at least one embodiment, the wipes are impregnated with approximately 1.5 g of liquid solution, but this amount can be affected by the size of the fabric (here, 4″×4″) and by the composition of the fabric and its absorbency (here, 50% viscose, 50% microfiber).
[0047] The wipes of the present invention can be packaged in a variety of different ways. In one embodiment, cell phone wipes will be packaged and sealed individually, allowing the users to remove one wipe from the box and take with him or her throughout the day, unwrapping and using the moist wipe when needed. Cell phone wipes are a mobile solution for a mobile device, cell phones. Thus, a tub-like dispenser or other multi-pack solutions are generally impractical because the busy cell phone user is not going to carry ten moist wipes with him or her. Single packaging allows users to take just one wipe with them on the road and use when needed, providing a more practical solution. Ideally, the wipes will be made compact (small) and convenient (disposable) so that they can travel with the device they are intended to clean. A typical size for a cell phone wipe is a rectangular sheet about 4″×4″ to 5″×5″.
[0048] While several particular forms of the invention have been illustrated and described, it will be apparent that various modifications can be made without departing from the spirit and scope of the invention.
|
A cleaning wipe with a plurality of stiff triangular or rectangular-cross-sectional projections rising from the surface of a non-woven cloth is designed to clean the nooks and crannies, various crevices and other hard to reach areas of cell phones or other electronic items with a myriad of buttons and/or camera lenses, charger outputs, mouthpieces, ear receivers and keypads which are designed in countless shapes and sizes. The projections, whether in the form of cones, pyramids, length-long ridges or other embodiments are specifically designed to clean the small crevices, the mouthpiece and earpiece and between small buttons such as keypads on a cell phone or other electronic device.
| 3
|
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Divisional of application Ser. No. 11/012,930, filed Dec. 15, 2004 now U.S. Pat. No. 7,083,234, which claims the benefit of U.S. Provisional Application No. 60/529,686 filed Dec. 15, 2003, and U.S. Provisional Application No. 60/589,297, filed Jul. 20, 2004.
BACKGROUND OF THE INVENTION
This invention relates generally to vehicle seating and more particularly to a tourist/coach class aircraft seating arrangement. Aircraft seating is typically divided into various classes, for example first class, business class, and coach or tourist class. For each class of seating, an individual passenger is allotted a preselected amount of space (both area and volume). First-class seats provide the most individual space, and also may include features to improve comfort, such as fully reclining sleeper functions. In contrast, the tourist/coach class is provided with a relatively small amount of space, in order to provide the most efficient transportation and lowest cost. However, this space limitation can produce passenger discomfort or possibly even physical ailments, and also makes it difficult for a passenger to find a comfortable position in which to sleep on long flights.
To alleviate discomfort, it is advantageous for a passenger to sit or lie in various non-conventional positions during a flight. Unfortunately, prior art coach class seats do not readily accommodate these varied seating positions.
BRIEF SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to provide a passenger seat accommodating varied seating positions.
It is another object of the invention to provide a passenger seat having a support member which moves in a cylindrical pivoting motion.
These and other objects of the present invention are achieved in the preferred embodiments disclosed below by providing a passenger seat for a vehicle includes a frame for being attached to a floor of a vehicle; a seat bottom carried by the frame for supporting a passenger; and an upwardly-extending seat back carried by the frame, wherein the seat back is pivotable in an arcuate motion about an upwardly-extending first axis which is not parallel to a long axis of the seat back.
According to another embodiment of the invention, the first axis passes through an upper end of the seat back and through a rear portion of the seat bottom.
According to another embodiment of the invention, the passenger seat further includes means for selectively locking the seat back in a desired orientation.
According to another embodiment of the invention, the seat bottom is pivotable in an arcuate motion about a generally longitudinally-extending second axis which is not parallel to a long axis of the seat bottom.
According to another embodiment of the invention, the second axis passes through a forward end of the seat bottom and through a lower portion of the seat back.
According to another embodiment of the invention, the passenger seat further includes means for selectively locking the seat back in a desired orientation.
According to another embodiment, a passenger seat for a vehicle includes: a frame for being attached to a floor of a vehicle; a seat bottom carried by the frame for supporting a passenger, wherein the seat bottom is pivotable in an arcuate motion about a generally longitudinally-extending first axis which is not parallel to a long axis of the seat bottom; and an upwardly-extending seat back carried by the frame.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject matter that is regarded as the invention may be best understood by reference to the following description taken in conjunction with the accompanying drawing figures in which:
FIG. 1 is a perspective view of a seat set incorporating a cylindrical motion back and bottom;
FIG. 2 is a perspective view of one of the seats shown in FIG. 1 ;
FIG. 3 is another perspective view of the seat shown in FIG. 1 , showing the details of its internal construction;
FIG. 4 is a perspective view of the seat shown in FIG. 1 , showing a passenger seated thereon;
FIG. 5 is a perspective view of a seat set having a pivotable seat back;
FIG. 6 is another perspective view of the seat set of FIG. 5 ;
FIG. 7 is a partial perspective view of the seat set of FIG. 5 , showing one of the seat backs thereof;
FIG. 8 is a perspective view of the seat back shown in FIG. 7 in a rotated position;
FIG. 9 is another partial perspective view of the seat set of FIG. 5 , showing one of the seat bottoms thereof; and
FIG. 10 is a perspective view of the seat bottom shown in FIG. 8 in a rotated position.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings wherein identical reference numerals denote the same elements throughout the various views, FIGS. 1-4 illustrate a passenger seat set 10 incorporating one or more cylindrical motion pivoting supports. The seat set 10 includes two seats 12 and 14 which are collectively provided with three arm rests 16 , 18 , and 20 , each shown in the lowered passenger use position. The seats include seat backs 22 and 22 ′, and seat bottoms 24 and 24 ′, respectively. The seats 12 and 14 are supported by a frame 26 . The frame 26 is mounted on legs 28 and 30 which are in turn mounted to the deck of the aircraft by track fittings of a known type. For illustrative purposes, the pivoting supports are only shown in detail with respect to the seat 14 , however it will be understood that the same type of supports may also be implemented on the other seat 12 .
Referring to FIG. 2 , the seat bottom 24 ′ has an internal structure which includes one or more stationary bottom members 32 a and 32 b, and a movable bottom member 34 . The stationary bottom members 32 cooperate to define an upper surface 36 having a cylindrical curvature with the axis of the defining cylinder aligned generally parallel to a longitudinal direction “A” of the aircraft. The movable bottom member 34 has an upper surface 38 for supporting a passenger's weight, and a lower surface 40 having a cylindrical curvature with the axis of the defining cylinder aligned generally parallel to a longitudinal direction “A” of the aircraft. The stationary and movable bottom members 32 and 34 may both be constructed of any material which will support the required weight and will remain sufficiently rigid to move relative to each other. One example of a suitable material is molded plastic.
The upper surface 38 of the stationary bottom member 32 and the lower surface 40 of the movable bottom member 34 may be made smooth to minimize the friction therebetween. In operation, the movable bottom member 34 can be slid or pivoted laterally relative to the stationary bottom member 32 so that its upper surface 40 lies in a tilted position, as shown in FIG. 4 . This movement could be effected manually, or the movable bottom member 34 could be connected to an actuator of a known type (not shown) for pivoting the movable bottom member 34 under power. Alternatively, the moveable bottom member 34 and the and the stationary bottom members 32 may be provided with suitable fasteners or connectors such that the moveable back member 34 may be physically disconnected from the stationary bottom member 32 and then reconnected in a different position. For example the stationary bottom member 32 and the moveable bottom member 34 may be provided with complementary hook-and-loop fasteners of a known type (not shown).
The seat back 22 ′ has an internal structure which includes a stationary back member 42 and a movable back member 44 . The stationary back member 42 defines a forward surface 46 having a cylindrical curvature with the axis of the defining cylinder aligned generally upright or vertical relative to the aircraft. The movable back member 44 has a forward surface 48 for supporting a passenger's weight, and a rear surface 50 having a cylindrical curvature with the axis of the defining cylinder aligned generally upright or vertical relative to the aircraft. The stationary and movable back members 42 and 44 may both be constructed of any material which will support the required weight and will remain sufficiently rigid to move relative to each other. One example of a suitable material is molded plastic. As shown, the movable back member 44 is relatively narrow and is designed to provided support for a seated passenger's spine without extending too far past the sides of the seat back 24 ′ even in a deflected position. However, the movable back member 44 could be made wider or of a different shape as required to suit a particular application.
The forward surface 46 of the stationary back member 42 and the rear surface 50 of the movable back member 44 may be made smooth to minimize the friction therebetween. In operation, the movable back member 44 can move in an arcuate motion relative to the stationary back member 42 so that its forward surface 48 lies in a tilted position, as shown in FIG. 4 . This movement could be effected manually, or the movable back member 44 could be connected to an actuator of a known type (not shown) for pivoting the movable back member 44 under power. Alternatively, the moveable back member 44 and the and the stationary back member 42 may be provided with suitable fasteners or connectors such that the moveable back member 44 may be physically disconnected from the stationary back member 42 and then reconnected in a different position. For example the stationary back member 42 and the moveable back member 44 may be provided with complementary hook-and-loop fasteners of a known type (not shown).
The seat 14 has a headrest 52 with an internal structure which includes a stationary headrest member 54 and a movable headrest member 56 . The stationary headrest member 54 defines a forward surface 58 having a cylindrical curvature with the axis of the defining cylinder aligned generally upright or vertical relative to the aircraft. The movable headrest member 56 has a forward surface 60 for supporting a passenger's weight, and a rear surface 62 having a cylindrical curvature with the axis of the defining cylinder aligned generally upright or vertical relative to the aircraft. The stationary and movable headrest members 54 and 56 may both be constructed of any material which will support the required weight and will remain sufficiently rigid to move relative to each other. One example of a suitable material is molded plastic. As shown, the movable headrest member 56 is relatively narrow and is designed to provided support for a seated passenger's spine without extending too far past the sides of the seat back 22 ′. However, the movable back member 56 could be made wider or of a different shape as required to suit a particular application.
The forward surface 58 of the stationary headrest member 54 and the rear surface 62 of the movable headrest member 56 are smooth to minimize the friction therebetween. In operation, the movable headrest member 56 can move in an arcuate motion relative to the stationary headrest member 54 so that its forward surface 60 lies in a tilted position, as shown in FIG. 4 . This movement could be effected manually, or the movable headrest member 56 could be connected to an actuator of a known type (not shown) for pivoting the movable headrest member 56 under power. Alternatively, the moveable headrest member 56 and the and the stationary headrest member 54 may be provided with suitable fasteners or connectors such that the headrest member 56 may be physically disconnected from the stationary headrest member 54 and then reconnected in a different position. For example the stationary headrest member 54 and the headrest member 56 may be provided with complementary hook-and-loop fasteners of a known type (not shown).
In the illustrated example, the seat back 22 ′ and seat bottom 24 ′ are covered with respective dress covers 64 and 66 which provide a unified appearance to the seat 14 and prevent debris from falling into the working parts of the seat 14 .
FIGS. 1 and 4 illustrate a representative passenger “P” seated on the seat 14 in a “side sleeping” posture in which his hips and shoulders are turned sideways, roughly 90° to a conventional seated position. The movable headrest, back, and bottom members 54 , 44 and 34 are positioned such that they provide lateral support and assist the passenger in comfortably maintaining this posture without muscular activity by the passenger. When the passenger wishes to return to a conventional seating posture the movable members are simply moved back to their centered positions.
FIGS. 5-10 illustrate a passenger seat set including a rotatable seat back and seat bottom, shown generally at reference numeral 110 . The seat set 110 includes two seats 112 and 114 which are collectively provided with three arm rests 116 , 118 , and 120 , each shown in the lowered passenger use position. The seats 112 and 114 are supported by a frame 122 . The frame 122 is mounted on legs 124 and 126 , which are in turn mounted to the deck of the aircraft by track fittings of a known type. For illustrative purposes, the rotatable seat back is only shown with respect to the seat 114 , however it will be understood that this feature may also be implemented on the other seat 112 . The seat 114 includes a seat back 128 and a seat bottom 130 .
The seat back 128 has an upper end 132 and a lower end 134 . The seat back 128 is able to rotate about an axis “A” (see FIG. 5 ) which passes through the center of the upper end 132 of the seat back 128 , at a pivot point “B”. The axis “A” is not parallel to the long axis “C” of the seat back 128 , and in this example it passes approximately through the center of the seat bottom 130 . The lower end 134 of the seat back 128 is provided with appropriate means to allow it to translate in an arc, such as a track or a rub strip (not shown), as well as means for locking the seat back 128 in the desired position. The seat back 128 is able to move left or right in a “conical” type motion to a deflected position, shown in solid lines in FIG. 7 , where it provides support for the back of a passenger who is seated in a “side sleep” position, helping the passenger to remain rotated relative to a normal sitting position.
The seat bottom 130 may also be able to rotate about an axis “D” (see FIG. 8 ) which passes through the center of the front end 136 of the seat bottom 130 , at a pivot point “E”. The axis “D” is not parallel to the long axis “F” of the seat bottom 130 , and in this example it passes approximately through the lower third of the seat back 128 . The rear end 138 of the seat bottom 130 is provided with appropriate means to allow it to translate in an arc, such as a track or a rub strip (not shown), as well as means for locking the seat bottom 130 in the desired position. The seat bottom 130 is able to move left or right in a “conical” type motion to a deflected position, shown in solid lines in FIG. 10 , where it provides support for a passenger who is seated in a “side sleep” position, helping the passenger to remain rotated relative to a normal sitting position. The motion of the seat bottom 130 may be independent, or it may be coordinated with the motion of the seat back 126 .
The foregoing has described a seating arrangement having an arcuate motion seat back and bottom. These seat features may be combined with each other as desired to produce a seat having multiple comfort features. While specific embodiments of the present invention have been described, it will be apparent to those skilled in the art that various modifications thereto can be made without departing from the spirit and scope of the invention. Accordingly, the foregoing description of the preferred embodiment of the invention and the best mode for practicing the invention are provided for the purpose of illustration only and not for the purpose of limitation, the invention being defined by the claims.
|
A passenger seat includes a frame, a bottom, a back, and a headrest, and incorporates a cylindrical motion support member. The support member includes a stationary member carried by the passenger seat, including a concave surface having a cylindrical curvature. A moveable member has a convex surface with a cylindrical curvature disposed in contact with the concave surface, and a support surface for supporting at least a part of a passenger's body The moveable member is selectively positionable along the concave surface. In another variation, the seat back and/or seat bottom is moveable in a conical motion.
| 1
|
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of U.S. patent application Ser. No. 11/055,934, filed Feb. 11, 2005, which claims the benefit of the filing date of U.S. provisional patent application No. 60/630,637, filed Nov. 24, 2004, the contents of which are all hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to photographic light diffusers and more particularly to portable light diffusers having compound geometry and separable components.
BACKGROUND
Diffuse lighting accessories are photography devices commonly used to provide soft lighting effects in photographs. To achieve a diffuse lighting effect, light can be either directly or indirectly passed through a semi-transparent material, or it may be reflected off a material which will cause it to scatter somewhat. Such diffuse lighting is commonly produced by light sources which are remote from the camera. Typically, such light diffusers are provided by stationary screens, umbrellas, soft boxes and the like. Such devices provide excellent lighting effects in fixed studio settings where there is no need to transport the lighting equipment including the diffusers from place to place.
Each particular shot to be lighted dictates the type and intensity of light needed to properly illuminate the subject. In some situations direct light from a light source without any alteration may be required. In other situations direct lighting may be too strong or cast overly distinct shadows, in which case a more diffuse light is desirable. In still other cases, an even more indirect diffuse light may be needed to create the proper lighting effect. It is important to have a certain amount of uniformity in the lighting used to illuminate the subject. This uniformity may be achieved using typical stationary diffusers provided that the equipment is of good quality and is employed in the proper fashion.
While the equipment described above provides good lighting effects in a fixed studio setting, it can be inconvenient if not impossible to use such stationary lighting accessories outside of the photography studio. For shoots which require the photographer to be mobile, outside of the photography studio. For shoots which require the photographer to be mobile, especially shoots where the photographer must capture action shots or cannot otherwise pose his subject, a small portable diffuser may be used which attaches directly to the camera itself. Such a light diffuser may be placed directly over an on-camera flash to provide a semi-transparent barrier to clear light transmission. Known diffusers exist which are small and portable with the camera and flash itself, and these diffusers are used by photographers in shoots where it is impractical to employ fixed lighting equipment. However, known portable diffusers for use with on-camera flashes are less than ideal in terms of the quality of lighting produced. These diffusers tend to create hotspots and may also leave noticeable, undesirable shadows.
SUMMARY OF THE INVENTION
In an exemplary embodiment, a photographic light diffuser is provided made from a translucent thermoplastic such as polypropylene or vinyl. In a further embodiment, the photographic light diffuser is made from flexible polyvinylchloride. The photographic light diffuser may be mounted directly to the head of an on-camera flash unit. The diffuser has a tapered cylindrical body which produces a soft, highly diffused and flattering light quality. The diffuser also includes a rectangular base with a flat surface to add an amount of specular or focused light. Because of the tapered cylindrical shape of the body of the diffuser, regardless of whether shots are taken in the vertical or horizontal position or under high or low ceilings the diffuser produces the same soft, flattering light quality. The present diffuser allows a photographer to achieve studio-quality lighting and greatly minimize shadows while providing a desirable light balance. In an alternative embodiment, the diffuser is provided with a removable dome which helps to diffuse light even further, especially in environments with low ceilings. Because the dome is removable, it allows one to easily shoot “flash direct” without needing to first remove the cowl that comprises the base of the diffuser.
In another exemplary embodiment, a photographic light diffuser comprises a semi-transparent cowl which is adapted to be mounted on a photographic light source, the cowl including an opening through which the photographic light source is visible when the cowl is mounted thereon, and a removable semi-transparent cover detachably mounted on the cowl.
In an alternative embodiment, a photographic light diffuser which is adapted to be mounted on a photographic light source comprises a base of a shape adapted to be mounted on a light source, a body extending from the base having both a generally convex outer surface as well as a smaller flat portion, and a cover connected to the body.
In yet another embodiment, a camera flash system comprises a camera flash unit, and a diffuser unit having an adaptor and a tapered cylindrical body. The adaptor is formed to match the shape of the housing of the camera flash unit so that it may be fitted thereto, and the adaptor extends between the camera flash unit and the tapered cylindrical body of the diffuser unit. The diffuser unit widens from the adaptor to meet the tapered cylindrical body.
In an exemplary embodiment, a photographic light diffusing device includes an at least partially transparent cowl adapted to be mounted on a photographic light source. The cowl includes a plurality of ribs and an opening through which the photographic light source is visible when the cowl is mounted on the photographic light source. The photographic light diffusing device can include a cover, where the cover at least partially fills the opening. The cover may be dome shaped and removable, and may extend outwardly or inwardly from the cowl. The cowl may be tinted and made from a flexible transparent material, and may include a flexible base adapted to fit on a plurality of different photographic light sources. The flexible base of the cowl may include a plurality of contact arms adapted to grip the photographic light source.
In another embodiment, the photographic light diffusing device includes an at least partially transparent cowl adapted to be mounted to a photographic light source. The cowl includes a base including a socket adapted to be mounted to the photographic light source. A tapered body with an opening opposite the base through which the photographic light source is directly visible when the base is mounted to the photographic light source. The tapered body further includes a convex portion through which light from the photographic light source is diffused. The photographic light diffusing device may include a cover adapted to fit over the opening. The cover may be removable and of a dome shape. The dome shape may extend outwardly or inwardly from the cowl. The tapered body of the cowl may be generally cylindrical. The cowl may be formed of a flexible transparent material and may include a plurality of ribs.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a front view of a photographic light diffuser according to one embodiment of the present invention;
FIG. 2 shows a bottom view of the photographic light diffuser of FIG. 1 ;
FIG. 3 shows a bottom view of an alternative embodiment of a photographic light diffuser;
FIG. 4 shows a side view in section of the photographic light diffuser of FIG. 3 ;
FIG. 5 shows a top view of the photographic light diffuser of FIG. 1 ;
FIG. 6 shows a cross section of a photographic light diffuser according to one embodiment of the present invention;
FIG. 7 shows a perspective view of the photographic light diffuser of FIG. 1 ;
FIG. 8 shows a perspective view of a diffuser in use atop a flash head; and
FIG. 9 shows a perspective view of an alternative embodiment of the photographic light diffuser.
Before any embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and arrangements of components set forth in the following description, or illustrated in the drawings. The invention is capable of alternative embodiments and of being practiced or being carried out in various ways. Also, it is to be understood that the terminology used herein is for the purpose of illustrative description and should not be regarded as limiting.
DETAILED DESCRIPTION
The present photographic flash diffuser provides high quality lighting effects when used with on-camera flashes, allowing photographers to achieve studio-quality lighting using electronic on-camera flashes without the need for separate lighting equipment. By doing so, the present diffuser does away with needing to carry around and use cumbersome lighting equipment such as brackets, umbrellas, soft boxes and the like, allowing for truly mobile, spontaneous photography.
FIG. 1 shows a front view of a photographic light diffuser 120 according to one embodiment of the present invention. This diffuser 120 may in one exemplary embodiment be formed from plastics using a vacuum molding process. It may also be made from other molding and non-molding plastic forming processes, as well as being formed from other appropriate semi-transparent or translucent materials as will be understood by one skilled in the art. The mold surface may be roughened to provide the diffuser 120 with a semi-transparent or translucent finish. This roughened surface may be created by treating the mold with a sand or bead blasting process. In one embodiment, the diffuser 120 may be formed having two separable parts. However, in an alternative embodiment, the diffuser 120 may be formed as a single piece having roughly the same overall shape as the embodiments shown.
As shown in the embodiment of FIG. 1 , the diffuser 120 is provided having two component parts; a cowl 130 and a removable dome 160 . The cowl 130 is provided with a generally rectangular base 140 allowing it to attach directly to the head of an on-camera flash unit. In one embodiment, the generally rectangular base 140 may be friction fitted to the head of the on-camera flash unit. In alternative embodiments, the generally rectangular base 140 of the diffuser 120 may be mounted on the flash unit using a bracket permanently or removably attached to the flash unit, or it may be mounted using a threaded collar, a bayonet style mount, using Velcro, or by other appropriate methods known to those skilled in the art.
FIG. 2 shows a bottom view of the photographic light diffuser 120 of FIG. 1 . FIG. 2 illustrates that the generally rectangular base 140 of the present diffuser 120 may be provided with a basal socket 170 of specific interior dimensions in order to match the exterior dimensions of standard camera flashes. This particular embodiment of a basal socket is designed to be friction fit to a Nikon SB-800 Speedlight flash unit. Other basal sockets may be configured for a friction fit with other models of camera flash units.
In yet another embodiment, FIGS. 3 and 4 show a photographic light diffuser with a generally rectangular base 240 that differs in size from the generally rectangular base 140 of the diffuser 120 shown in FIG. 2 . In this embodiment, the basal socket 270 of the diffuser 220 is of a predetermined size to accept any one of a number of different adaptors 290 , and it is the adaptor 290 , rather than the basal socket 270 , which sized to fit the exterior dimensions of the desired camera flash. The adaptor 290 may be a gasket-style adapter made from a flexible material to fit various flash units from different manufacturers, or it may be made from a stiffer material and designed to fit a single flash unit. The use of a diffuser with a “universal-mount” base of this embodiment permits a single diffuser to be used with various different flash units of widely different shapes by use of different adaptors.
Returning to the diffuser 120 of FIG. 2 , in an exemplary embodiment the base 140 extends past a minimum length of about one half inch to permit the base to fit over a flash unit, as well as to provide a generally rectangular base 140 between the flash unit itself and the body of cowl 130 of the diffuser 120 through which light from the flash travels. This relatively small generally rectangular base 140 adds an amount of direct or specular lighting to the flash effect created by the diffuser 120 . This effect is caused by the close proximity of the walls of the diffuser 120 in the area of the generally rectangular base 140 to the flash itself, causing light to be refracted through this area of the diffuser 120 with a greater intensity than through the tapered cylindrical body 150 of the diffuser 120 .
Accordingly, the lighting properties of the diffuser 120 can be varied by varying the relative proportions of the diffuser 120 , specifically the length and breadth of the passage through the generally rectangular base 140 with respect to the size of the tapered cylindrical body 150 of the diffuser 120 . A shorter passage and a larger tapered cylindrical body would cause the diffuser 120 to provide less of a direct and more of a diffused lighting effect. Conversely, a relatively longer passage and smaller tapered cylindrical body would affect the balance of the lighting effect created by the diffuser 120 in the opposite manner.
While the purpose the of the diffuser 120 is to ameliorate the harsh effects of direct lighting, some amount of direct light, or “key light” is desirable to provide an amount of specularity in an exposed image. The higher intensity gives a catchlight to the eyes of photographic subjects and prevents the image from appearing too soft. The compound geometry in the present diffuser 120 is designed to strike a balance between an image that is too harsh and one that is too soft.
As shown in FIG. 1 , the rectangular base of the diffuser 120 melds seamlessly into the tapered cylindrical body 150 , which helps to reduce hot spots and smoothly transitions the light distribution of the diffuser 120 from the more direct light of the rectangular base to the more diffuse light provided by the tapered cylindrical body 150 . The side view of the diffuser 120 of FIG. 1 also shows a cowl 130 of which the tapered cylindrical body 150 is a part, as is the generally rectangular base 140 . To this cowl 130 is connected the removable dome 160 . In contrast, FIG. 5 shows a top view of a photographic light diffuser 120 having a dome 160 . Finally, FIG. 7 shows a perspective view of a photographic light diffuser 120 according to one embodiment of the present invention having a cowl 130 comprising a generally rectangular base 140 and a tapered cylindrical body 150 , and a dome 160 attached thereto.
Returning now to FIG. 1 , an exemplary embodiment of the present diffuser 120 is shown wherein the tapered cylindrical body 150 is radially symmetric with respect to an axis extending along the direction of the flash unit on which the diffuser 120 is mounted. In this embodiment, the tapered cylindrical body 150 of the diffuser 120 is slightly tapered, flaring out as it extends away from the rectangular base. This tapered shape, while not required, helps to further reduce the hot spots which would otherwise occur as the light energy from the flash strikes the nearer parts of the tapered cylindrical body 150 with greater intensity than the farther, reducing the diffuse effect otherwise created by the tapered cylindrical body 150 . While some direct lighting effect is desired as discussed above, it can be provided more evenly and reliably by the generally rectangular base 140 , and as such it is desirable in the embodiment shown to emphasize the diffuse lighting function of the tapered cylindrical body 150 at the expense of the direct lighting function by providing this taper. With the present diffuser 120 , the softness of the lighting effect produced comes as much if not more so from the shape of the diffuser 120 itself and especially the manner in which light is evenly refracted through the surface of the tapered cylindrical body 150 as from the dispersal of light around the room, including light reflected by the walls and ceilings.
In one embodiment, the tapered cylindrical body 150 of the diffuser 120 allows it to provide similar lighting effects when used in either the vertical or horizontal positions, regardless of its orientation. Accordingly, unlike prior art diffusers, no flash bracket is needed with the present diffuser 120 to keep the flash in an upright position during both vertical and horizontal photography. In alternative embodiments, the tapered cylindrical body 150 of the diffuser 120 may form an ellipse in cross section, or one of a set of n-sided polygons. In still other embodiments, the tapered cylindrical body 150 may be longer or shorter than is shown in the figures, or may be of a cylindrical or other shape such as a non-tapered shape. In one embodiment, the height and width of the diffuser are about equal to one another. In another embodiment, the diffuser is generally spherical in shape. In yet another embodiment, the diffuser is proportioned so that it is easy to pack and transport in that it may be placed over the camera's lens when packed together with a camera in a standard camera/gadget bags, thus saving space. For example, the cowl 130 of the diffuser 120 may be placed directly over the lens of the camera, and the dome 160 may be placed in turn over the generally rectangular base 140 of the diffuser 120 . In this way, the parts of the diffuser nest within each other in a compact arrangement.
In an exemplary embodiment, the present diffuser 120 is convertible for use with both low and high ceilings. To this end, FIG. 1 additionally shows the diffuser 120 provided with dome 160 which may be removably attached to the cowl 130 so that the diffuser 120 can be used to provide a more diffuse lighting effect with the dome 160 in place while easily converting for direct flash lighting by removing the dome 160 .
When shooting with the diffuser in a vertical position in environments with high ceilings, the cowl 130 may be employed without the dome 160 . In one embodiment, the cowl 130 is provided with an open top which lets light energy from the flash shine upwards to reflect off the ceiling in the absence of the dome 160 . Due to the shape and orientation of the cowl 130 , enough light strikes the sides of the tapered cylindrical body 150 of the cowl 130 to cast some amount of light forward onto the subject even without employing the removable dome 160 . This gives a great lighting ratio for shots taken with the diffuser in the vertical position, reducing-shadows on the subject and giving a diffuse, soft light all around the room as well as on the subject. For large group shots, the lighting quality is soft, beautiful and diffuse. The open top allows a great deal of light to bounce off the ceiling onto the subject yielding a beautiful, natural lighting effect.
The dome 160 is provided for indoor environments with low ceilings where reflected light from the ceiling would cast harsh shadows on the subject. In one embodiment, the dome 160 acts as a diffusion device to spread light evenly all around the room, lighting the subject as well as brightening dark backgrounds and ceilings. The dome 160 may snap directly onto the cowl 130 of the diffuser 120 to accomplish this diffusion. Specifically, FIG. 6 shows a cross section of a photographic light diffuser detailing one embodiment of a snap-on system for connecting the dome 160 to the tapered cylindrical body 150 , wherein the former is provided with a recess which fits over a snap ridge 185 on the latter. Furthermore, the present combination of cowl 130 and dome 160 loses less power than other diffusers, making it more efficient. With the employment of the dome 160 with the diffuser 120 for use with low ceilings, studio-quality lighting using a flash can be achieved with a portable photography platform.
Additionally, when it is desirable to directly light a subject, it is not necessary to remove the entire diffuser 120 from the flash unit of the camera. The dome 160 only may be removed, and the flash pointed directly at the subject through the open top of the cowl 130 which remains attached to easily and directly illuminate the subject with no power loss.
On occasion, photographers will want the reflected light in their shots to have a particular color quality. This can be provided with alternative embodiments of the present diffuser wherein the material of the entire diffuser itself, or specific portions of the diffuser such as the cowl or the base are formed having a particular hue. For example, the dome 160 can be made amber for inside shots to provide warmer skin tones and for overall warming in flash filled available light shots, and green for shots where there is a good deal of florescent lighting.
FIG. 8 shows a perspective view of a diffuser 120 in use atop a flash unit 610 . In the embodiment shown, the diffuser 120 is employed without the removable dome shown in the previous figures. The generally rectangular base 140 of the diffuser 120 is socketed over the head of the flash unit 610 so that the light emitted by the flash may be diffused by the components of the cowl 130 of the diffuser 120 , specifically the generally rectangular base 140 and the tapered cylindrical body 150 .
FIG. 9 shows a perspective view of an alternative embodiment of a diffuser 300 in use atop a flash unit 610 . A cowl 301 of the diffuser 300 includes a neck portion 302 and a body portion 304 . The diffuser 300 can be formed from any suitable material. For example, the diffuser can be formed of a vinyl material which is capable of stretching. The vinyl used to form the diffuser 300 can be clear and bead blasted, which allows for greater dispersion of light through the diffuser. In this embodiment, a variety of flash units having different shapes can be inserted into the cowl 301 without the need to use the adaptor 290 (see FIG. 3 ). The neck portion 302 of the cowl 301 stretches to fit many flash units of various manufacturers, which are placed into the cowl 300 as described above. Contact arms 306 may extend along the basal socket 170 (see FIG. 2 ) from the bottom of the cowl 301 along the inside thereof. The contact arms 306 grip the flash unit 610 to ensure that the diffuser 300 does not fall off the flash unit during camera operation.
Ribs 308 extend along an inside surface in the body portion 304 of the cowl 301 . The ribs can extend substantially parallel to the flash unit 610 , or, they can extend around the circumference of the body portion 304 of the cowl 301 . The ribs 308 can also extend on an outer surface of the cowl 301 . The ribs 308 allow light to be more effectively diffused as it passes through the cowl 301 and into the area in which a photograph is being taken.
The cowl 301 can be operated by itself or in conjunction with a dome cover 310 which may optionally include ribs 312 . When the cowl 301 is used by itself, the light from the flash unit 610 escapes from the top without being diffused, throwing a concentration of direct light upward into the surrounding area. In an enclosed space, the direct light can lighten the room in colliding with the ceiling, without casting the harsh light of the flash directly onto the subject. An upper portion of the body portion of the cowl 301 can be trimmed around a circumference of the cowl 301 as desired to allow a greater amount of light to escape from the top without being diffused.
Where the room is sufficiently lighted such that the direct light is not needed, the dome cover 310 can be used in an upright or an inverted position to avoid the effects of direct flash lighting. The inverted dome 310 can be snapped into the cowl 301 , or can be formed integrally with the cowl 301 .
As in previous embodiments discussed herein, the diffuser 300 can be tinted with amber or another color to vary the color and intensity of the light on the subjects of the photograph. Due to its flexible nature, the diffuser 300 can be easily stored and transported in a camera bag. A photographer carrying many different diffusers can stack them for ease in storage and transport.
|
A photographic light diffusing device is provided. A flexible, transparent cowl is adapted to be mounted on a photographic light source, the cowl including a plurality of ribs and an opening through which the photographic light source is visible when the cowl is mounted on the photographic light source. The cowl elastically deforms to fit onto the photographic light source. A removable, flexible cover is placed over the opening of the cowl.
| 6
|
FIELD OF THE INVENTION
This invention relates to a heat-sensitive recording paper and, more particularly, to a heat-sensitive recording paper which does not undergo disappearance of recorded color image and background fogging due to various chemicals and oils.
BACKGROUND OF THE INVENTION
Heat-sensitive recording papers provide images by utilizing physical or chemical change of a substance caused by heat energy. A considerable number of such processes have been studied.
Recently, heat-sensitive recording papers have come into use as recording papers for recording outputs from facsimile or computers utilizing their merits or primary coloration and the lack of a need for a developing step. An example of such recording papers is referred to a dye-type, and is disclosed in Japanese Patent Publication Nos. 4160/68 and 14039/70 (U.S. Pat. Nos. 2,663,654 and 2,967,785), and Japanese Patent Application (OPI) No. 27253/80 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") (corresponding to U.S. Pat. No. 4,283,458).
In general, the use of heat-sensitive recording paper as a recording paper is desirable because the recording devices can be made lighter in weight and smaller in size. Accordingly, such paper has rapidly come into use. On the other hand, the heat-sensitive recording paper is not desirable when chemicals or oils are deposited thereon, images recorded thereon disappear or fogs are formed. These defects are serious from the practical point of view; thus promoting efforts to eliminate such defects.
Japanese Utility Model Laid-Open No. 125354/81 proposes a means of improving resistance against color disappearance with a plasticizer by providing a coating layer of a water-soluble high polymer on a heat-sensitive color forming layer for preventing permeation of the plasticizer. However, this process is insufficient for imparting resistance against various chemicals or oils.
Japanese Patent Application (OPI) No. 146794/81 proposes a means of imparting water resistance as well as resistance against color disappearance with a plasticizer by providing a coating layer containing a hydrophobic high polymer and/or water resistance-imparting agent in addition to the water-soluble high polymer. According to this proposal, an intermolecular cross-linking agent such as formalin, glyoxal, or melamine resin is used as a water resistance-imparting agent. When a coating layer of intermolecularly cross-linked water-soluble high polymer is provided, resistance against various chemicals and oils is improved to some extent as compared to that wherein only a coating layer of water-soluble high polymer is provided, but the resistance is still insufficient.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a heat-sensitive recording paper having sufficient resistance against various chemicals and oils.
This object of the present invention has been successfully attained by a heat-sensitive recording paper having a coating layer containing polyvinyl alcohol and boric acid provided on a heat-sensitive color forming layer containing as color forming components an almost colorless electron donating dye and an organic acid capable of forming color when in contact with said dye.
DETAILED DESCRIPTION OF THE INVENTION
Boric acid is known to form a monodiol type chemical bond with polyvinyl alcohol, and is essentially different from the intermolecular cross-linking agents such as formalin, glyoxal, melamine resin, etc.
The degree of saponification of the polyvinyl alcohol used in the coating layer of the present invention is 80 to 100 mol%, preferably 90 to 100 mol%, more preferably 98 to 100 mol%. If the degree of saponification is less than 80 mol%, there results insufficient resistance against various chemicals and oils. The polyvinyl alcohol used in the present invention has a molecular weight of 500 to 1,700, preferably 900 to 1,700, and the polyvinyl alcohol is preferably applied in a coating amount of 2 to 4 g/m 2 .
Boric acid is used in an amount of 1 to 20 parts by weight, preferably 3 to 12 parts by weight, per 100 parts by weight of polyvinyl alcohol. If the amount of boric acid is less than 1 part by weight, there results an insufficient resistance against various chemicals and oils, and if more than 20 parts by weight, the coating is impossible because of gelation of the coating solution.
A coating layer solution comprising polyvinyl alcohol and boric acid in the above-described proportion is prepared and coated on a heat-sensitive color forming layer to be described hereinafter. The coating is then dried to form the intended coating layer.
The heat-sensitive color forming layer of the present invention is described below.
Typical examples of the electron donating colorless dye (color former) used in the present invention include (1) triarylmethane compounds, (2) diphenylmethane compounds, (3) xanthene compounds, (4) thiazine compounds, and (5) spiropyran compounds, and specific examples thereof are described in U.S. Pat. No. 4,283,458. The color former is preferably used in an amount of 0.3 to 1 g/m 2 . Specific examples of triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (namely, Crystal Violet lactone), 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-5-dimethylaminophthalide, 3,3-bis(2-phenylindol-3-yl)-5-dimethylaminophthalide and 3-p-dimethylaminophenyl-3-(1-methylpyrrol-2-yl)-6-dimethylaminophthalide. Specific examples of diphenylmethane compounds include 4,4'-bisdimethylaminobenzhydrin benzyl ether, N-halophenyl leuco Auramine and N-2,4,5-trichlorophenyl leuco Auramine. Specific examples of xanthene compounds include Rhodamine B anilino lactam, Rhodamine (p-nitroanilino)lactam, Rhodamine B (p-chloroanilino)lactam, 7-dimethylamino-2-methoxyfluoran, 7-diethylamino-2-methoxyfluoran, 7-diethylamino-3-methoxyfluoran, 7-diethylamino-3-chlorofluoran, 7-diethylamino-3-chloro-2-methylfluoran, 7-diethylamino-2,3-dimethylfluoran, 7-diethylamino(3-acetylmethylamino)fluoran, 7-diethylamino(3-methylamino)fluoran, 3,7-diethylaminofluoran, 7-diethylamino-3-(dibenzylamino)fluoran, 7-diethylamino-3-(methylbenzylamino)fluoran, 7-diethylamino-3-(chloroethylmethylamino)fluoran and 7-diethylamino-3-(diethylamino)fluoran. Specific examples of thiazine compounds include benzoyl leuco Methylene Blue and p-nitrobenzyl leuco Methylene Blue. Specific examples of spiropyran compounds include 3-methyl-spirodinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxybenzo)spiropyran and 3-propyl-spiro-dibenzopyran. These compounds may be used alone or as a mixture.
Above all, xanthene type color former, many of which form less fog and provide high coloration density, are preferable.
Preferred organic acids used in the present invention include phenol derivatives and aromatic carboxylic acid derivatives, with bisphenols being particularly preferable. The organic acids are preferably used in an amount of 2 to 5 parts by weight per 1 part by weight of the color former.
Specific examples of the phenol derivatives include p-octylphenol, p-tert-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl)propane, 2,2-bis(p-hydroxyphenyl)propane, 1,1-bis(p-hydroxyphenyl)pentane, 1,1-bis(p-hydroxyphenyl)hexane, 2,2bis(p-hydroxyphenyl)hexane, 1,1-bis(p-hydroxyphenyl)-2-ethyl-hexane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, etc.
Useful aromatic carboxylic acid derivatives include benzyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, 3,5-di-tert-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid and polyvalent metal salts of these carboxylic acids.
Upon preparing a coating solution for producing heat-sensitive recording paper, it is necessary to disperse the above-described materials for producing heat-sensitive recording paper using water as a dispersion medium. Accordingly, the use of a water-soluble high polymer such as polyvinyl alcohol, hydroxyethyl cellulose or starch derivative is preferable. Dispersion of the material for producing heat-sensitive recording material using the dispersion medium is conducted by adding 10 to 50 wt% (based on the weight of the dispersion solution) of an electron donating dye or an organic acid to a dispersion medium generally containing 1 to 10 wt% (based on the weight of the dispersion medium), preferably 2 to 5 wt%, of a water-soluble high polymer, and using a dispersing machine such as a ball mill, sand mill, attritor, colloid mill, etc.
To a mixture of the above-described dispersions are added, if necessary, an oil-absorbing pigment, wax, metallic soap, etc., to prepare a coating solution for producing heat-sensitive recording paper. The resulting solution is coated on a support such as paper or plastic to obtain the intended heat-sensitive color forming layer.
The oil-absorbing pigment is selected from among kaolin, calcined kaolin, talc, pyrophyllite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea-formalin filler, cellulose filler, etc.
Examples of useful waxes include paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, higher fatty acid amides (e.g., stearic acid amide, ethylenebisstearoamide, etc.), and higher fatty acid esters.
Useful metallic soaps include polyvalent metal salts of higher fatty acids such as zinc stearate, aluminum stearate, calcium stearate and zinc oleate.
The present invention will now be described in more detail by the following examples which, however, are not to be construed as limiting the present invention in any way.
EXAMPLE 1
20 g of 3-diethylamino-6-chloro-7-(β-ethoxyethyl)aminofluoran was dispersed in 100 g of a 10% aqueous solution of polyvinyl alcohol (saponification degree: 98%; polymerization degree: 500) in a 300-ml ball mill for about 24 hours to obtain dispersion (A). Similarly, 10 g of 2,2-bis(4-hydroxyphenyl)propane and 10 g of stearic acid amide were dispersed in 100 g of a 10% polyvinyl alcohol aqueous solution in a 300-ml ball mill for about 24 hours to obtain dispersion (B).
The dispersion (A) and the dispersion (B) were mixed with each other in a weight ratio of 3:20, and 500 g of calcium carbonate fine powder was added to 200 g of the resulting mixture and well dispersed to prepare a coating solution for forming a heat-sensitive color forming layer.
This coating solution was coated on a base paper of 50 g/m 2 in basis weight in a coating amount of 6 g/m 2 by air-knife coating, and dried at 50° C. for 2 minutes to form a heat-sensitive color forming layer.
On the thus-formed heat-sensitive color forming layer was coated a coating solution for forming a coating layer having the following formulation in a coating amount of 3 g/m 3 , then dried at 50° C. for 2 minutes to form a coating layer. Thus, a heat-sensitive recording paper of the present invention was obtained.
______________________________________Coating Solution for Forming Coating Layer: parts by weight______________________________________5% Polyvinyl alcohol (saponifica- 100tion degree: 98%; polymerizationdegree: 1,700) aqueous solution3% Boric acid aqueous solution 10______________________________________
COMPARATIVE EXAMPLE 1
In the same manner as in Example 1 except for not providing the coating layer, a comparative heat-sensitive recording paper was obtained.
COMPARATIVE EXAMPLE 2
In the same manner as in Example 1 except for providing the coating layer by applying the following coating solution, another comparative heat-sensitive recording paper was obtained.
______________________________________Coating Solution for Providing Coating Layer: parts by weight______________________________________5% Polyvinyl alcohol (saponifica- 100tion degree: 98%; polymerizationdegree: 1,700) aqueous solution30% Melamine resin aqueous 3solution______________________________________
Comparing Tests
Tests for comparing the heat-sensitive recording paper obtained in Example 1 with those obtained in Comparative Examples 1 and 2 were conducted as follows.
(1) Fogging and color forming properties:
Recording was carried out by providing energy in an amount of 2 ms/dot and 50 mJ/m 2 to the recording element in a density of 5 dots/mm in main scanning and 6 dots/mm in sub-scanning. The fog (density of background before conducting recording procedure) and the density of the colored product after recording (initial density) were measured by means of a Macbeth Model RD-514 reflection densitometer (using a visual filter).
(2) Tests on resistance against various chemicals and oils:
Various chemicals and oils were individually applied to the colored product in a thickness of about 0.5 μm. The product was then left for 24 hours in an atmosphere of 25° C. and 65% RH. The fog (background density) and the density of the colored product were then measured.
The results of the comparing tests are shown in Table 1.
It is seen from Table 1 that, as compared to the comparative heat-sensitive recording papers, the heat-sensitive recording paper of the present invention undergoes less color disappearance of the colored product due to the effects of chemicals and oils and has excellent fogging resistance.
TABLE 1__________________________________________________________________________ Resistance against Chemicals and Oils Diethylene Glycol Di-n-butyl Monomethyl Initial Ethanol Phthalate Ether Castor Oil Density Density Density Density Density of of of of of Color Color Color Color ColorRun No. Fog Image Fog Image Fog Image Fog Image Fog Image__________________________________________________________________________Heat-sensitive 0.06 1.26 0.07 1.24 0.06 1.15 0.07 1.25 0.07 1.20recording paperobtained in Example 1Heat-sensitive 0.06 1.26 0.85 1.20 0.06 0.10 0.69 1.20 0.16 0.31recording paperobtained inComparative Example 1Heat-sensitive 0.06 1.24 0.55 1.21 0.06 0.51 0.44 1.22 0.16 0.77recording paperobtained inComparative Example 2__________________________________________________________________________
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
|
A heat-sensitive recording paper is disclosed. The paper is comprised of a support base having a heat-sensitive color forming layer coated thereon. The color forming layer contains color forming components comprising an almost colorless electron donating dye and an organic acid capable of forming color when contacted with the dye. The color forming layer is coated with a coating layer containing polyvinyl alcohol and boric acid. Due to the existence of the coating layer the recording paper has substantial resistance to decrease the recording density and occur the fog by various chemicals and oils.
| 8
|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present disclosure relates generally to inertial igniters and more particularly to inertial igniters for thermal batteries or other pyrotechnic type initiated devices for munitions such as gun fired or mortar rounds or rockets with safety arm.
2. Prior Art
Thermal batteries represent a class of reserve batteries that operate at high temperature. Unlike liquid reserve batteries, in thermal batteries the electrolyte is already in the cells and therefore does not require a distribution mechanism such as spinning. The electrolyte is dry, solid and non-conductive, thereby leaving the battery in a non-operational and inert condition. These batteries incorporate pyrotechnic heat sources to melt the electrolyte just prior to use in order to make them electrically conductive and thereby making the battery active. The most common internal pyrotechnic is a blend of Fe and KClO 4 . Thermal batteries utilize a molten salt to serve as the electrolyte upon activation. The electrolytes are usually mixtures of alkali-halide salts and are used with the Li(Si)/FeS 2 or Li(Si)/CoS 2 couples. Some batteries also employ anodes of Li(Al) in place of the Li(Si) anodes. Insulation and internal heat sinks are used to maintain the electrolyte in its molten and conductive condition during the time of use. Reserve batteries are inactive and inert when manufactured and become active and begin to produce power only when they are activated.
Thermal batteries have long been used in munitions and other similar applications to provide a relatively large amount of power during a relatively short period of time, mainly during the munitions flight. Thermal batteries have high power density and can provide a large amount of power as long as the electrolyte of the thermal battery stays liquid, thereby conductive. The process of manufacturing thermal batteries is highly labor intensive and requires relatively expensive facilities. Fabrication usually involves costly batch processes, including pressing electrodes and electrolytes into rigid wafers, and assembling batteries by hand. The batteries are encased in a hermetically-sealed metal container that is usually cylindrical in shape. Thermal batteries, however, have the advantage of very long shelf life of up to 20 years that is required for munitions applications.
Thermal batteries generally use some type of igniter (initiator) to provide a controlled pyrotechnic reaction to produce output gas, flame or hot particles to ignite the heating elements of the thermal battery.
There are currently two distinct classes of igniters that are available for use in thermal batteries. The first class of igniter operates based on electrical energy. Such electrical igniters, however, require electrical energy, thereby requiring an onboard battery or other power sources with related shelf life and/or complexity and volume requirements to operate and initiate the thermal battery. The second class of igniters, commonly called “inertial igniters”, operates based on the firing acceleration. These (mechanical) inertial igniters do not require onboard batteries for their operation and are thereby often used in high-G munitions applications such as in gun-fired munitions and mortars.
In munitions, the need to differentiate accidental and initiation accelerations, i.e., the so-called no-fire and all-fire (set-back) accelerations, respectively, by the resulting impulse level of the event necessitates the employment of a safety system which is capable of allowing initiation of the igniter only during high total impulse levels. In mechanical inertial igniters, the safety mechanism can be thought of as a mechanical delay mechanism, after which a separate initiation system is actuated or released to provide ignition of the pyrotechnics. Such mechanical inertial igniters that combines such a safety system with an impact based initiation system of different types are described, for example, in U.S. Pat. Nos. 7,437,995; 7,587,979; 7,587,980; 7,832,335; 8,042,469; and 8,061,271; U.S. Patent Application Publication Nos. 2010/0307362; 2011/0171511; 2012/0180680; 2012/0180681; 2012/0180682; 2012/0205225 and 2012/0210896 and U.S. patent application Ser. Nos. 12/794,763; 12/955,876 and 13/180,469; the disclosures or each of which are incorporated by reference.
Inertia-based (mechanical) igniters must therefore comprise two components so that together they provide the aforementioned mechanical safety (delay mechanism) and to provide the required striking action to achieve ignition of the pyrotechnic elements. The function of the safety system is to fix the striker in position until a specified acceleration time profile actuates the safety system and releases the striker, allowing it to accelerate toward its target under the influence of the remaining portion of the specified acceleration time profile. The ignition itself may take place as a result of striker impact, or simply contact or proximity. For example, the striker may be akin to a firing pin and the target akin to a standard percussion cap primer. Alternately, the striker-target pair may bring together one or more chemical compounds whose combination with or without impact will set off a reaction resulting in the desired ignition.
As an example, the isometric cross-sectional view of an inertial igniter described in U.S. Patent Application Publication No. 2011/0171511 is shown in FIG. 1 , referred to generally with reference numeral 200 . The full isometric view of the inertial igniter 200 is shown in FIG. 2 . The inertial igniter 200 is constructed with igniter body 201 , consisting of a base 202 and at least three posts 203 . The base 202 and the at least three posts 203 , can be integrally formed as a single piece but may also be constructed as separate pieces and joined together, for example by welding or press fitting or other methods commonly used in the art. The base 202 of the housing can also be provided with at least one opening 204 (with a corresponding opening(s) in the thermal battery—not shown) to allow ignited sparks and fire to exit the inertial igniter and enter into the thermal battery positioned under the inertial igniter 200 upon initiation of the inertial igniter pyrotechnics 215 , or initiation of a percussion cap primer when used in place of the pyrotechnics.
A striker mass 205 is shown in its locked position in FIG. 1 . The striker mass 205 is provided with guides for the posts 203 , such as vertical surfaces 206 , that are used to engage the corresponding (inner) surfaces of the posts 203 and serve as guides to allow the striker mass 205 to ride down along the length of the posts 203 without rotation with an essentially pure up and down translational motion.
In its illustrated position in FIGS. 1 and 2 , the striker mass 205 is locked in its axial position to the posts 203 by at least one setback locking ball 207 . The setback locking ball 207 locks the striker mass 205 to the posts 203 of the inertial igniter body 201 through the holes 208 provided in the posts 203 and a concave portion such as a dimple (or groove) 209 on the striker mass 205 as shown in FIG. 1 . A setback spring 210 , which is preferably in compression, is also provided around but close to the posts 203 as shown in FIGS. 1 and 2 . In the configuration shown in FIG. 1 , the locking balls 207 are prevented from moving away from their aforementioned locking position by the collar 211 . The setback spring 210 can be a wave spring with rectangular cross-section. The rectangular cross-section eliminates the need to fix or otherwise retain the striker spring 210 to the collar 211 , which is an expensive process; the flat coil spring surfaces minimizes the chances of coils slipping laterally (perpendicular to the direction of acceleration 218 ), which can cause jamming and prevent the release of the striker mass 205 (preventing the collar to move down enough to release the locking balls). Furthermore, wave springs generate friction between the waves at contact points along the spring wire, thereby reducing the chances for the collar 211 to rapidly bounce back up and preventing the striker mass 205 from being released.
The collar 211 is preferably provided with partial guide 212 (“pocket”), which are open on the top as indicated by the numeral 213 . The guide 212 may be provided only at the location of the locking balls 207 as shown in FIGS. 1 and 2 , or may be provided as an internal surface over the entire inner surface of the collar 211 . The advantage of providing local guides 212 is that it results in a significantly larger surface contact between the collar 211 and the outer surfaces of the posts 203 , thereby allowing for smoother movement of the collar 211 up and down along the length of the posts 203 . In addition, they prevent the collar 211 from rotating relative to the inertial igniter body 201 and make the collar stronger.
The collar 211 rides up and down on the posts 203 as can be seen in FIGS. 1 and 2 , but is biased to stay in its upper most position as shown in FIGS. 1 and 2 by the setback spring 210 . The guides 212 are provided with bottom ends 214 , so that when the inertial igniter is assembled as shown in FIGS. 1 and 2 , the setback spring 210 which is biased (preloaded) to push the collar 211 upward away from the igniter base 202 , would “lock” the collar 211 in its uppermost position against the locking balls 207 . As a result, the assembled inertial igniter 200 stays in its assembled state and would not require a top cap to prevent the collar 211 from being pushed up and allowing the locking balls 207 from moving out and releasing the striker mass 205 .
In the embodiment 200 , a one part pyrotechnics compound 215 (such as lead styphnate or other similar compound) can be used as shown in FIG. 1 . The striker mass can be provided with a relatively sharp tip 216 and the igniter base surface 202 is provided with a protruding tip 217 which is covered with the pyrotechnics compound 215 , such that as the striker mass is released during an all-fire event and is accelerated down (opposite to the arrow 218 illustrated in FIG. 1 ), impact occurs mostly between the surfaces of the tips 216 and 217 , thereby pinching the pyrotechnics compound 215 , thereby providing the means to obtain a reliable initiation of the pyrotechnics compound 215 . Alternatively, a two-part pyrotechnics, e.g., potassium chlorate (first part), can be provided on the base 202 over the exit hole 204 and a second part consisting of red phosphorus can be provided on the lower surface of the striker mass surface 205 over the area of the sharp tip 216 .
Alternatively, instead of using the pyrotechnics compound 215 , FIG. 1 , a percussion cap primer or the like can be used. A striker tip is generally provided at the tip 216 of the striker mass 205 to facilitate initiation upon impact.
The basic operation of the embodiment 200 of the inertial igniter of FIGS. 1 and 2 is as follows. If the inertial igniter is subjected to any non-trivial acceleration in the axial direction 218 which can cause the collar 211 to overcome the resisting force of the setback spring 210 will initiate and sustain some downward motion of the collar 211 . The force due to the acceleration on the striker mass 205 is supported at the dimples 209 by the locking balls 207 which are constrained inside the holes 208 in the posts 203 . If an acceleration amplitude and duration in the axial direction 218 imparts a sufficient impulse (i.e., an impulse greater than a predetermined threshold) to the collar 211 , it will translate down along the axis of the assembly until the setback locking balls 205 are no longer constrained to engage the striker mass 205 to the posts 203 . If the acceleration event is not sufficient to provide this motion (i.e., the acceleration time profile provides less impulse than the predetermined threshold), the collar 211 will return to its start (top) position under the force of the setback spring 210 .
Assuming that the acceleration time profile was at or above the specified “all-fire” profile, the collar 211 will have translated down past the locking balls 207 , allowing the striker mass 205 to accelerate down towards the base 202 . In such a situation, since the locking balls 207 are no longer constrained by the collar 211 , the downward force that the striker mass 205 has been exerting on the locking balls 207 will force the locking balls 207 to move outward in the radial direction. Once the locking balls 207 are out of the way of the dimples 209 , the downward motion of the striker mass 205 is no longer impeded. As a result, the striker mass 205 is accelerated downward, causing the tip 216 of the striker mass 205 to strike the pyrotechnic compound 215 on the surface of the protrusion 217 with the requisite energy to initiate ignition.
In the embodiment 200 of the inertial igniter shown in FIGS. 1 and 2 , the setback spring 210 is illustrated as a helical wave spring type fabricated with rectangular cross-sectional wires (such as the ones manufactured by Smalley Steel Ring Company of Lake Zurich, Ill.). The use of such rectangular cross-section wave springs or the like has the following significant advantages over helical springs that are constructed with wires with circular cross-sections. Firstly and most importantly, as the spring is compressed and nears its “solid” length, the flat surfaces of the rectangular cross-section wires come in contact and generate minimal lateral forces that would otherwise tend to force one coil to move laterally relative to the other coils as is usually the case when the wires are circular in cross-section. Lateral movement of the coils can, in general, interfere with the proper operation of the inertial igniter since it could, for example jam a coil to the outer housing of the inertial igniter (not shown), which is usually desired to house the igniter 200 or the like with minimal clearance to minimize the total volume of the inertial igniter. In addition, the laterally moving coils could also jam against the posts 203 thereby further interfering with the proper operation of the inertial igniter. The use of such wave springs with rectangular cross-section eliminates such lateral movement and therefore significantly increases the reliability of the inertial igniter and also significantly increases the repeatability of the initiation for a specified all-fire condition. The second advantage of the use of the aforementioned wave springs with rectangular cross-section, particularly since the wires can and are usually made thin in thickness and relatively wide, the solid length of the resulting wave spring can be made to be significantly less than an equivalent regular helical spring with circular cross-section. As a result, the total height of the resulting inertial igniter can be reduced. Thirdly, since the coil waves are in contact with each other at certain points along their lengths and as the spring is compressed, the length of each wave is slightly increased, therefore during the spring compression the friction forces at these contact points do a certain amount of work and thereby absorb a certain amount of energy. The presence of such friction forces ensures that the firing acceleration and very rapid compression of the spring would to a lesser amount tend to “bounce” the collar 211 back up and thereby increasing the possibility that it would interfere with the exit of the locking balls from the dimples 209 of the striker mass 205 and the release of the striker mass 205 . The above characteristic of the wave springs with rectangular cross-section therefore also significantly enhances the performance and reliability of the inertial igniter 200 while at the same time allowing its height (and total volume) to be reduced.
In the prior art inertial igniters similar the one illustrated in FIGS. 1 and 2 , by varying the mass of the striker 205 , the mass of the collar 211 , the spring rate of the setback spring 210 , the distance that the collar 211 has to travel downward to release the locking balls 207 and thereby release the striker mass 205 , and the distance between the tip 216 of the striker mass 205 and the pyrotechnic compound 215 (and the tip of the protrusion 217 ), the designer of the disclosed inertial igniter 200 can match the all-fire and no-fire impulse level requirements for various applications as well as the safety (delay or dwell action) protection against accidental dropping of the inertial igniter and/or the munitions or the like within which it is assembled.
Briefly, the safety system parameters, i.e., the mass of the collar 211 , the spring rate of the setback spring 210 and the dwell stroke (the distance that the collar 210 has to travel downward to release the locking balls 207 and thereby release the striker mass 205 ) must be tuned to provide the required actuation performance characteristics. Similarly, to provide the requisite impact energy, the mass of the striker 205 and the aforementioned separation distance between the tip 216 of the striker mass and the pyrotechnic compound 215 (and the tip of the protrusion 217 ) must work together to provide the specified impact energy to initiate the pyrotechnic compound when subjected to the remaining portion of the prescribed initiation acceleration profile after the safety system has been actuated.
The inertial igniters of the type described above have been shown to be capable of being miniaturized and provide highly reliable means of initiating thermal batteries or the like. In certain applications, particularly in applications in which the firing (setback) acceleration for initiating the thermal battery is relatively low and/or its duration is relatively short, then the acceleration levels that the inertial igniter could accidentally be subjected to might be even higher than the intended all-fire (setback) acceleration and/or duration. This would also be the case if the munitions in which the inertial igniter is used are required to survive shock loading due to drops from relatively high heights of the order of 40 feet or nearby explosions without the thermal battery (inertial igniter) initiation. In such situations, the aforementioned safety mechanisms would not prevent inertial igniter initiation since shock impulse that could be experienced by the inertial igniter could be higher than that of the firing setback. In such applications, it is highly desirable to provide the inertial igniter integrated thermal battery with safing arm (pin) that has to be removed (actuated or inserted or the like) to make the inertial igniter operational in response to the prescribed all-fire shock profile.
SUMMARY OF THE INVENTION
A need therefore exists for novel miniature inertial igniters for thermal batteries used in munitions such as certain gun fired and mortar rounds and rockets, which require safing arms (pins) to prevent them from being accidentally initiated by dropping or nearby explosions or the like relatively high and long duration shock loading. The innovative inertial igniters can be scalable to thermal batteries of various sizes. Such inertial igniters must be safe in general and in particular they should not initiate when subjected to certain prescribed no-fire shock loading profile; should not initiate with the safing arm (pin) on; should be able to be designed for high firing accelerations, for example up to 20-50,000 Gs or higher; and should be able to be designed to ignite (initiate) at specified acceleration levels when subjected to such accelerations for a specified amount of time as specified by the firing (all-fire) acceleration profile. Reliability is also of much concern since the rounds should have a shelf life of up to 20 years and could generally be stored at temperatures of sometimes in the range of −65 to 165 degrees F. This requirement is usually satisfied best if the igniter pyrotechnic is in a sealed compartment. The inertial igniters must also consider the manufacturing costs and simplicity in design to make them cost effective for munitions applications.
Accordingly, inertial igniters and ignition systems for use with thermal batteries or the like that are equipped with safing arms (pins) that when in place would prevent the inertial igniter and thereby the thermal battery from being activated are provided. In the disclosed embodiments of the present invention, the basic method used to provide the inertial igniters with safe arming capability is based on using certain mechanisms that in the presence of the “safing arms” (pins), the full operation of the aforementioned safety mechanism (delay mechanism) in releasing the striker mass is prevented by mechanical interference, i.e., by providing stops in the path of movement of the safety (striker release) mechanism. Thereby, even if the inertial igniter is subjected to the prescribed all-fire (or higher) acceleration time profile, the safing arm would prevent the safety mechanism from releasing the striker mass, thereby preventing the inertial igniter from activation.
The disclosed safing arm equipped inertial igniter embodiments of the present invention have the following highly desirable characteristics:
They provide hermetically sealed inertial igniters that are readily integrated with thermal batteries to form a hermetically sealed thermal battery; The safing arm (pin) will prevent inertial igniter activation even when it is subjected to acceleration levels that are significantly higher than the all-fire acceleration levels even if the applied acceleration duration is also infinitely long; The safing arm (pin) can be readily removed to make the inertial igniter, thereby the thermal battery, operational; Once the safing arm is removed, the safing arm mechanism does not interfere with proper and reliable operation of the inertial igniter.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects, and advantages of the apparatus of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where:
FIG. 1 illustrates an isometric cut away view of an inertial igniter assembly known in the art.
FIG. 2 illustrates a full isometric view of the inertial igniter assembly of FIG. 1 .
FIG. 3 illustrates the plane of the cross-sectional view C-C of the prior art inertial igniter assembly of FIGS. 1 and 2 .
FIG. 4 is the view of the C-C cross-section of FIG. 3 of the prior art inertial igniter assembly of FIGS. 1 and 2 .
FIG. 5 illustrates the first embodiment of inertial igniter with safing arm (pin) of the present invention as assembled on a thermal battery with the safing arm in position.
FIG. 6 illustrates the first embodiment of inertial igniter with safing arm (pin) of the present invention as assembled on a thermal battery following the safing arm removal and arming of the inertial igniter.
FIG. 7 illustrates a second embodiment of inertial igniter with safing arm (pin) of the present invention as assembled on a thermal battery with the safing arm in position.
FIG. 8 illustrates the second embodiment of inertial igniter with safing arm (pin) of the present invention as assembled on a thermal battery following the safing arm removal and arming of the inertial igniter.
FIG. 9 illustrates a third embodiment of inertial igniter with safing arm (pin) of the present invention as assembled on a thermal battery with the safing arm in position and removed.
FIG. 10 illustrates an example of the use of different safing arm geometries in the disclosed embodiments of the inertial igniter of the present invention.
FIG. 11 illustrates one embodiment of a normally non-operational (inert) inertial igniter of the present invention shown in its non-operational state without the inserted arming pin.
FIG. 12 illustrates the embodiment of the normally non-operational (inert) inertial igniter of FIG. 11 in its armed state with the inserted arming pin.
FIG. 13 illustrates an example of a “U” shaped arming pin that can be used to arm the normally non-operational (inert) inertial igniter of FIGS. 11 and 12 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The aforementioned inertia-based (mechanical) igniters were shown to comprise of two basic components (mechanisms) and together they provide the aforementioned mechanical safety (delay mechanism) and provide the required striking action to achieve ignition of the pyrotechnic elements. As it was previously described, the function of the safety system (mechanism) is to fix the striker in position until a specified acceleration time profile actuates the safety mechanism and releases the striker, allowing it to accelerate toward its target under the influence of the remaining portion of the specified acceleration time profile. The ignition itself may take place as a result of striker impact, or rubbing action or simply contact or proximity. For example, the striker may be akin to a firing pin and the target akin to a standard percussion cap primer.
The following embodiments operate based on the use of certain type of mechanisms that are actuated by the provided safing arm (pin) to prevent the aforementioned mechanical safety (delay) mechanism to fully operate, thereby preventing the striker element of the inertial igniter to be released (become operational) for the required striking action to achieve ignition of the pyrotechnic elements. In the following, the different safing arm embodiments, their methods of design and their operation are described using the prior art inertial igniter of FIGS. 1 and 2 .
The section C-C ( FIG. 3 ) of the inertial igniter of FIGS. 1 and 2 is shown in FIG. 4 . The schematic of the first embodiment 100 of inertial igniter with safing arm (pin) as attached to a thermal battery 103 is shown in FIG. 5 . The inertial igniter uses the basic inertial igniter 200 of FIGS. 1 and 2 , the cross-sectional C-C ( FIG. 3 ) of which is shown in FIG. 4 . In this embodiment of the inertial igniter with safing arm, the mechanical safety (delay) mechanism of the inertial igniter 200 is modified by adding a flange 101 ( FIG. 5 ) to the safety mechanism collar 211 ( FIGS. 2 and 4 ), as shown in FIG. 5 and enumerated as 102 . The modified inertial igniter would otherwise function as previously described for the inertial igniter 200 of FIGS. 1 and 2 .
The base 202 of the modified inertial igniter 200 shown in the schematic of FIG. 5 is attached and sealed to the top surface 104 of the thermal battery 103 . A housing element, such as a “bellow” element 105 is assembled over the modified inertial igniter 200 , and is attached and sealed preferably to the side 106 of the base 202 of the modified inertial igniter 200 as shown in the schematic of FIG. 5 . Alternatively, the “bellow” element 105 may be attached directly to the top 104 of the thermal battery 103 . The “bellow” element 105 thereby forms an enclosed sealed volume within which the modified inertial igniter 200 is positioned. The “bellow” element 105 has an extended rigid ring portion 108 , which is positioned between a top elastic portion 109 and a bottom elastic portion 110 . The inertial igniter with safing arm embodiment 100 is provided with a (preferably) “U-shaped” safing arm 111 , the two prongs of which are shown in the schematic of FIG. 5 . The safing arm 111 may be provided with a pulling handle or string (not shown) for ease of removal.
In the “safe” configuration shown in FIG. 5 , the safing arm 111 is positioned under the exterior portion of the ring 108 , thereby placing the bottom elastic portion 110 of the bellow element 105 in tension and the top elastic portion 109 of the bellow element 105 in compression. As a result, if the inertial igniter 100 and the thermal battery 103 assembly is accelerated (i.e., subjected to shock loading) in any direction including the direction of the inertial igniter activation shown by the arrow 112 , the safety mechanism collar 102 can displace downward only until its flange 101 comes into contact with the top surface of the rigid ring 108 of the bellow element 105 .
However, if the safing arm 111 is removed, the bellow 105 returns to its configuration shown in the schematic of FIG. 6 . The rigid ring 108 is then moved down to the indicated position in FIG. 6 , thereby freeing the safety mechanism collar 102 to travel down when subjected to the specified acceleration time profile (for gun-fired munitions, all-fire setback acceleration), causing the striker mass 205 to be released and activate the inertial igniter pyrotechnic material 215 ( FIG. 2 ) as was previously described for the inertial igniter 200 of FIGS. 1 and 2 . The ignition flame and sparks are generally passed through a provided opening ( 204 in FIG. 2 ) into the thermal battery 103 through an opening 113 on the surface of its housing (top surface 104 for the thermal battery 103 ) to activate the thermal battery.
The schematic of a second embodiment 170 of inertial igniter with safing arm (pin) as attached to a thermal battery 114 is shown in FIG. 7 . The inertial igniter uses the basic inertial igniter 200 of FIGS. 1 and 2 , the cross-sectional C-C ( FIG. 3 ) of which is shown in FIG. 4 . In the embodiment 170 of the inertial igniter with safing arm, the mechanical safety (delay) mechanism of the inertial igniter 200 is modified as was described for the embodiment 100 of FIG. 5 by adding the flange 101 to the safety mechanism collar 211 ( FIGS. 2 and 4 ), which is enumerated 102 in the schematic of FIG. 7 . The modified inertial igniter would otherwise function as previously described for the inertial igniter 200 of FIGS. 1 and 2 .
The base 202 of the modified inertial igniter 200 shown in the schematic of FIG. 7 is also attached and sealed to the top surface 115 of the thermal battery 114 . A housing element 116 is used to enclose the modified inertial igniter 200 , and is attached and sealed preferably to the side 106 of the base 202 of the modified inertial igniter 200 as shown in the schematic of FIG. 7 . Alternatively, the housing element 116 may be attached directly to the top 115 of the thermal battery 114 . The housing element 116 thereby forms an enclosed sealed volume within which the modified inertial igniter 200 is positioned.
The housing element 116 is provided with at least one and preferably two laterally flexible and axially relatively rigid curved surface portions 117 on its opposite sides as shown in FIG. 7 , which in their free configuration spring out (bulge out) to the positions 118 as shown in FIG. 8 . The laterally flexible and axially relatively rigid curved surface portions 117 may, for example, be formed as a section of a sphere or similar curved surface with relatively thin walls out of materials such as stainless steel that is usually used in the construction of bellow type elements. The inner surfaces of the flexible curved surface portions 117 ( 118 in its free configuration) are provided with relatively rigid stops 119 . The inertial igniter with safing arm embodiment 170 is provided with a (preferably) “U-shaped” safing arm 120 , the two prongs of which are shown in the schematic of FIG. 7 . The safing arm 120 may be provided with a pulling handle or string (not shown) for ease of removal.
In the “safe” configuration shown in FIG. 7 , the two prongs of the safing arm 120 are used to press against the laterally flexible and axially relatively rigid curved surface portions 117 to force them into the configuration shown in FIG. 7 , in which configuration, the relatively rigid stops 119 are positioned below the flange 101 of the safety mechanism collar 102 as shown in FIG. 7 . As a result, if the inertial igniter 170 and the thermal battery 114 assembly is accelerated (i.e., subjected to shock loading) in any direction including the direction of the inertial igniter activation shown by the arrow 121 , the safety mechanism collar 102 can displace downward only until its flange 101 comes into contact with the top surface of the relatively rigid stops 119 .
However, if the safing arm 120 is removed, the laterally flexible and axially relatively rigid curved surface portions 117 will spring back to its free configuration 118 shown in FIG. 8 , and the relatively rigid stops 119 are moved laterally away from the flange 101 of the safety mechanism collar 102 as shown in FIG. 8 , thereby freeing the safety mechanism collar 102 to travel down when subjected to the specified acceleration time profile (for gun-fired munitions, all-fire setback acceleration) in the direction of the arrow 121 , causing the striker mass 205 to be released and activate the inertial igniter pyrotechnic material 215 ( FIG. 2 ) as was previously described for the inertial igniter 200 of FIGS. 1 and 2 . The ignition flame and sparks are generally passed through a provided opening ( 204 in FIG. 2 ) into the thermal battery 114 through an opening 122 on the surface of its housing (top surface 115 for the thermal battery 114 ) to activate the thermal battery.
The schematic of a third embodiment 140 of inertial igniter with safing arm (pin) as attached to a thermal battery 123 is shown in FIG. 9 . The inertial igniter uses the basic inertial igniter 200 of FIGS. 1 and 2 , the cross-sectional C-C ( FIG. 3 ) of which is shown in FIG. 4 . In the embodiment 140 of the inertial igniter with safing arm, the mechanical safety (delay) mechanism of the inertial igniter 200 is modified as was described for the embodiment 100 of FIG. 5 by adding the flange 101 to the safety mechanism collar 211 ( FIGS. 2 and 4 ), which is enumerated 102 in the schematic of FIG. 9 . The modified inertial igniter would otherwise function as previously described for the inertial igniter 200 of FIGS. 1 and 2 .
The base 202 of the modified inertial igniter 200 shown in the schematic of FIG. 9 is also attached and sealed to the top surface 124 of the thermal battery 123 . A housing element 125 is used to enclose the modified inertial igniter 200 , and is attached and sealed preferably to the side 106 of the base 202 of the modified inertial igniter 200 as shown in the schematic of FIG. 9 . Alternatively, the housing element 125 may be attached directly to the top 124 of the thermal battery 123 . The housing element 125 thereby forms an enclosed sealed volume within which the modified inertial igniter 200 is positioned.
The housing element 125 is provided with at least one and preferably two laterally positioned cavities 126 on its opposite sides as shown in FIG. 9 . Inside each cavity 126 a translating element 127 is positioned, which is free to move laterally, and which is provided with a spring element (not shown for clarity) that biases the translating element 127 laterally away from the flange 101 of the modified inertial igniter. As a result, the translating element 127 would normally be “pulled” away from the path of downward travel of the safety collar 102 and its flange 101 . Each translating element 127 is provided with a magnet element 128 , which is oriented such that its N (S), i.e., its North (South), pole is facing the outer surface of the cavity 126 .
The inertial igniter with safing arm embodiment 140 is provided with a (preferably) “U-shaped” safing arm 129 , the two prongs of which are provided with a “U” shaped end (the sides of which are enumerated 130 in FIG. 9 ), which engage the outer surface of the cavities 126 as shown in the schematic of FIG. 9 . Each prong of the safing arm 129 is also provided with a magnet 131 , the N (S) pole of which faces the N (S) pole of the magnet element 128 of the translating element 127 . As a result, when the safing arm 129 engages the inertial igniter 140 as shown in FIG. 9 , the magnets 131 of the safing arm 129 repulse the magnets 128 of the translating elements 127 , thereby pushing the translating elements 127 under the flange 101 of the safety collar 102 (shown in broken lines).
The safing arm 129 may be provided with a pulling handle or string (not shown) for ease of removal.
It is appreciated that since all components of inertial igniters are constructed with nonmagnetic materials, usually stainless steel and brass, therefore they would not interfere with the operation of the disclosed safing arm mechanism of the inertial igniter 140 .
In the “safe” configuration shown in FIG. 9 , the two prongs of the safing arm 129 position the N pole of the magnets 131 against the outer surfaces of the cavities 126 , thereby repelling the facing N pole of the magnet 128 of the translating elements 127 , thereby forcing the translating elements 127 towards the inertial igniter body and under the flange 101 of the safety collar 102 as shown with broken lines in FIG. 9 and indicated by the numeral 132 . As a result, if the inertial igniter 140 and the thermal battery 123 assembly is accelerated (i.e., subjected to shock loading) in any direction including the direction of the inertial igniter activation shown by the arrow 133 , the safety mechanism collar 102 can displace downward only until its flange 101 comes into contact with the top surface of the translating elements 127 .
However, if the safing arm 129 is removed, the aforementioned biasing spring (not shown) would return the translating elements 127 to the position shown in solid lines in FIG. 9 , i.e., away from under the flange 101 of the safety collar 102 , thereby freeing the safety mechanism collar 102 to travel down when subjected to the specified acceleration time profile (for gun-fired munitions, all-fire setback acceleration) in the direction of the arrow 133 , causing the striker mass 205 to be released and activate the inertial igniter pyrotechnic material 215 ( FIG. 2 ) as was previously described for the inertial igniter 200 of FIGS. 1 and 2 . The ignition flame and sparks are generally passed through a provided opening ( 204 in FIG. 2 ) into the thermal battery 123 through an opening 134 on the surface of its housing (top surface 124 for the thermal battery 123 ) to activate the thermal battery.
It is appreciated by those skilled in the art that the safing arms used in the embodiments of FIGS. 5-9 may have different geometries and that those shown in the illustrations are for presenting the basic operating features of these embodiments without intending to indicate limitation to a single geometrically shaped and operating safing arm. As previously indicated, the function of the safing arm (pin) is to prevent the operation of the safety element (safety collar 102 in the embodiments of FIGS. 5-9 ). It is appreciated by those skilled in the art that such safing arms (pins) can be designed in various geometries to perform the same function as those shown in said embodiments. For example, the safing arm 111 may be replaced by the safing arm 135 as shown for the embodiment 150 in the schematic of FIG. 10 . In the schematic of FIG. 10 , the safing arm 135 has “C” shaped ends, the top portion 137 of which engages the top surface 107 of the bellow 105 and the bottom portion 136 of which engages the bottom surface of the rigid ring portion 108 of the bellow 105 , thereby preventing the safety collar 102 from moving down enough (in response to accelerations in the direction of the arrow 112 ) to release the striker mass 205 , thereby rendering the inertial igniter 150 non-operational (safe). The inertial igniter is rendered operational with the removal of the safing arm 135 ( FIG. 6 ) as was previously described for the embodiment 100 ( FIGS. 5-6 ).
In the above embodiments of the inertial igniter with safing arm (pin) illustrated in the schematics of FIGS. 5-9 , the inertial igniters become operational, i.e., can be initiated when subjected to the prescribed all-fire condition (setback acceleration) if the safing arm (pin) has been removed. In other words, the inertial igniter embodiments of FIGS. 5-9 are “normally operational” and are rendered non-operational (inert) with the insertion of the safing arm (pin).
Alternatively, such inertial igniters may be designed such that they are normally non-operational (inert) and become operational only following insertion of the “safing arm (pin)”. Such normally non-operational inertial igniters are particularly useful for applications in which there is a chance that the safing arm of the aforementioned normally operational inertial igniters be accidentally pulled or drop out during transportation, etc. In general, the basic design of any one of the aforementioned normally operational inertial igniters and those that are disclosed below can be readily modified to make them normally non-operational. As examples, such modifications to the normally operational inertial igniter embodiments of FIGS. 7-8 and 9 are described below. It is, however, appreciated by those skilled in the art that such modifications can also be made to any of the disclosed embodiments.
The schematic of the inertial igniter embodiment 170 of FIG. 7 without the safing arm 120 as attached to a thermal battery 114 is reconfigured in FIG. 11 and indicated with the numeral 160 . Similar to the embodiment 170 of FIG. 7 , the housing element 116 which encloses and seals the modified inertial igniter 200 is provided with at least one and preferably two laterally flexible and axially relatively rigid curved surface portions 117 on its opposite sides, which in their free configuration are in the configuration shown in FIG. 11 in contrast to the embodiment 170 , in which they are in the configuration shown in FIG. 8 . The inner surfaces of the flexible curved surface portions 117 are similarly provided with relatively rigid stops 119 . In addition, “T” shaped elements 161 are also provided on the outside surface of the flexible curved surface portions 117 , preferably opposite to the inner stops 119 as shown in FIG. 11 .
In its free state, the laterally flexible and axially relatively rigid curved surface portions 117 are in the configuration shown in FIG. 11 , therefore the relatively rigid stops 119 are positioned below the flange 101 of the safety mechanism collar 102 . As a result, if the inertial igniter 160 and the thermal battery 114 assembly is accelerated (i.e., subjected to shock loading) in any direction including the direction of the inertial igniter activation shown by the arrow 121 , the safety mechanism collar 102 can displace downward only until its flange 101 comes into contact with the top surface of the relatively rigid stops 119 , thereby the striker mass 205 is prevented from being released and cause the inertial igniter to be initiated as was previously described. Thus, in the state shown in FIG. 11 , the inertial igniter is non-operational or inert.
For the normally non-operational (inert) inertial igniter of FIG. 11 , the arming pin (arm) 162 is preferably a “U” shaped element similar to the arming pin 162 shown in the schematic of FIG. 13 . The arming pin 162 may be provided with a pulling handle or string (not shown) for ease of removal. The “U” shaped arming pin 162 is provided with slots 163 that would engage the “T” shaped elements 161 on outside surface of the flexible curved surface portions 117 as shown with dashed lines in FIG. 11 and solid lines in FIG. 12 . The front side 164 of the “U” shaped arming pin 162 is sized to engage the “T” shaped elements 161 on outside surface of the flexible curved surface portions 117 in their position shown in the schematic of FIG. 11 (dashed lines). On the back side 165 , the prongs of the “U” shaped arming pin 162 are spaced wider such that as the arming pin 162 engages the “T” shaped elements 161 and is pushed forward against the inertial igniter casing 116 , the “T” shaped elements 161 and thereby the opposing flexible curved surface portions 117 are pulled apart, thereby bring them into the configuration shown in dashed lines in FIG. 12 .
As a result, with the insertion of the arming pin 162 , the laterally flexible and axially relatively rigid curved surface portions 117 are forced to the configuration shown in FIG. 12 with dotted lines, moving the relatively rigid stops 119 laterally away from the flange 101 of the safety mechanism collar 102 , thereby freeing the safety mechanism collar 102 to travel down when subjected to the specified acceleration time profile (for gun-fired munitions, all-fire setback acceleration) in the direction of the arrow 121 , causing the striker mass 205 to be released and activate the inertial igniter pyrotechnic material 215 ( FIG. 2 ) as was previously described for the inertial igniter 200 of FIGS. 1 and 2 . The ignition flame and sparks are generally passed through a provided opening ( 204 in FIG. 2 ) into the thermal battery 114 through an opening 122 on the surface of its housing (top surface 115 for the thermal battery 114 ) to activate the thermal battery.
As another example, the inertial igniter embodiment 140 of FIG. 9 , which is a normally operational inertial igniter, i.e., with the safing arm 129 removed, the inertial igniter can be initiated when subjected to the aforementioned prescribed all-fire setback acceleration. The inertial embodiment 140 can be readily turned into a normally non-operational inertial igniter by firstly modifying the biasing spring of the translating element 127 to instead bias the said translating elements 127 laterally towards the flange 101 . As a result, with the safing arm 129 removed, the translating elements 127 are in the position indicated by 132 in FIG. 9 , and the inertial igniter 140 in non-operational (inert). The second required modification is the switching of the N pole of the magnet 131 with its S pole (or placing the S pole of the magnet attached to the translating element instead of its N pole to face the magnet 131 of the safing arm 129 ). As a result, when the safing arm 129 (in this case the arming arm or pin 129 ) is positioned on the inertial igniter 140 as shown in the schematic of FIG. 9 , then the translating elements 127 are pulled away from under the flange 101 of the safety collar 102 , thereby rendering the inertial igniter operational.
In the embodiments of FIGS. 5-12 , translating elements (vertically translating element 108 in the embodiment 100 of FIG. 5 ; and laterally translating elements 119 and 127 in the embodiments of FIG. 7 and FIGS. 9 and 11 , respectively) are used to position these mechanically blocking elements in the path of motion of the safety element (collar in the present embodiments) to prevent the release of the striker mass that function to initiate the igniter pyrotechnic material. It is, however, appreciated by those in the art that the mechanically blocking elements may be similarly positioned via mechanisms undergoing other types of motions such as by undergoing rotational motion or flextural bending motion or the like, all actuated similarly by the motion of the bellows, flexural surfaces, magnets, or the like as in the disclosed embodiments of the present invention.
While there has been shown and described what is considered to be preferred embodiments of the invention, it will, of course, be understood that various modifications and changes in form or detail could readily be made without departing from the spirit of the invention. It is therefore intended that the invention be not limited to the exact forms described and illustrated, but should be constructed to cover all modifications that may fall within the scope of the appended claims.
|
A method for actuating an inertial igniter. The method including: moving a mass contained within an interior of a body towards one of a pyrotechnic material or primer when an all-fire acceleration profile is experienced; hermetically sealing the interior of the body from an outside environment; restraining the movable mass from contacting the one of the pyrotechnic material or primer for acceleration profiles less than the all-fire acceleration profile; at least indirectly blocking the movable mass from movement towards the one of the pyrotechnic material or primer under acceleration profiles equal to or greater than the all-fire acceleration profile; and manually removing the blocking such that the movable mass can move towards and contact the one of the pyrotechnic material or primer when the all-fire acceleration profile is experienced to actuate the inertial igniter.
| 5
|
SUMMARY OF THE INVENTION
This invention deals generally with heat transfer, and more specifically with a wick structure for heat pipes.
Heat pipes are sealed, evacuated devices that transfer heat by evaporating and condensing a working fluid. They are passive devices which require no external power for their operation. In a typical heat pipe, heat is put into the evaporator section, which is usually located at one end of the pipe-like casing structure, and the heat entering the heat pipe evaporates some of the working fluid. This increases the vapor pressure in the region of the evaporator and causes the vapor to flow through the vapor space of the heat pipe toward the condenser section, which is usually at the other end of the structure. Since the heat pipe is set up so that the condenser section is cooler than the evaporator section, the vapor condenses in the condenser section giving up the heat which was put in the evaporator section, and the resulting liquid is returned to the evaporator by capillary action in a wick structure within the heat pipe. At the evaporator, the cycle begins again.
The wick structure of a heat pipe, which is usually composed of adjacent layers of screening or a sintered powder structure with interstices between the particles of powder, can sometimes be the limiting factor in a heat pipe's ability to transfer heat. Such a circumstance occurs when the liquid forming in the condenser section of the heat pipe is transported back to the evaporator section at a slower rate than the vapor which forms the liquid is moved toward the condenser region. In that situation, liquid will accumulate in the condenser section until none of the liquid in the heat pipe is available at the evaporator for evaporation and removal of heat. This condition is aggravated in heat pipes which are particularly long, because greater quantities of vapor in the vapor space and liquid in the wick are in transit, and are therefore not available to the evaporator. Such a "drying out" condition can cause overheating at the evaporator and can even destroy a heat pipe. Therefore, there has been considerable effort to improve the liquid transport capability of heat pipe wicks, and to thus improve the heat transfer limits of heat pipes.
One such effort has been the addition of arteries within or adjacent to the wick. An artery is essentially a small pipe through which liquid also moves from the condenser to the evaporator, and, like the wick itself, it moves the liquid by means of capillary pumping. Since arteries have cross section dimensions orders of magnitude larger than the interstices within a wick structure, they generally have much less resistance to liquid flow. Unfortunately, however the same larger cross sectional dimensions which reduce flow resistance also decrease the capillary pumping ability of arteries. Heat pipe designs have therefore hit another liquid transport limitation.
The present invention overcomes this limitation by furnishing capillary structures within bonded powder wicks which have high pumping capability, and which also have low resistance to liquid flow.
This is accomplished in the preferred embodiment of the invention by constructing a very thin but very wide capillary structure within a plastic bonded powdered metal wick. The thickness of the capillary structure is actually of the same order of magnitude as the grains of powder in the granular powder wick structure itself, and, therefore, the capillary structure has the same strong capillary pumping capability as the wick. However, the large width dimension of the capillary structure provides low liquid flow resistance, so that the capillary structure furnishes all the benefits desired from such a structure.
In the preferred embodiment, the capillary structure is constructed as an annular ring within a plastic bonded aluminum powder wick. The annular capillary structure is actually two layers of stainless steel wire cloth separated by grains of powdered metal. The capillary spacing of the annular structure, which is determined by its smallest dimension, is therefore essentially the same as that of the wick itself. In the width dimension, however, the annular configuration gives the structure a comparatively unlimited dimension, many orders of magnitude larger than the very small thickness, so that resistance to liquid flow is low.
Actual measurements on the preferred embodiment of the invention indicate that the plastic bonded aluminum powder wick with the annular capillary structure has a permeability three times greater than that of such a wick without the annular structure, and that the structure of the preferred embodiment has a permeability nine times greater than a simple sintered aluminum powder wick. The present invention is therefore ideal for long, small diameter heat pipes in which it greatly increases both performance and reliability.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross section view across the axis of a heat pipe which includes the wick of the preferred embodiment.
FIG. 2 is a cross section view across the axis of a heat pipe which includes an alternate embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiment of the invention is shown in FIG. 1 which is a cross section view of a simple cylindrical heat pipe, with the cross section taken across the heat pipe axis in either the condenser region or in the adiabatic region, the region between the condenser and the evaporator. FIG. 1 shows heat pipe 10 including casing 12 forming the vacuum tight enclosure, centrally located vapor space 14, wick 16 and annular capillary structure 18. Except for the presence of annular capillary structure 18 and the particular construction of wick 16, the construction of heat pipe 10 is quite conventional.
It should be appreciated that FIG. 1 is not drawn to scale, and, particularly, that the thickness of capillary structure 18 is exaggerated in order to better show its structure.
As in most heat pipes, casing 12 is a relatively long cylinder, and vapor space 14 is an open space along the axis of heat pipe 10, although the location of vapor space 14 and the shape of casing 12 has no bearing on the present invention.
In the preferred embodiment of the invention, wick 16 is constructed of plastic bonded aluminum powder. The technique involves coating small granules of aluminum powder with a polymer coating, forming the coated powder into a desired structure, and subjecting the structure to heat to solidify it. This technique is well understood in the art of powdered metal structures.
In the preferred embodiment, such a plastic bonded aluminum powder structure is formed into cylindrical wick 16 on the inside of casing 12 by pouring the coated powder granules into the casing while a mandrel is located in the position of vapor space 14. Also, during the formation of wick 16, capillary structure 18 is held within casing 12 in a location so that wick 16 is actually formed into two separated sections, 20 and 22. After the bonding of wick 16, the central mandrel within vapor space 14 is withdrawn, and heat pipe 10 appears as shown in FIG. 1, with capillary structure 18 locked firmly within wick 16.
Capillary structure 18 itself is constructed in a unique manner prior to its placement within heat pipe 10. Capillary structure 18 is composed of two layers of perforated material, 24 and 26, such as screen or perforated sheet, separated only by granules of metal powder 28. In the preferred embodiment, the perforated material used is stainless steel wire cloth with a 250×250 mesh, and the metal powder granules have an average diameter of 0.0045 inches which is approximately the same size as the pores in the 125 mesh powder of the wick. In order to make the capillary structure self priming the separator granules should be no less then one-half and no more than twice the diameter of the average pore size within the powdered wick within which the capillary structure is located.
Capillary structure 18 is essentially formed by bonding the separator granules to one perforated sheet and then placing the second perforated sheet on the separator granules and attaching the sheets together. One method of accomplishing this is by simply sprinkling plastic coated metal granules upon one sheet of wire cloth, heating the assembly to bond the metal granules in place on the sheet of wire cloth, and then placing the other sheet of wire cloth on top of the metal granules and welding the edges of the wire cloth layers together. After capillary structure 18 is constructed, it can easily be rolled into a cylinder so that it will fit within heat pipe 10 as shown in FIG. 1.
Other methods of construction of the capillary structure can also be used. For instance, the annular structure can be built by forming a cylinder of one layer of the perforated sheet material and then coating another sheet with a water soluble adhesive, sprinkling the separator granules on the second sheet, wrapping the second sheet and the attached granules around the first sheet, and then washing out the adhesive.
Wick 16 including capillary structure 18 formed and located in this manner results in a wick with permeability superior to that of previous wicks, but the configuration of the capillary structure of the invention need not be limited to a cylinder.
FIG. 2 shows one alternate embodiment of the invention, with several capillary structures 30 shaped as planar structures and located on radii of the axis of casing 12. This configuration and others, such as multiple coaxial annular rings, or even non-coaxial tubes formed of the granule separated screening, could be used.
The benefit derived from the wick structure of the invention is that the small spacing between the screen layers provides excellent capillary pumping while the relatively large width dimension along the screen assures low resistance to liquid flow.
It is to be understood that the form of this invention as shown is merely a preferred embodiment. Various changes may be made in the function and arrangement of parts; equivalent means may be substituted for those illustrated and described; and certain features may be used independently from others without departing from the spirit and scope of the invention as defined in the following claims.
For example, the shape of the heat pipe into which the wick of the present invention is placed may be varied, and the specific materials and bonding method used to construct the wick and the capillary structure may also be changed. For instance, polymer powder can be used for the wick, or conventional sintering can be used to form the wick. Furthermore, the capillary structure may include more than two layers of screen.
|
A high permeability wick structure for heat pipes. A thin capillary liquid transport structure is encased within relatively thick sections of a plastic bonded aluminum powder wick. The capillary structure is formed of two layers of fine mesh screen separated only by small, randomly located, powdered metal granules. The capillary liquid transport structure can be built in numerous cross sectional configurations, including annular rings or spoke like radial sections.
| 5
|
BACKGROUND
1. Field
The present invention relates generally to a heat dissipation device, and more particularly to a heat dissipation device using heat pipes for enhancing heat removal from heat-generating components.
2. Prior Art
As computer technology continues to advance, electronic components such as central processing units (CPUs) of computers are being made to provide faster operational speeds and greater functional capabilities. When a CPU operates at high speed in a computer enclosure, its temperature can increase greatly. It is desirable to dissipate the heat quickly, for example by using a heat dissipation device attached to the CPU in the enclosure. This allows the CPU and other electronic components in the enclosure to function within their normal operating temperature ranges, thereby assuring the quality of data management, storage and transfer.
A conventional heat dissipation device comprises a heat sink and at least a pair of heat pipes. The heat sink comprises a base and a plurality of fins extending from the base. The base defines two grooves in the top surface thereof, and bottom surface of the base is attached to an electronic component. Each heat pipe has an evaporating portion accommodated in one of the grooves and a condensing portion inserted in the top fins. The base absorbs heat produced by the electronic component and transfers heat directly to the fins through the heat pipes. By the provision of the heat pipes, heat dissipation efficiency of the heat dissipation device is improved.
However, due to structural limitation, the contact area between the heat pipes and the fins is limited, which results in that the heat removal efficiency by the prior art heat dissipation device still cannot meet the increasing heat removing requirement for the up-to-the minute heat-generating electronic devices.
SUMMARY OF THE INVENTION
What is needed is a heat dissipation device with heat pipes which has an improved heat dissipation efficiency.
A heat dissipation device in accordance with a preferred embodiment of the present invention comprises a heat sink and at least one serpent heat pipe. The heat sink comprises a base contacting with an electrical component, a heat dissipation fins group extending from the base and a cover attached to the heat dissipation fins group. The heat dissipating fins group defines a notch at one side thereof. Evaporating and condensing portions of the at least one serpent heat pipe are respectively connected to the base and the cover, and a middle portion of the heat pipe is accommodated in the notch and thermally engages with the heat dissipating fins group.
Other objects, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an assembled view of a heat dissipation device in accordance with a preferred embodiment of the present invention;
FIG. 2 is an exploded view of FIG. 1 ;
FIG. 3 is a view similar to FIG. 1 with some parts thereof removed to more clearly show relationship between heat pipes and heat dissipation fins of the heat dissipation device; and
FIG. 4 is a side view of FIG. 1 , showing heat transferring paths of the heat dissipation device.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a heat dissipation device in accordance with a preferred embodiment of the present invention. The heat dissipation device comprises a heat sink 10 , heat pipes 22 , 24 and a fan assembly 30 located beside the heat sink 10 .
Referring to FIGS. 2-3 , the heat sink 10 comprises a base 12 , a cover 16 spaced opposite to the base 12 , and a heat dissipating fins group 14 sandwiched between the base 12 and the cover 16 . The base 12 has a bottom surface for being attached to an electrical component (not shown) and a top surface opposite to the bottom surface. The base 12 defines a pair of first grooves 120 in the top surface and a pair of first screw holes 122 at a pair of opposite sides thereof. The cover 16 defines a pair of second grooves 160 on a bottom surface thereof and a pair of second screw holes 162 at a pair of opposite sides thereof. The heat dissipating fins group 14 comprises a plurality of spaced heat dissipating fins 140 . The spaced heat dissipating fins 140 define a plurality of air passageways 143 therebetween. Each heat dissipation fin 140 defines a cutout at a side thereof (see FIG. 3 ). An abutting flange 142 laterally extends from the heat dissipation fin 140 around the cutout for contacting the heat pipe 22 . The cutouts together form a notch 148 at a side of the heat dissipating fins group 14 . The notch 148 comprises a first section 1480 and a second section 1482 along the lateral direction wherein the first section 1480 adjacent to a right side of the heat dissipation device as seen from FIG. 1 , and is shorter than the second section 1482 along the lateral direction. Furthermore, the first section 1480 has an inner portion that is larger than that of the second section, thereby facilitating mounting of the heat pipe 22 in the notch 148 . A bottom surface of the heat dissipating fins group 14 defines a first channel 144 corresponding to the first grooves 120 . The first channel 144 cooperates with the first grooves 120 to form a first passage 44 . A top surface of the heat dissipating fins group 14 defines a pair of second channels 146 corresponding to the second grooves 160 . Each second channel 146 cooperates with a corresponding second groove 160 to form a second passage 46 . The heat pipe 22 is S-shaped and the heat pipe 24 is U-shaped. The heat pipe 22 comprises three parallel heat-exchange portions, namely a first parallel-portion 220 , a second parallel-portion 222 and a third parallel-portion 224 . The first parallel-portion 220 and the third parallel-portion 224 are respectively accommodated in a corresponding first groove 120 and a corresponding second groove 160 by means of soldering. An upper turning corner of a connecting-portion between the first parallel-portion 220 and the second parallel-portion 222 is accommodated in the first section 1480 . The second parallel-portion 222 is inserted in the second section 1482 and is soldered to and thermally contacts with the flanges 142 . The U-shaped heat pipe 24 comprises an evaporating portion 240 and a condensing portion 244 . The evaporating portion 240 and the condensing portion 244 are respectively accommodated in corresponding first and second grooves 120 , 160 . The fan assembly 30 comprises a fan 32 and a fan holder 34 . The fan holder 34 has a pair of flanges 340 on a pair of opposite sides thereof. Each flange 340 defines holes 342 corresponding to the first, second screw holes 122 , 162 . Screws (not shown) are used to extend through the holes 342 and screwed into the screw holes 122 , 162 , whereby the fan assembly 30 is attached to a rear side of the heat dissipating fins group 14 . An airflow generated by the fan 32 flow through the air passageways 143 to take heat away therefrom. In the present invention, the cover 16 is soldered to a top surface of the heat dissipating fins group 14 and the base is soldered to a bottom surface of the heat dissipating fins group 14 . The first-parallel portion 220 of the S-shaped heat pipe 22 and the evaporating portion 240 of the U-shaped heat pipe 24 are soldered in the first grooves 120 and the first channel 144 so that the portions 220 , 240 are thermally connected with the base 12 and the heat dissipating fin group 14 . The third-parallel portion 224 of the S-shaped heat pipe 22 and the condensing portion 244 of the U-shaped heat pipe 24 are soldered in the second grooves 160 and the second channels 144 so that the portions 224 , 244 are thermally connected with the cover 16 and the heat dissipating fin group 14 .
Referring to FIG. 4 , heat transferring paths of the heat dissipation device are shown, the base 12 absorbs heat and a major part of the heat is directly transferred to the first parallel-portion 220 of the heat pipe 22 and the evaporating portion 240 of the heat pipe 24 . The first parallel-portion 220 is an evaporating portion of the heat pipe 22 . A minor part of the heat is conducted upwardly through the fins 140 . The major part of the heat received by the heat pipes 22 , 24 causes liquid in the portions 220 , 240 thereof to evaporate into vapor. The vapor flows upwardly as shown by arrows in the heat pipes 22 , 24 . Following the upward movement of the vapor, the major part of the heat is transmitted to the fins 140 in contact with the heat pipes 22 , 24 . Finally the vapor is condensed into liquid in the condensing portion 244 and the third-parallel portion 224 (which is a condensing portion of the heat pipe 22 ) and returns to the first-parallel portion 220 and the evaporating portion 240 of the heat pipes 22 , 24 along wick structures of the heat pipes 22 , 24 .
In the present invention, by the use of the S-shaped and U-shaped heat pipes 22 , 24 , and the specially designed heat dissipating fins group 14 , the contacting areas between the heat pipes 22 , 24 and the fins 140 are significantly increased, whereby heat transferred by the heat pipes 22 , 24 can be more efficiently taken away, thereby meeting the requirement of heat dissipation of up-to-the minute electronic devices.
It is understood that the invention may be embodied in other forms without departing from the spirit thereof. Thus, the present examples and embodiments are to be considered in all respects as illustrative and not restrictive, and the invention is not to be limited to the details given herein.
|
A heat dissipation device includes a heat sink ( 10 ) and at least a serpent heat pipe ( 22 ). The heat sink ( 10 ) comprises a base ( 12 ) contacting with an electrical component, a heat dissipation fins group ( 14 ) secured to the base ( 12 ) and a cover ( 16 ) attached to a top of the heat dissipation fins group ( 14 ). The heat dissipating fins group ( 14 ) defines a notch ( 148 ) at one side thereof. Two end portions of the heat pipe ( 22 ) are respectively connected to the base ( 12 ) and the cover ( 16 ), and a middle portion of the heat pipe ( 22 ) is accommodated in the notch ( 148 ).
| 5
|
FIELD OF THE INVENTION
[0001] The present invention is directed to an agricultural cultivating and seeding machine, having a frame that is provided with tillage devices and/or a land roller and at least one seeding unit, wherein actuators are provided for adjusting the working depth and/or the working pressure of at least two different working elements.
BACKGROUND OF THE INVENTION
[0002] Seeder machines equipped with tillage devices, also designated as cultivating and seeding combinations, are known in the prior art. They can be used after a plowing or stubble operation. In many seeder machines the working depth of the seeding units and/or tillage devices can be changed.
[0003] For example, in the Väderstad Rapid F seeder, the depth setting of the disk pair can be adjusted to a pre-set delivery depth by hydraulic cylinders. The Horsch DS/D 6 seeder comprises tillage devices on an equipment carrier that can be hydraulically adjusted in height. The Amazone Airstar Xpress drilling machine makes it possible to adapt the share pressure, and the pressure on the rake that follows the share, to the particular soil conditions hydraulically. Its tillage device, which is mounted in front, can be mechanically adjusted in height. DE 198 21 394 A describes a cultivating combination in which a tillage device can be adjusted in height relative to a carrier frame. A height-adjustable land roller is provided on the back side of the cultivating combination, on which roller the cultivating combination is supported.
[0004] The coupling of several elements of seeders to each other and adjusting them in common is also known. Thus, DE 198 04 293 A, DE 198 06 467 A and DE 198 55 937 A suggest fastening seeding shares, with spring-suspension roller elements in front, to a share frame. The share frame can be adjusted in height, relative to a carrier frame of the cultivating combination, by a coupling device. Thus, the seeding share and the roller elements are jointly adjusted in height. DE 196 20 016 A discloses a cultivating combination in which a land roller and tillage devices are fastened to a common frame fastened to the main frame. The land roller can be adjusted in height relative to the tillage devices such that its position defines the working depth of the tillage devices. DE 196 41 765 A additionally suggests that the height of the drawbar in such a cultivating combination be adjusted in order to adjust the working depth of the tillage devices or a leveling track in front of this equipment. According to DE 198 36 780 A, a land roller that is height-adjustable and defines the working depth of the tillage device is associated with the tillage device of a cultivating combination. The land roller is adjusted in height jointly with the tillage device.
[0005] In sum, it can be determined in the prior art that either different elements of the seeder are adjusted individually, which has the disadvantage that changing adjustment of several elements, which can be necessary if the soil properties change or the seed changes, is complex and time-consuming; or several elements are mechanically coupled together. This, however, limits the degree of freedom.
SUMMARY OF THE INVENTION
[0006] It is an object of the present invention to provide a cultivating and seeding machine having a controller that can bring several working implements readily into their respective working positions.
[0007] The cultivating and seeding machine is provided with a seeding machine and a tillage device and/or a land roller. The seeding machine is provided with a seeding actuator for controlling the sowing depth of the seeding machine. The tillage device is provided with a tillage actuator for controlling the tillage downward pressure of the tillage device. The land roller is provided with a land roller actuator for controlling roller downward pressure. In the illustrated embodiment the actuators are hydraulic cylinders, although rotating hydraulic or electric motors can also be used. At least two of the actuators are connected to a controller that controls the operating parameters of the actuators. The controller controls the flow of pressurized hydraulic fluid to the actuators with or without feedback from an appropriate sensor. The controller is loaded with data records containing information for adjusting at least two of the actuators. The actuators, and with them the working elements, are respectively brought into the positions required using the data records.
[0008] It is possible in this manner to bring several working elements of the cultivating combination into their prescribed positions by retrieving a single data record. Operation of the cultivating and seeding machine is significantly simplified.
[0009] It is not absolutely necessary to store complete data records for controlling all actuators if the data records are derived by the controller from stored data. Thus, for example, data dependent on the soil type can be filed in a table, and data records can be retrieved from another table using this table or calculated algorithmically using appropriate mathematical instructions. The advantage is a reduction of the amount of data to be stored and the possibility of interpolation. It is also conceivable to derive the parameters for two working elements from the selectable data for one working element. Thus, the operator can input a value for the sowing depth and the controller can set the pressure of the land roller and the position of the tillage devices using the selected sowing depth.
[0010] In an especially simple embodiment of the invention, the data records can in particular be retrieved by an operator manually. The data record considered to be significant, as a function, e.g., of the soil type, soil moisture or of other conditions is selected by a keyboard or a touch-sensitive screen or by speaking.
[0011] As an alternative or in addition, a map can be stored in which the data records, or data from which the data records can be derived, are stored as a function of the particular position. The data is retrieved from the stored map using the actual position of the cultivating combination, or of a vehicle pulling it, determined by a position detection system (e.g., GPS, DGPS or some other satellite system or an inertial navigation system), and [said data is] used to control the actuators.
[0012] The soil type, soil moisture, air and/or soil temperature, type of seed, and weather conditions such as the current or forecast amount of rain, solar radiation, etc., or any combination of these can be cited as data on which the operating values of the actuators can be dependent. Using suitable computer instructions, the data records for defining the prescribed operating values for the actuators are determined from this data, which can be input or detected by appropriate sensors or transmitted by remote data transmission.
[0013] During road travel and/or in headlands, the operating values of the actuators of the cultivating combination differ from the operating values when working a field since in these instances the working elements must be raised. In order to facilitate the work for the operation it is possible to design a data record to be retrieved for headland or road travel. This can be effected by manually pressing a key or by using a position detection system that makes it possible to recognize, using a map, whether a field is to be worked or a headland or a road is to be traveled.
[0014] Such a position detection system avoids unintended double working of a section of a field by comparing the actual position with stored information about the already worked areas. If the comparison shows that the particular area being traversed has already been worked, the working elements are automatically moved to a non-operational position. A manual override control is of course conceivable.
BRIEF DESCRIPTION OF THE DRAWING
[0015] [0015]FIG. 1 is a side view of a cultivating combination in accordance with the invention, coupled to a tractor.
DETAILED DESCRIPTION
[0016] [0016]FIG. 1 shows an agricultural cultivating combination 10 . It comprises frame 12 that is supported by ground engaging wheels 14 . The front of the frame 12 is provided with a forwardly extending tongue 16 that is coupled to a hitch 20 extending rearwardly from a tractor 18 .
[0017] A seed hopper 22 is mounted to the frame 12 in front of ground engaging wheels 14 . A seed meter, not shown, meters the seed contained in the seed hopper. The metered seed is then transported to seeding units 24 by seed hoses, also not shown. Each of the seeding units 24 comprises a furrow opener 26 in the form of a disk, a plow share 30 , and closing wheels 28 . The plow share 30 has a passage defining a seed tube for receiving metered seed from the seed hoses and directing the metered seed into the planting furrow formed by the furrow opener 26 . The closing wheels 28 close the planting furrow with the metered seed contained therein.
[0018] A plurality of seeding units 24 are supported on the transversely extending tool carrier 32 . These seeding units 24 are arranged side-by-side on the tool carrier 32 . The tool carrier 32 is supported on and extends rearwardly from frame 12 . The seeding units 24 are pivotally mounted to the tool carrier 32 so they can pivot about an axis parallel to the longitudinal axis of the tool carrier 32 . The pivot angle of the seeding units 24 , and thereby the sowing depth, is fixed by seeding actuator 34 in the form of a hydraulic cylinder, extending between mount 33 on frame 12 and arm 35 coupled to seeding units 24 .
[0019] A carrier frame 36 is fastened to the bottom of frame 12 in front of seed hopper 22 . Carrier frame 36 holds pivot frame 38 that can pivot about horizontal pivot axis 44 that extends transversely to the direction of travel. A tillage device 42 in the form of a disk harrow is supported on this pivot frame 38 via U-shaped spring 40 . A tillage actuator 46 , in the form of a hydraulic cylinder, is arranged between frame 12 and pivot frame 38 . The tillage actuator 46 defines the pivot angle of pivot frame 38 about pivot axis 44 . Tillage actuator 46 can be operated with an adjustable pressure and in this manner controls the tillage downward pressure with which tillage device 42 acts on the ground. In place of the illustrated disk harrow, any other tillage device 42 can be used.
[0020] Mount 48 is pivotally attached to the carrier frame 36 and pivots about a pivot axis that is parallel to the pivot axis 44 . In the illustrated embodiment, the mount 48 is located behind the tillage device 42 . A land roller 50 in the form of a tire packer is attached on the lower end of the mount 48 . A land roller actuator 52 , in the form of a hydraulic cylinder, extends between carrier frame 36 and mount 48 and defines the pivot angle of mount 48 . Land roller actuator 52 can be loaded with an adjustable pressure and in this manner controls the roller downward pressure with which land roller 42 acts on the ground. Instead of a tire packer, any type of roller could be used, e.g., oblique-rod packer rollers, tubular-rod packer rollers, disk packer rollers, toothed packer rollers, spiral packer rollers, and polygon rollers. Land roller 50 could also be designed as a front tire packer or support roller wherein the roller supports at least a part of the weight of the cultivating combination. In addition, the rollers 50 can also control the depth of penetration of the cultivating combination, in the course of which wheels 14 should be lifted up during a seeding operation. Instead of the rigid attachment of land roller 50 to mount 48 as shown, a spring may be interposed between the mount 48 and the rollers 50 . Also, each individual wheel of land roller 50 could be controlled via an associated actuator 52 .
[0021] It should be noted that U-shaped springs 40 connected to pivot frame 38 are arranged on both lateral ends of tillage device 42 . Also, mounts 48 are arranged on both lateral ends of land roller 50 and are connected to carrier frame 36 . Tillage device 42 and land roller 50 can be composed of three or more sections arranged side by side, of which the outermost can be folded up in a known manner for road transport. Appropriate drives in the form of hydraulic cylinders are to be provided for this purpose.
[0022] A rake 66 is connected to the carrier frame 36 between the tillage device 42 and land roller 50 .
[0023] Tractor 18 is provided with controller 54 for directing pressurized hydraulic fluid to and from actuators 34 , 46 and 52 from pressurized hydraulic fluid source 58 by means of hydraulic lines, not shown. The controller 54 controls this flow by a valve device 56 preferably containing proportional valves. In the embodiment shown, actuators 34 , 46 and 52 are double-acting hydraulic cylinders in order to be able to lift up the working elements of cultivating combination 10 in headlands or during road travel. However, single-acting hydraulic cylinders are also conceivable. Controller 54 is thus designed to set the pressure of actuators 46 , 52 . Information about the position of actuator 34 is supplied to controller 54 via a sensor 60 , so that the sowing depth of seeders 24 can be regulated by controller 54 by means of valve device 56 .
[0024] Signals containing information about the actual position of tractor 18 is supplied to controller 54 from satellite receiver antenna 62 designed to receive GPS (global positioning system) signals. A target value map is filed in memory 64 , this having been prepared on a computer before a tilling event and transferred in any manner (by an exchangeable data storage medium such as a diskette or in a wireless manner) to memory 64 . The target value map was prepared using available information about the type of soil, type of seed and various other parameters to be taken into consideration when tilling. The farmer can test and modify the above. The map contains site-dependent information about the pressure of tillage device 42 on the ground, the pressure of land roller 50 on the ground and the sowing depth.
[0025] Data records containing information about the prescribed pressure of tillage device 42 , the prescribed pressure of land roller 50 , and the prescribed sowing depth are read out from the target value map in memory 64 when tilling a field using the information generated by satellite receiver antenna 62 about the correct location. A recalculation for compensating the offset between the position of satellite receiver antenna 62 and cultivating combination 10 or its working elements 24 , 42 and 50 is also possible. Actuators 34 , 46 and 52 are controlled in accordance with the data records by control 54 and valve device 56 . Constant contact with the ground and a uniform, optimally adjusted soil pressure are possible by controlling the pressure of land roller 50 . Actuators 34 , 46 and 52 are caused to lift up the working elements of cultivating combination 10 , that is, tillage device 42 , land roller 50 and seeding device 24 at the headlands at the edges of a field.
[0026] Having described the preferred embodiment, it will become apparent that various modifications can be made without departing from the scope of the invention as defined in the accompanying claims.
|
A cultivating and seeding machine is provided with a seeding unit and a tillage device and/or a land roller. The seeding unit is provided with a seeding actuator, the tillage device is provided with a tillage actuator and the land roller is provided with a land roller actuator. The seeding actuator regulates the sowing depth of the seeding unit, whereas the tillage and land roller actuators regulates the downward pressure of these two implements, respectively. A controller having a memory loaded with information for adjusting the working implements, controls the various actuators in response to these data records.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
Pursuant to 35 U.S.C. § 119(a), this application claims the benefit of earlier filing date and right of Korean Patent Application No. 10-2003-16629, filed on Mar. 17, 2003, the content of which is hereby incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus and method for processing image data in an interactive media player, and more particularly to an apparatus and method for equalizing bit depths of pixels according to a predetermined hardware specification while processing additional image data.
2. Description of the Related Art
High-density optical discs (e.g., digital versatile discs (DVDs)) are capable of recording and storing digital data. The DVDs are high-capacity recording mediums capable of permanently recording and storing not only high-quality digital audio data, but also high-quality moving picture data.
A DVD includes (1) a data stream recording area for recording a digital data stream, such as moving picture data, and (2) a navigation data recording area for recording navigation data needed for controlling playback of the moving picture data.
Thus, a general DVD player first reads the navigation data recorded on the navigation data recording area if the DVD is seated in the player, stores the read navigation data in a memory provided in the player, and reproduces the moving picture data recorded on the data stream recording area using the navigation data. The DVD player reproduces the moving picture data recorded on the DVD, such that a user can see and hear a movie recorded on the DVD.
Additional contents (control or additional information, i.e., enhanced navigation data) associated with the playback of audio/video (A/V) data are recorded on the DVD in form of a file written in a hypertext markup language (HTML). Standardization work of an interactive digital versatile disc (I-DVD or Enhanced Digital Versatile Disc (eDVD)) is ongoing. The A/V data recorded on the I-DVD is reproduced according to the user's interactive request. Based on a current provisional standard of the I-DVD, the ENAV data can be received from an external server instead of the I-DVD, and can be reproduced in association with the A/V data recorded on the I-DVD. Where I-DVDs are commercialized, the supply of contents through digital recording mediums will be more prevalent.
The ENAV data is comprised of a variety of files (e.g., html files, image files, sound files, and moving picture files). Image data (containing animation data) from among the ENAV data may be formed to have a variety of bit depths for every pixel (under a monochrome signal) or color.
However, because an I-DVD player uses only one unit (application, video memory, or hardware, etc.) for processing image data, it will be preferable for the I-DVD player to control the image data at only one fixed bit depth, resulting in easier hardware implementation and superior display performance of the I-DVD player. Therefore, it is necessary for the I-DVD player to effectively process image data created at various bit depths.
SUMMARY OF THE INVENTION
A method for processing image data in an interactive media player is provided. The method comprising receiving a plurality of image sources from at least one of an interactive recording medium and external server; converting a bit depth of at least a first image source to another bit depth so that the first image source has same bit depth as a second image source.
Converting the bid depth comprises increasing the bit depth to match a first value. The first value is approximately equal to a highest bit depth value chosen from among respective bit depths associated with each of the plurality of image sources. In one embodiment converting the bit depth comprises repeating a unit pixel value a predetermined number of times to increase the bit depth.
According to one or more embodiments, a color value of image data is repeated a predetermined number of times to increase the bit depth. The bit depth is increased within a range of approximately 2m to 2n, where n>m≧0, for example. The bit depth is increased by discarding at least one low-order bit of image data of the first image source. The low-order bit is discarded after at least a unit pixel or color value is repeated. In certain embodiments, the bit depth of the first image source is reduced to a target bit-conversion value, if the bit depth of the first image source is greater than a target value.
In accordance with another embodiment, a method for processing image data in an interactive media player comprises receiving a plurality of image sources, each image source associated with a respective bit depths; comparing at least one of the respective bit depths with a predetermined reference bit-depth; and converting the respective bit depth to another bit depth, if the respective bid depths is different from the predetermined reference bit-depth.
Converting the respective bid depth comprises increasing the bit depth to match a first value. The first value is approximately equal to the predetermined reference bit-depth. Converting the respective bit depth may also comprise repeating a unit pixel or color value a predetermined number of times to increase the bit depth. In certain embodiments, the respective bit depth is reduced to a target bit-conversion value, if the respective bit depth is greater than the target bit-conversion value.
In accordance with one embodiment, an interactive media player system comprises a storage unit for storing a plurality of image sources read from a recording medium, each image source having a respective bit depth; a decoder for decoding the plurality of image sources, confirming the respective bit depths of the image sources to determine whether or not the respective bit depths are to be converted to another bit depth; and a converter for converting at least one of the respective bit depths into another bit depth.
A mixer for mixing video data reproduced from the interactive recording medium and image data with a converted bit depth, may be also included in the system. The converter converts at least one of the respective bit depths to another bit depth when at least a first image source stored in the storage unit has a different bit depths than a second image source. In some embodiments, at least one of the respective bit depths to another bit depth when at least a first image source stored in the storage unit has a different bit depths than a reference bit depth. The converter may increase at least one of the respective bit depths by repeating a unit pixel or color value. The bit depth is increased in a range of approximately 2m to 2n.
In some embodiments, the converter increases at least one of the respective bit depths by discarding at least a low-order bit of the image data or the converter reduces at least one of the respective bit depths by discarding at least a low-order bit of the image data.
These and other embodiments of the present invention will also become readily apparent to those skilled in the art from the following detailed description of the embodiments having reference to the attached figures, the invention not being limited to any particular embodiments disclosed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
FIG. 1 is a block diagram illustrating an interactive media player for processing image data in accordance with one embodiment of the invention;
FIG. 2 is a directory structure of an interactive recording medium, in accordance with one embodiment of the invention;
FIGS. 3 a ˜ 3 b are flowcharts illustrating one or more methods for processing image data in the interactive media player in accordance with one embodiment of the invention;
FIG. 4 is an exemplary table format of image sources containing image data in one or more embodiments; and
FIG. 5 illustrates an exemplary case in which a video layer containing equalized images of the same bit depth is mixed with another image layer to form a display signal.
Features, elements, and aspects of the invention that are referenced by the same numerals in different figures represent the same, equivalent, or similar features, elements, or aspects in accordance with one or more embodiments of the system.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a block diagram illustrating an interactive media player adapted to an inventive apparatus and method for processing image data in accordance with the present invention. Referring to FIG. 1 , the interactive media player includes: a signal processor 11 for reading signals recorded on an interactive recording medium seated in the player, processing the read signals, and restoring resultant signals into digital data; a DVD decoder 12 for decoding compressed A/V data generated from the signal processor 11 .
Provided also is a network interface 13 for performing a network interface function, a web browser function; an ENAV buffer 14 for temporarily storing ENAV data therein; an iDVD processor 15 for interpreting a document such as an html text, and controlling a screen layout; and a media decoder 16 for decoding media data such as a compressed image or animation; a media buffer 22 for storing the decoded media data while being classified according to sources. The interactive media player further includes a bit converter 23 for equalizing different bit depths of image data stored in the media buffer 22 , and forming predetermined uniform bit depths.
Some embodiments may also comprise a mixer 21 for receiving video data generated from the DVD decoder 12 and individual image data of more than one source generated from the bit converter 23 , selecting output locations of the individual image data on the basis of layout control data of the iDVD processor 15 , and controlling the image data to be displayed as video signals at the selected output locations; and a controller 30 for controlling user's key inputs, communications with external devices, and overall operations of the aforementioned components needed for reading the I-DVD being an interactive recording medium.
A directory structure of the I-DVD 1 is as shown in FIG. 2 . An additional contents directory “DVD_ENAV” 203 arranged under a root directory includes: a start-up file “StartUp.xml” 204 containing information for system environment setting to be necessarily performed before data of the I-DVD is reproduced; an information file “EnDVD.Inf” required for reproducing A/V data recorded on the I-DVD; an initial screen setup file “index.html” for playback; a synchronization file “index.syn” for the synchronization between data items of different attributes, etc. The directory “DVD_ENAV” 203 further includes a fonts directory 206 storing font files required for outputting a text of the additional contents; and an additional contents directory 207 containing the additional contents for providing additional A/V contents, i.e., ENAV data files 208 . The additional contents directory 207 can include additional contents, e.g., subdirectories 209 , on the basis of a hierarchical structure.
A video title set directory “Video_TS” 201 containing video data and an audio title set directory “Audio_TS” 202 containing audio data are arranged under the root directory. An item of disc version information associated with the I-DVD and an item of contents manufacturer information are recorded in the “EnDvd.inf” file of the directory 203 . Further, uniform resource identifier (URI) information associated with a contents server for providing, through the Internet, the additional contents information relating to A/V data to be read and reproduced from the I-DVD can be recorded in the directory 203 .
Items of setup information for the initial screen setting at a time of reproducing the data of the interactive DVD can be recorded in the setup file “index.html” of the directory 203 . Items of time stamp information required for performing the synchronization between the A/V data and ENAV data to be read and reproduced from the I-DVD are recorded in the synchronization file “index.syn”.
Moreover, before data of the I-DVD is reproduced, various information items for system environment setting to be necessarily performed are recorded in the start-up file “StartUp.xml”. The various information items include: information of contents to be loaded in a memory before the playback; location information of a source for providing the contents information; information of a parental ID indicating a right to access the recorded A/V data; information of language of the additional contents; information of a web-site connection during the playback; memory management information; information of a file to be processed after the start-up file is processed; and information of a version of the start-up file, etc.
To reproduce data of the I-DVD 1 recording therein the aforementioned data, ENAV data serving as additional contents needs to be pre-loaded in the ENAV buffer 14 . For this operation, the iDVD processor 15 read and interprets a start-up file “StartUp.xml” stored in the “DVD-ENAV” directory 203 , confirms a parental ID as a level of a right to reproduce data of the I-DVD, a region code, etc., and sets up a requisite playback system state.
Then, the iDVD processor 15 confirms a version of a preloading list from the start-up file, and transmits the confirmed version information to a specified server through the network interface 13 . Location information of the specified server can be confirmed from information designated in the start-up file or from URL information recorded in the “EnDvd.inf” file. A corresponding server receiving the version information transmits the preloading list of a latest version to the player if the latest version higher than the received version exists in the server. On the other hand, if the latest version higher than the received version does not exist, the corresponding server notifies the player of the fact that the received version is the latest version.
If the preloading list is downloaded through the network interface 13 , the downloaded list is used as preloading information. If the preloading list is not downloaded, the preloading list contained in the start-up file is used as the preloading information. Contents recorded in the preloading list are referred to and necessary ENAV data (e.g., html files, image files, sound files, text files, etc.) is read from the interactive recording medium 1 or received from an external server, and then stored in the ENAV buffer 14 .
If the ENAV data recorded in the preloading list is completely preloaded, the controller 30 begins to reproduce data of the interactive recording medium 1 seated in the player. If the controller 30 begins to reproduce data of the disc 1 , then it rotates the seated interactive recording medium 1 , the signal processor 11 reads signals recorded in the interactive recording medium 1 , converts the read signals into digital data, and transmits the digital data to the DVD decoder 12 . Then, the DVD decoder 12 decodes the received data using video and audio data, and transmits the decoded result to the mixer 12 . The mixer 21 outputs the decoded video data as video signals according to an A/V data output window contained in a specified layout determined at the iDVD processor 15 .
In the meantime, a method for processing image data according to a preferred embodiment of the present invention is also performed during the playback time of the above-identified A/V data.
The iDVD processor 15 reads files written in a mark-up language from ENAV data preloaded in the ENAV buffer 14 at step S 10 , interprets the read files, sets up a screen layout on the basis of the interpreted information, reads requisite files from the ENAV buffer 14 at step S 10 , and applies the requisite files to the media decoder 16 .
In this case, the iDVD processor 15 recognizes the number of image sources (including not only images but also animation frames) to be outputted on the same display screen. If a plurality of image sources exist at step S 11 , the iDVD processor 15 controls the media decoder 16 to activate a data conversion. Then, the video decoder 16 compares bit depths for every pixel (under monochrome signals) or bit depths for every color at step S 12 . Individual image sources have the same internal configuration as in FIG. 4 .
Individual bit depths for every pixel or color can be recognized from data values (e.g., 1, 2, 4 or 8) recorded in a “Bit Depth” field contained in an image header. For example, provided that a specified value “8” is recorded in the “Bit Depth” field according to the display method of RGB data, one pixel has a depth of 24 bits (i.e., the number of colors (3)×bit depths for every color (8)=24 bits).
If the recognized bit depths are different from each other, the media decoder 16 requests the bit converter 23 to perform a bit conversion operation. In this case, a bit depth and a bit-conversion target value of each image source are transmitted to the bit converter 23 . Preferably, the target value is the same as the highest bit-depth of the image sources. For example, provided that bit depths for every color of three image sources are 2, 4, and 8, respectively, the target value transmitted to the bit converter 23 is to be “8”.
Simultaneously with performing the bit conversion request and transmitting the bit-conversion target value, the media decoder 16 reads image or animation data, designated by the ENAV buffer 14 , while being classified according to individual image sources, decodes the read image or animation data. Then, the read image or animation data is stored in the media buffer 22 while being classified according to fields.
The bit converter 23 refers to bit depths and bit-conversion target values of image sources received from the media decoder 16 . If it is determined that any image source having the bit depth lower than the target value exists, the bit depth is increased according to the following method at step S 13 . In more detail, in the case of increasing the bit depth for every pixel or color, a predetermined value “K” is multiplied by a specified bit “X” to be increased, resulting in a target bit value “Y”. Therefore, a prescribed value denoted by
K ( = 2 n - 1 2 m - 1 )
(where n=target bit depth, and m=bit depth to be converted) needs to be multiplied by a predetermined number to be converted.
Provided that a 4-bit value is increased to a 8-bit value, the above value “K” can be denoted by a specified number “10001”. In this case, a resultant value of the multiplication between the value “K” denoted by “10001” and the 4-bit value “X” is identical with a repetition value “XX” (=Y) of the 4-bit value “X”. Therefore, if the 4-bit value is increased to the 8-bit value, the 4-bit value needs to be repeated once to obtain the desired 8-bit value. Likewise, if a 2-bit value is converted to a 8-bit value, the value “K” is denoted by a binary number “1010101” so that it is necessary for the bit converter 23 to repeat the 2-bit value “X” four times to create a desired value “XXXX” (=Y).
However, if the bit depth is unable to be increased in the form of 1→2→4→8, for example, if a 6-bit value needs to be increased to a 8-bit value, the above-mentioned value “K” cannot be denoted by a natural number, such that it is impossible for the bit converter 23 to obtain the desired 8-bit value by means of the repetition of the 6-bit value. In this case, the 6-bit value needs to be repeated once to create a 12-bit value, and four low-order bits are then discarded, resulting in a desired 8-bit value.
The bit converter 23 sequentially increases bit depths of individual image data, stored in the media buffer 22 while being classified according to image sources, and at the same time outputs the increased bit depths of the image data to the mixer 21 . Here, image data of the highest bit depth is only read without increasing its bit depth.
The mixer 21 receives data of individual image sources, and controls the data to be outputted at corresponding locations according to layout setup data received from the iDVD processor 15 , thereby creating an image layer at step S 14 .
FIG. 5 illustrates a video layer 501 composed of one output window and an image layer 502 composed of two image windows according to the present invention. The mixer 21 creates the video layer 501 using video data received from the DVD decoder 12 , creates the image layer 502 , and mixes the video layer 501 and the image layer 502 in such a way that one output display screen 503 is completely formed at step S 15 . Therefore, a user can view moving picture data being reproduced and additional contents associated with the moving picture data at the same time.
In the case where input image sources respectively have a bit depth of a maximum 4-bit at a time of starting reproduction of their data, the bit converter 23 is preset to a predetermined function for increasing image data having 1 or 2 bit-depth. In this case, if a new input image source has a bit depth of 8 bits, the bit converter 23 reduces the bit depth of the input image source having the 8-bit bit depth. That is, the bit converter 23 removes low-order bits corresponding to a desired number of bits from the whole bit depth of 8 bits.
Such an image data conversion method can be performed differently from that of FIG. 3 a . FIG. 3 b illustrates a specified example in which bit depth of image data to be outputted is fixed using a hardware device, and bit depths of input image data are converted to a fixed bit depth.
The media decoder reads a bit depth of a media file from the ENAV buffer 14 at step S 20 , and compares the read bit depth of the media file with a bit depth of image data designed for the mixer 21 at step S 21 . If the read bit depth of the media file is different from the bit depth of image data designed for the mixer 21 at step S 22 , the media decoder 16 notifies the bit converter 23 of increase or reduction of a bit depth of a corresponding image source. If the read bit depth of the media file is identical with the bit depth of image data at step S 22 , the media decoder 16 bypasses data of the corresponding image source.
The bit converter 23 increases or reduces bit depths of image data contained in a corresponding field of the media buffer 22 allocated to a bit-conversion-requested image source at step S 23 , and then outputs the resultant data to the mixer 21 .
For example, if the mixer 21 is designed to control and process image data having a specified bit depth of 8 bits, image data of a bit depth of 4 bits is repeated once to create 8-bit data, or another image data having a specified bit depth of 12-bit discards its low-order 4 bits to create the same 8-bit data.
Then, the image layer 502 is configured at step S 24 , and is then mixed with the video layer 501 (or video signal) at step S 25 , in the same way as in FIG. 3 a.
As apparent from the above description, an apparatus and method for processing image data in an interactive media player according to the present invention can output a plurality of image data having different bit depths for every pixel or color on one display screen, resulting in efficiency of hardware design and reduction of production costs of an interactive media player.
It should also be understood that the programs, modules, processes, methods, and the like, described herein are but an exemplary implementation and are not related, or limited, to any particular computer, apparatus, or computer programming language. Rather, various types of general-purpose computing machines or devices may be used with logic code implemented in accordance with the teachings provided, herein. Further, the order in which the steps of the present method are performed is purely illustrative in nature. In fact, the steps can be performed in any order or in parallel, unless indicated otherwise by the present disclosure.
The method of the present invention may be performed in either hardware, software, or any combination thereof, as those terms are currently known in the art. In particular, the present method may be carried out by software, firmware, or macrocode operating on a computer or computers of any type. Additionally, software embodying the present invention may comprise computer instructions and be stored in a recording medium. (e.g., ROM, RAM, magnetic media, punched tape or card, compact disk (CD), DVD, etc.). Furthermore, such software may be transmitted in the form of a computer signal embodied in a carrier wave, or through communication networks by way of Internet websites, for example. Accordingly, the present invention is not limited to any particular platform, unless specifically stated otherwise in the present disclosure.
Thus, methods and systems for processing image data are provided. The present invention has been described above with reference to preferred embodiments. However, those skilled in the art will recognize that changes and modifications may be made in these preferred embodiments without departing from the scope of the present invention.
The embodiments described above are to be considered in all aspects as illustrative only and not restrictive in any manner. Thus, other exemplary embodiments, system architectures, platforms, and implementations that can support various aspects of the invention may be utilized without departing from the essential characteristics described herein. These and various other adaptations and combinations of features of the embodiments disclosed are within the scope of the invention. The invention is defined by the claims and their full scope of equivalents.
|
An interactive media player is provided. The player comprises a storage unit for storing a plurality of image sources read from a recording medium, each image source having a respective bit depth; a decoder for decoding the plurality of image sources, confirming the respective bit depths of the image sources, and determining whether or not the confirmed bit depths are to be converted to another bit depth; and a converter for converting at least one of the respective bit depths into another bit depth.
| 6
|
ORIGIN OF THE INVENTION
The invention described herein was made in the performance of work under a NASA contract and is subject to the provisions of Public Law 96-517 (35 USC 202) in which the Contractor has elected not to retain title.
TECHNICAL FIELD
A distributed computing system comprising a plurality of interconnected computers operating in a novel distributed variation of dataflow execution mode to provide flexible fault tolerance, to ease software design and concurrency specification, and to dynamically balance the loads; a distributed operating system resident on all computers; a real-time multiple-access global bus using Lanning code arbitration with deterministic access delay; and a point-to-point circuit-switched network.
DESCRIPTION OF THE PRIOR ART
Future spacecraft computers will require greater autonomy, flexibility, fault tolerance and higher throughput. The necessary solution is a new flexible computational system that will support a wide range of instruments, attain a tolerable arbitrary level of fault and damage tolerance, and provide a greater range of throughput capability. Designers of future spacecraft systems will confront a variety of new applications in onboard computing. The traditional roles of spacecraft computers are expanding to encompass tasks previously assigned to ground based systems. Increased autonomy is becoming a major goal at all levels to improve both efficiency and reliability. Greater flexibility will be needed to accommodate evolving requirements for existing spaceborne systems. Also, new instruments and engineering subsystems will require greater computational throughput.
Considering the range of payloads on such diverse systems as the Space Station, Earth Observing System, planetary spacecraft, and a host of Space Shuttle experiments, there exists the potential need for many hundreds of general purpose computing systems. The Space Station alone may require dozens, if not hundreds, of computers when payloads are included.
Reliability issues include the operating environment as well as fault and damage tolerance. One environmental issue that has plagued current generation computing components is their intolerance to ionizing radiation damage and to a single event upset (SEU). SEUs arise in small feature size parts due to trapped ions, solar flares and cosmic rays. The ability for space systems to evolve to a newer, high density technology such as VHSIC is a daunting problem. Solutions, in many cases, may have to come from architectural restructuring in new and novel ways.
Computer system architectures have various facets. There is the structure of the computers themselves, i.e. one or many. Operating systems and the associated support software can be configured in many ways. Then there is the consideration of how multiple computers will communicate with one another. Early systems employed one large computer doing the work on a batch input basis. Later, data acquisition and processing functions were made "real time" in many cases but still employing one large computer to do the work. Sometimes, priority levels were assigned to the various tasks within the computer and the tasks shared the computing ability of the hardware on an unequal basis with the more important tasks being done first and the tasks of lesser importance being done on a time available basis. The advent of multi-processors (i.e. multiple computers linked together to perform a common function) created many new problems for the computer architects. Particularly sensitive in the military and space environments are the concepts of fault tolerance and "graceful degradation"; that is, with one computer, when it is not working, nothing gets done, but, with multiple computers, if a portion of the computing capability is inoperative for any reason, it is expected that the remaining capability will take over at least critical functions and keep them operational.
A few examples of various architectural approaches known in the computer art are depicted in simplified form in FIGS. 1-4. FIG. 1 depicts a contemporary token ring network 10 wherein a plurality of computer nodes 12 are disposed along a circular communications path 14. To send messages between one another, each node samples the data on the path 14 looking for a "token" (i.e. a particular bit pattern not otherwise appearing) signifying the end of a message. When the token is located, the node 12 puts its message on the path 14 immediately following the found token and appends a new token at the end of its message to flag the end thereof. If a token is not found within a given time, the node 14 puts its message on anyway assuming network failure of some sort and hopes for the best. In such case, the network 10 degrades into what is referred to as a "contention" network wherein each node simply puts its messages on the network at will and if they are not acknowledged by the receiver as having been properly received within a given time, repeats the process until successful sending and receiving has been achieved. Some inter-computer communications networks operate on that basis all the time. Obviously, in either the token ring approach or the contention approach, some nodes can dominate the communications path and prevent other nodes from communicating at all. All in all, such approaches which may be acceptable in some ground based general computer systems are not acceptable for systems employed in the space applications being considered herein.
A common prior art approach to both hardware and software interconnection and hierarchy is depicted in FIG. 2. In this case, a plurality of task-oriented, working level computers 16 are interconnected in a multi-processor environment. The software in the computers 16 is primarily that required to perform user functions or tasks such as data acquisition and processing. Supervising computers 18 are connected to monitor the computers 16 and contain operating system type software for assigning and reassigning tasks to the computers 16 for the purpose of distributing the workload for maximum system efficiency and to accomplish fault tolerance and graceful degradation as necessary. Typically, there is a master computer 20 which has ultimate control of the whole system. The master computer 20 provides the system interface and is used to start up and configure the system in general, among other tasks. As can be appreciated, such an approach is complex to create, complex to debug, and subject to high overhead problems. Moreover, there must be redundancy on the supervising and master computer levels to prevent system failure if one of those computers fails or is destroyed.
FIG. 3 depicts a data-driven approach to computer architecture which is known in the art. Each task 22 is caused to execute when the data from the preceding tasks 22 required for its execution are provided by those preceding tasks.
Finally, FIG. 4 depicts a basic eight node element of a so-called "hypercube" approach to computer architecture wherein as many as 64,000 individual computing nodes 16 are interconnected. The hypercube is characterized by implementing an approach such as that depicted in FIG. 2. The nodes 16 are interconnected by a first communications network 24 over which the nodes 16 transfer their data, etc. The supervising computers 18 are connected to the nodes 16 by a second communications network 26 over which reconfiguration and redistribution/reassignment of task instructions are sent so that the same communications paths are not employed for the two different purposes.
Many fault tolerance approaches with prior art computer architectures are hardware intensive, requiring elaborate hardware synchronization mechanisms. Even with this investment in hardware, the application software is often subject to constraints, and requires additional overhead to support the underlying architecture. The degree of fault tolerance achieved in these designs is dictated by the architecture, not by the needs of the software designer. Furthermore, damage tolerance is not currently achievable by the same mechanisms which provide fault tolerance, without significant performance penalties.
Finally, there is the issue of software cost and reliability. Very large real-time programs for uniprocessors are difficult enough to write and test. Distributed computing systems aggravate the problem by adding topological considerations. To be fully effective, future multiprocessing systems must consider software development issues.
What is required is a single architectural concept to deal with these requirements. The intent is to provide the spacecraft system designer with a system capable of handling a general class of computing applications, e.g., payload controllers, smart sensors, robotics, engineering subsystems and moderate throughput signal processing. The required capability is not intended to supplant special purpose hardware such as high throughput signal processors, or incircuit microprocessors.
There is presently no flexible design which will support arbitrary levels of fault and damage tolerance and provide a range of throughput capability through modularity and parallelism. There is also no present software environment which deals cleanly with the issues of concurrency, productivity, reliability, and fault tolerance while permitting the generation of applications software using commercially available tools.
DISCLOSURE OF THE INVENTION
The present invention has achieved its desired objectives through use of modularity and parallel computation, based on a multiprocessor system interconnected by a global bus and an independent data network, employing a distributed operating system operating in dataflow mode of task execution. A multiprocessor architecture was chosen since it offers easy expandability and also provides the necessary basis for a fault-tolerant and gracefully degradable system. More specifically, the present invention is a multicomputer system consisting of loosely coupled processor/memory pairs connected by global and point-to-point communication systems. This approach is preferable to a shared memory implementation which would require hardware intensive approaches to fault tolerance.
More particularly, this invention is a computer system comprising, a plurality of computers, each computer having first input/output interface means for interfacing to a communications network and second input/output interface means for interfacing to a communications network, each second input/output interface means including bypass means for bypassing the associated computer with a bit stream passing through the second input/output interface means; global communications network means interconnecting respective ones of the first input/output interface means for providing respective ones of the computers with the ability to broadcast messages simultaneously to the remainder of the computers; and, meshwork communications network means interconnecting respective ones of the second input/output interface means for providing respective ones of the computers with the ability to establish a communications link with another of the computers through the bypass means of the remainder of the computers.
The preferred embodiment includes several additional features to accomplish the overall objectives thereof. Specifically, each computer is controlled by a resident copy of a common operating system. Communications between respective ones of the computers is by means of split tokens each having a moving first portion which is transmitted from computer to computer and a resident second portion which is disposed in the memory of at least one of computers and wherein the location of the second portion is part of the first portion. As a major point of novelty, the split tokens represent both functions to be executed by computers and data to be employed in the execution of the functions.
Additionally, the first input/output interface means each includes means for detecting a collision between messages being broadcast over the global communications network means and for terminating the broadcasting of a message in favor of a message with superior right to use of the global communications network means whereby collisions between messages from a plurality of computers are detected and avoided.
Additionally, the bypass means of the second input/output interface means at each computer includes a receiver for receiving inputs to the associated computer, a transmitter for transmitting outputs from the associated computer, a plurality of inputs and outputs connected to respective ones of the inputs and outputs of others of computers interconnected by the meshwork communications network means, and crossbar switch means interconnecting the inputs and the outputs for bypassing the receiver and the transmitter at the associated computer and for interconnecting one of the plurality of inputs to one of the plurality of outputs whereby a bypass link between the ones of the plurality of inputs and outputs is established; and, the bypass means of the second input/output interface means at each computer includes means for sensing a unique signal on the meshwork communications network means indicating that the bypass link is to be terminated and for causing the crossbar switch means to open the bypass link when the unique signal is sensed.
DETAILED DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified drawing representing a prior art token passing ring computer network.
FIG. 2 is a simplified drawing representing a prior art computer network in which multiple levels of software system control are implemented.
FIG. 3 is a simplified drawing representing a prior art approach of driving a system by data tokens.
FIG. 4 is a simplified drawing representing a socalled hypercube in which multiple computers are interconnected with a data network and connected to a supervisory computer via a separate control message network.
FIG. 5 is a simplified block diagram drawing of the computer system of the present invention showing the operating system duplicated in each of the computer modules, the modules connected to a global bus for intermodule communication, and the modules loosely interconnected by a meshwork providing module-to-module linking for the transfer of data and functions.
FIG. 6 is a simplified block diagram of a representative module in the present invention showing the connection to the global bus, the connection to the meshwork providing module bypass for intermediate modules, the providing of global time via the global bus, and the common operating system resident in each of the modules.
FIG. 7 is a drawing showing how the function/data tokens employed in the present invention are split into moving and resident portions.
FIG. 8 is a drawing of the structure of a typical message as broadcast over the global bus in the present invention.
FIG. 9 is a drawing showing the intermessage structure of message according to FIG. 8 when there is a contention between modules in progress for the global bus.
FIG. 10 is a drawing showing the intermessage structure of message according to FIG. 8 when there is not a contention between modules for the global bus.
FIG. 11 is a block diagram of the meshwork interface.
FIG. 12 is a block diagram of the meshwork controller.
FIG. 13 is a drawing showing the effect of interconnecting wires between the transmitters and receivers in narrowing the data pulses and changing their orientation to the clock. FIG. 14 is a circuit diagram of the repeaters employed in the present invention to eliminate the problem shown in FIG. 13.
FIG. 15 is a block diagram showing how meshwork controllers can be interconnected to increase their capacity according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The main difficulties which arise in implementations for real-time applications on interconnected multiple computer systems are the distribution of event data in a timely fashion as well as software synchronization and scheduling. Other issues include an efficient interconnecting communication system, methods for distribution of control, task migration, support for fault tolerance, and input/output handling. The present invention employs a concurrency technique which offers solutions to most of these problems in the form of low resolution dataflow.
Dataflow is central to the architecture of the present invention. The order in which various functions are performed and the means by which data and functions are associated is fundamental to a computer's architecture. In a von Neuman architecture, instruction execution is directed by an instruction pointer which passes control from one function to the next. There is no inherent concurrency. Data is identified through its location in memory.
In a dataflow architecture, the execution of each function is enabled by the presence of the data required by that function. Data is encapsulated in tokens which identify the functions to which the data is destined. The use of the token by a function consumes the token. Functions produce results in the form of new tokens. Tokens are created, used (read) and then destroyed. There is no correspondence between a data item and its location in memory because of the encapsulation of data within tokens. Dataflow functions are thus constrained to be functions with no "side effects".
In the present invention, a particular function becomes ready for execution (fireable) as soon as it has received all of the necessary input tokens. Therefore, several functions may be fireable at any moment. If the functions are distributed over the processing units of the system, all fireable functions are executed at the earliest opportunity. Hence, the maximum concurrency potential in the algorithm is extracted.
Dataflow systems can be categorized by the granularity of their data and functions. In a high resolution dataflow system, data items are quantities such as numbers and booleans. Correspondingly, functions consist of arithmetic and logical operations, simple decisions, and so on. A high resolution dataflow program consists of a very large number of functions requiring a large number of special purpose processors to extract all of the potential concurrency of a program.
Lower resolution dataflow implies increased complexity of both data structures and functions. In a low resolution system as implemented by the present invention, data might consist of lists, arrays, and other such data structures. Similarly, functions could be complex routines such as sorting, and matrix inversion. Low resolution dataflow extracts less potential concurrency from an algorithm, but it does this with less scheduling and synchronization overhead. This is an important consideration in the achieving of the overall objectives of the present invention.
Dataflow programs can be represented in a number of ways. Languages such as LUCID are similar in appearance to conventional high-level languages and are designed to ease the translation of source code into dataflow primitives. A dataflow program can also be expressed as a directed graph in which each node represents a function, and connecting arcs define the paths of tokens from source to destination. This is substantially an implementation of the representation of FIG. 3.
Many features of low resolution dataflow are appealing from an architectural point of view. For example, there is the ease of concurrency expression. In a dataflow graph, concurrency potential exists both explicitly in the form of parallel paths which may be executed simultaneously, as well as implicitly through pipelining in which the processing of consecutive inputs may overlap. Dataflow gracefully handles transient loadings which might arise from asynchronous inputs or variable computing times. Tagged dataflow systems provide automatic queuing of all data without the necessity of providing a separate queue for each input to a function. The absence of side effects and a one-to-one relationship of inputs to outputs makes programs easier to integrate and debug. This is a proven method of increasing software reliability. A graph may be verified with little regard to the algorithms which implement its functions. Any problems traced to the improper execution of a function can be debugged solely at the function level, and off-line. There is no sense of history in a function and all functions are operationally isolated form each other. The requirements on a function may be specified with no reference to other elements of the program, except for adherence to the structure of the tokens passed from one function to the next. Dataflow functions may be tested in isolation and changed without regard to the remainder of the program as long as the data structure conformity is preserved.
With low resolution dataflow, consecutive inputs to a function may be processed in separate processing units without re-entrancy concerns. There is no implied context to save or transfer. If any "memory" is required from one function activation to the next, the context must be explicitly carried by loops in the dataflow graph. Having thus described the basic attributes of the approach implemented by the present invention, the specifics of it will now be addressed in greater detail.
As depicted in the simplified drawing of FIG. 5 and generally indicated as 28 therein, the computer system of the present invention consists of clusters of computer modules 30 interconnected by two different communication mechanisms, the global bus 32 and the meshwork 34.
Each module 30 is a self-contained computer with ports connecting it to the meshwork 34 and the global bus 32 as depicted in FIG. 6. The global bus 32 and meshwork 34 as employed in the present invention are novel in their own regard and will be considered in detail later herein. Each module 30 operates autonomously. This is a major point of novelty of the present invention. Additionally, the operating system is replicated on all the modules, resulting in a fully distributed system--which is also a major point of novelty of the present invention over the prior art. A module 30 also contains timers, interrupt controllers, and the capability for general purpose memory mapped I/O via an extension bus as known in the art. By attaching special purpose boards to the extension bus, the capabilities of a module 30 can be enhanced in the usual way. For example, a mass storage device such as a digital tape recorder with limited or no computing capability could be directly connected to a module 30. The system can also support a non-homogeneous node configuration where individual nodes have unique capabilities such as I/O, storage, or computational capability. Another module enhancement might be an array processing unit, where a module 32 would serve as a front end, having the role of exchanging input and output tokens over the meshwork 34. This type of capability enhancement and the use of so-called "servers", and the like, in a networked system are well known in the art and, per se, form no point of novelty of the present invention
The global bus 32 is a broadcast bus used for operating system and software synchronization functions. It should be noted at this point that "software synchronization" refers to coordination of activities for example, not starting one activity until a previous activity upon which it depends is finished. It is not the same as hardware synchronization involving clock signals (the global bus, for example, uses an asynchronous protocol), nor is it the same as synchronization of the global bus times which involve a combination of software and hardware mechanisms. A cluster of modules 30 share a common global bus 32. The meshwork 34 is a circuit-switched point-to-point communications network, used to transport data between modules 30. Every module 30 is connected to a number of other modules 30 in the system, in a topology that best suits a particular application; that is, the meshwork 34 does not require a "regular" pattern of interconnection as in the case of the typical prior art inter-computer communications network such as those described with respect to FIGS. 1, 2 and 4. Rather, modules 30 having a high degree of potential inter-module communication can be directly connected while modules 30 having little or no inter-module communication traffic can be connect so as to require connection through a more circuitous route. The meshwork 34 is also used to communicate between clusters of modules 30. It should be noted with particularity that the present invention incorporates two distinct communication pathways. The global bus 32 is a carrier sense multiple access serial broadcast bus with collision detection/avoidance and equal access capability on a priority basis to prevent module lockout from access to the bus. The meshwork 34 is a point-to-point circuit-switched communications network with module bypass capability.
THE GLOBAL BUS
The global bus 32 is used for token announcement and synchronization. It is characterized by its broadcast capabilities, and transmission integrity mechanisms. As depicted in simplified form in FIG. 6, the interface at each module 30 to the global bus 32 employs read circuitry 36 and transmit circuitry 38. There is also a global bus time 40 available which is synchronized across the bus 32 so that each module 30 can get a common bus time for time tagging, and such. There may be more than one global bus 32 per module 30 as when multiple clusters are interconnected; however, for purposes of simplicity in the discussion herein, only one bus 32 is shown. Each time a node in a dataflow graph completes its assigned task, it broadcasts to all the participating modules 30 over the global bus 32 that is has completed the task, as well as the identification of the tokens that it produced The actual data, encapsulated in one or more tokens, remains resident in the module 30 where it was produced A module that requires the use of one or more of the tokens just produced will request and acquire them over the much higher bandwidth meshwork 34. This unique approach of the present invention is depicted in simplified form in FIG. 7 and is worthy of note by a brief digression at this point.
As depicted in FIG. 7, the concept of a "token" in the present invention is different from the traditional approaches to a token such as, for example, that described above with respect to prior art token passing ring communications networks. In the present invention, the token is "split"; that is, a token 42 comprises a moving portion 44 and a resident portion 46. As symbolically represented in the figure, the token 42 can be thought of as a whole which has been split into two different sized portions. This approach to a token is substantially the same for function tokens as well as data tokens. It should be noted in passing at this point that while data tokens are known in the art, the concept of a function token is a unique and novel aspect of the present invention which permits it to achieve many of its objectives. In either. case, the moving portion 44 is a small message packet containing information about the function/data contained in the resident portion 46. For each function, there is a master copy of the code defining it in one or more of the modules 30. For data, the resident portion is located in the module 30 which produced it. It is the moving portion 44 which is broadcast on the global bus 32. As indicated in FIG. 7, the moving portion 44 as transmitted to and as received by the modules 30 includes such necessary information as a checksum of the moving portion 44 for message checking by recipient modules 30, a pointer to the master copy of functions or data, a time tag indicating the time of creation (for numerous purposes), etc. The resident portion remains in its module 30 and a copy is only transferred to another module 30 for use if necessary for function performance as will be discussed shortly in greater detail.
As a further major point of novelty of the present invention as mentioned briefly earlier, the global bus 32 is a serial, multiple access broadcast bus which performs a unique round-robin access if a collision is detected and avoided. Note that the global bus 32 of the present invention detects and avoids collisions of data and does not destroy two (or more) messages requiring the retransmission thereof as in the prior art contention systems mentioned earlier herein. To this end, the read/transmit circuitry portions 36, 38 of the bus 32 require incorporation of a physical link having passive and active states to support "wired-or" arbitration. In the embodiment of the present invention being built for testing by applicants, the data link protocol will be controlled by a VLSI global bus controller (GBC) 60. The description contained hereinafter contains specific reference to field lengths and word sizes with respect to that test embodiment; however, those skilled in the art will recognize that actual lengths and sizes will depend on the equipment employed in the actual building of a system. Reference should be made to FIGS. 8-10 with respect to the discussion which follows immediately hereinafter.
A global bus message 48 consists of a sequence of asynchronously transmitted 19-bit words 50. The key point here is that the message 48 is comprised of a sequence of fixed length portions instead of comprising a continuous bit steam delineated by a header block and an ending token as in the prior art. Each word 50 includes a synchronizing start bit, a 2-bit field which identifies the word type and a 16-bit information field. A complete message consists of an identification word 52, two domain destination words 54 (specifying the recipients of the message--either limited or "all"), an optional time tag word (not shown in the example), and any number of data words 56, followed by a 16-bit cyclic redundancy check (CRC) word 58, which provides a checksum of all the preceding information for message receipt checking in a manner well known in the art.
The identification word 52 incorporates a 3-bit software alterable priority field, a 12-bit hardware defined module-unique identification field, and a single contention bit, which is appended as appropriate. The domain destination words 54 can identify logical grouping of modules 30 within a cluster. The contention bit is used to implement a round-robin arbitration mechanism among the other modules when a contention has occurred.
The message identification code is used to detect and avoid collisions. Each transmitting GBC 60 both transmits and listens to the bus traffic. It transmits the next bit of its message if and only if it did not detect any discrepancies between the data transmitted and received for the previous bit. This scheme permits only the GBC 60 transmitting the message 48 with the numerically highest priority and identification to proceed with the transmission of its message Any module 30 which "collides" during the above-described bit-by-bit message identification phase, stops transmitting the balance of its message and transmits an active high "one" during the contention bit time, which is merged into the message with which it potentially collided. If the contention bit is detected by a transmitting module 30, that module 30 will abstain from transmitting again until all the remaining (lower priority) contending modules 30 are successful in acquiring the bus 32, or until the bus 32 becomes idle. Thus, it can be seen that with the unique global bus and method of operation thereof of the present invention, not only are actual undesirable collisions avoided, but, in addition, all modules 30 are guaranteed access to the bus 32 within a known finite time interval and lockout of modules 30 as possible in the prior art is absolutely avoided.
The domain destination words 54 are followed by an optional 16-bit time tag word indicating the transmitter's local broadcast time as obtained from the bus time 40. The optional time tag word is followed by one or more 16-bit data words 56. The trailing CRC word 58 is calculated over all transmitted bits (except the start bits and the contention bit).
At the end of the CRC field 58, there is an acknowledgement bit time frame 62. If any receiving module 30 has discovered a transmission error it notifies the participating modules 30 during the hardware acknowledge bit time 62. In this event, the preceding message 48 previously received is deleted by all participating modules 30, and the original transmitting module 30 reschedules the transmission of the same message. If no non-acknowledgement ("NACK") is indicated within the acknowledgment bit time frame 62, successful transmission is assumed. This, of course, is completely contrary to the prior art approach requiring active acknowledgment of successful receipt by all recipients addressed by a message. This is an important distinction because, logically, there is no difference between "no non-acknowledgment" and "all acknowledge". The use of passive acknowledgment as employed by the present invention, however, is much more efficient. Active acknowledgement on a shared medium requires time multiplexing of responses and global knowledge of at least the number of respondents. The present invention's passive approach eliminates all that.
Immediately after the reception of a word 50, all receiving modules 50 activate their local transmitter. Before the transmitting module 30 can transmit the next word 50 in the message 48, all participating modules 50 must indicate that they are ready to receive. They do so by inactivating their local transmitters. Normally, messages 48 are separated by idle periods which are at least equal to the transmission time of one word 50. As shown in FIGS. 9 and 10, when a contention is in progress, the idle period is shortened to less than one word length.
THE MESHWORK As indicated in simplified form in FIG. 6, each module 30 includes an interface 64 to the point-to-point meshwork 34 used to transport data between modules 30. The meshwork interface 64 incorporates bi-directional ports 66 connected through a bypass switch 68. As depicted in FIG. 5, discussed briefly above, the meshwork 34 is used to interconnect the modules 30 in an arbitrary manner as best suited to the application; that is, there is no regular interconnection scheme as in prior art networks as described above. In the above-mentioned testing embodiment of applicants, a bank of seven 1-to- 6 multiplexers perform the port switching and the data link utilizes source-clocked NRZ or Manchester II encoded HDLC packets. The meshwork interface 64 is shown in greater detail in FIGS. 11-15.
In applicants testing embodiment, a meshwork interface 64 consists of a least one VLSI meshwork controller 70. A meshwork controller 70, in turn, is comprised of three receivers 72, one transmitter 74, and a switch and extension section, generally indicated as 76, used to provide intercontroller connections within the meshwork interface 64. Two controllers 70 may be interconnected to obtain six non-blocking bidirectional meshwork ports as depicted in simplified form in FIG. 15. Additional ports may be obtained by connecting more than two controllers 70; however, in such case, blocking within the interface 64 is possible.
It should be noted at this point with respect to applicants' testing embodiment and the results found therefrom that the serial transmitter and receivers used are not ideal. The combination of the transmitter 74, interconnecting wire 82, and the receiver 72 can have an unequal rise and fall time. This presents a problem when transmissions must go through several modules, such as in circuit switching. With each successive module, the transmitted signal would get narrower, and the data would begin to lose its orientation with the clock as illustrated in FIG. 13. In the present invention, special repeaters 84 are used in the meshwork controller 70 to help eliminate this problem. A typical repeater 84 is shown in FIG. 14. Skewing of the clock is compensated for by transmitting the inverted version of the received clock. The effects of one node, therefore, are negated by the effects of another. Skewing of the data, with respect to the clock, is eliminated by resampling the data with the new clock.
The object of the meshwork interfaces 64 is to establish a direct connection between two modules 30 bypassing, in each case, the modules 30 along the meshwork 34 between the two ends of the connection. An end-to-end, circuit-switched connection is established initially by the originating module 30 sending an "open channel request" packet. This packet is sent by the originating module 30 to the first intermediate module 30 and contains the destination address. At the intermediate module 30, the packet is intercepted by one of the interface receivers 72. An available forwarding port is found and a connection is established between the incoming and outgoing links through the interface crossbar switch 78. The "open channel request" packet is then forwarded to the next intermediate module 30. If an intermediate module 30 determines that the appropriate output link is busy or has failed, it issues a "negative acknowledgement" message to the module 30 which made the request. The requesting module 30 can then either pause before retransmitting or send the message through an alternate path. Those skilled in the art will recognize that the foregoing description combines functions of the meshwork hardware operating in conjunction with system software. Routing and acknowledgment decisions, for example, are made in software.
When the packet reaches its destination, a "circuit established acknowledgement" is sent to the originating module 30 through the link established. Note that once a link is established, it is physically symmetric. Only the software protocol dictates the order of messages; in fact, they can be simultaneous since the link in the present invention is intended to be full duplex. Once the link is established, the originating module 30 is free to transmit its data. Upon receipt of the data, the destination module 30 checks the data integrity and sends an acknowledgement to the source module 30. The circuit is maintained until one of the linked modules 30 issues a "BREAK" signal, which propagates to all intermediate modules 30. Within each interface 64 there is a completion monitor 80 which watches for the BREAK signal. When it is sensed, the connection at the local crossbar switch 78 is disconnected, thereby breaking the circuit from end to end.
THE DISTRIBUTED OPERATING SYSTEM
The operating system is designed to support the unique dataflow architecture of the present invention wherein, as previously mentioned, moving portions 44 of tokens 42 are employed to indicate the locations and vital characteristics of data and function resident portions 46 distributed throughout the system and the modules 30 thereof. The operating system of the present invention is a layered system consisting of a multi-tasking, event-driven kernel, a data manager, and a graph execution manager. The operating system resides in each module. There is no central controller in the system. As mentioned earlier but worthy of note once again, this is a major point of novelty over prior art approaches to the problems solved by the present invention. The use of a fully distributed and autonomous operating system makes graceful degradation a virtually inherent feature rather than a complex "add-on".
The kernel supports standard features such as creation and deletion of processes, inter-process communication, priority scheduling, time event management, and related functions. The kernel is augmented with routines for input and output, communications, and interrupt handling. The data manager supports sequentially structured data. It provides a virtual access for local processes to all token sets distributed throughout a cluster The graph execution manager schedules dataflow tasks within its module 30. It evaluates firing rules and executes tasks based on the locality of tokens and on function priority. Cooperation among the modules 30 is accomplished through use of the global bus 32. Global token status is broadcast via the global bus 32 and is redundantly maintained in each module 30.
The graph execution manager creates process templates within which functions are executed. These templates may be given different priority levels under the kernel multitasking system. Efficient dataflow graph execution requires a method of limiting token accumulation. Also, the resolution of recursive evaluations, and intelligent scheduling, need to be efficiently managed. Assigning priorities to graph nodes provides a mechanism for these purposes. The priority system allows other processing to occur in the intervals during which tokens may be en route to a temporarily blocked high priority node. Input and output from a dataflow graph is handled by system calls from the node function programs.
The operating system executes multiple dataflow graphs which may be independent or may exchange tokens. In addition, dataflow graphs are divided into subgraphs to aid software modularity, fault protection, and efficient load distribution. Each subgraph is assigned to a domain consisting of one or more of the cluster's modules 30. A particular module 30 may execute more than one subgraph and may be a member of more than one domain. Each global bus message 48 identifies the domain(s) to which it is directed as previously discussed. Only those modules 30 assigned to such domains) accept the message 48. Global bus messages may also be directed to other clusters via the meshwork 34 connecting the clusters.
A graph "node" (as opposed to the concept of a computer being a "node" in token ring networks, and the like) may be either a function or another graph. A node is a self-contained function written in any language. Tokens 42 may not be modified by the function. No reference is made within the function code to the dataflow graph of which it is a part nor to the identity or tag of any tokens 42 used or produced. Thus any function may be used at more than one node in a graph, and even in other graphs. A graph which is referenced as a node in one or more other graphs has external input and output arcs. These arcs connect to arcs in the referencing graph(s). A referenced graph is defined as either queuing or non-recursive.
Recursive graphs are separately instantiated on each reference to them in other graphs. They will behave as if a copy of them were included in each graph referencing them. A recursive graph may reference itself, although in this case there can be no loops in the graph. The recursion is stopped when an instantiation of the graph does not output any tokens to itself.
Queuing graphs are instantiated only once in the system. Such graphs have a single input node and a single output node. There may be an arbitrary graph between these nodes. The input node is fireable when tokens 42 received from a referencing graph satisfy its firing rules. The firing rules are evaluated separately for each reference from other graphs. Each firing of the input node must cause exactly one firing of the output node so that the output tokens can be routed back to the graph whose tokens caused the input node's firing. Queuing graphs provide an efficient, transparent mechanism for sharing large data structures.
The code which implements a function at a graph node is itself a token. Each node has an input arc from which it receives this code as a token 42. This feature has several advantages and it is a substantial and major point of novelty of the present invention. First, the migration of code (for functions) and data may be handled by the same software mechanisms. It may be more efficient in some cases to move the code to the data than the data to the code. Treating data and code equivalently allows the design of allocation heuristics which can exploit this option. Thus, the dynamic allocation of tasks to modules 30 for load balancing is handled efficiently without need of special mechanisms as employed and necessary in the prior art. The integrity of all transferred tokens 42 is guaranteed by the error protection features of the meshwork 34.
Second, checkpointing the state of the system is just a matter of capturing its tokens 42, for this also captures the code. An interrupted task is resumed by reloading a checkpointed collection of tokens 42. An overlay may be produced by replacing code tokens that are no longer required with new tokens.
In long-duration space missions, updates to an executing program (known as patches) may be necessary. In a system according to the present invention, "patching" merely consists of replacing a code token 42. This is accomplished without regard to disturbing proper software execution because node firings are atomic It is worthy of note at this point, at least in passing, that the atomicity of node firings in the present invention (i.e. how input tokens are consumed, the node function is evaluated, and output tokens are created, all in one. non-divisible operation) is accomplished with global bus message processing and token management techniques which are beyond the scope of the present discussion.
A graph node becomes executable when the tokens 42 at its inputs satisfy the node's firing rules. High-resolution dataflow systems have simple firing rules since nodes have few inputs and there are simple functions at each node. The low-resolution dataflow system of the present invention allows more inputs to a node and has a versatile set of firing rules. The graphical description of a dataflow graph is simplified and execution efficiency improved by allowing token merging and selection to occur at node inputs rather than requiring separate nodes for such operations. Similarly, the output tokens 42 from a node may be automatically duplicated onto several output arcs without the use of duplication nodes.
In the present invention, the inputs to a node are logically arranged into groups. Each of the inputs to a group is either a normal consumable arc, a non-consumable arc, or a round-robin collection of arcs. A node is fireable when the firing rules for each of its input groups are satisfied. After a token on a normal consumable arc is assigned to a node firing, it is unavailable for subsequent node firings and will be consumed when the node firing completes. After a token on a non-consumable arc is assigned to node firing, it remains on the arc and is available for subsequent node firings. An input with a round-robin collection of arcs feeding it has a token 42 available whenever there is a token 42 on any of its arcs. The arcs are linked in a ring with equal priority given to each arc. After a token 42 from one of the arcs is assigned to a node firing, the other arcs will be checked for tokens 42 to assign to subsequent node firings. Thus, an arc that always has tokens 42 on it cannot block tokens 42 on other arcs. The individual arcs in a round-robin collection are either consumable or non-consumable. The simplest input group is a single input (which may be a round-robin collection). There must be a token 42 at the input for its node to be fireable.
A "merge" group is a set of two or more input arcs whose firing rules are satisfied whenever at least one of the input arcs has a token 42. These input arcs are given unique priorities. If more than one input arc has a token 42 when the node is fired, only the token 42 from the highest priority arc is assigned to the node firing. Other tokens 42 remain available for subsequent firings. A token 42 is blocked and will not be used as long as there are tokens 42 on higher priority arcs. Each of the input arcs to a merge group may be consumable, non-consumable or a round-robin collection.
A "select" group is a set of two or more input arcs with a select-control input arc. Tokens 42 on the select-control arc have integer values which select one of the group's input arcs. The group's firing rules are satisfied when there is a token 42 on the select-control arc and on the selected arc. When the node is fired, both the select-control token 42 and the selected token 42 are assigned to the firing. The input and select-control arcs in a merge group may be consumable, non-consumable or round-robin collections.
In a system according to the present invention, fault protection is entirely a matter of preserving tokens 42. As with graceful degradation, this makes fault protection easy instead of complex. Tokens 42 may be lost, or damaged, or extraneous tokens 42 may be generated. The only other matter of concern is the integrity of I/O. Successfully dealing with these problems will make the system fault tolerant. In applications requiring a modest level of fault protection, occasional checkpointing and rollback recovery techniques may be adequate. When greater levels of protection are needed, "voting" is required and can be implemented easily within the operating environment of the present invention. Redundant subgraphs are scheduled on separate modules in order to generate independent results. Redundant graph nodes which have identical input data should produce identical tokens 42. In applicants' testing embodiment, at selectable points in the redundant subgraphs, the operating system will vote on the checkwords of corresponding tokens 42. Damaged or missing tokens 42 will be detected with high probability.
When noisy inputs from redundant hardware need to be voted, the voting is done within a redundantly executed graph node. Each instantiation of the voting node receives all of the redundant hardware inputs. Thus, each voting node should produce identical output tokens 42, allowing the operating system to do all further software voting based on checkwords.
In a dual redundant system the detection of an error is sufficient to indicate a fault in one of the modules 30, but does not provide the means for isolation and recovery. This is adequate for systems having the requirement to halt when an error is detected. Coupled with checkpointing, this may be sufficient for functions which require correct results, but not in a time critical fashion. When timely automatic recovery is required, dual redundancy is not sufficient. A triply redundant system in which three sets of tokens 42 are exchanged provides the means to detect damaged, lost or extraneous tokens 42. .Through voting, it also makes possible the regeneration and repair of token sequences. Other functions can continue while recovery processes work to isolate and remove the source of error. Even higher levels of fault coverage are possible by extending voting to four or more redundant inputs. It should also be noted that varying levels of coverage can be applied to different graph nodes. Overhead for redundancy need only be paid for critical functions. This is a novel fault tolerance feature of the present invention.
The hardware features provided in applicants' testing embodiment of the present invention to support fault tolerance include a fail-safe identification system on all inter-module communications and interface circuits designed to restrict hardware faults to a single module 30 or communication link. The inter-module communication protocol guarantees error-free transmission. The alteration of routing algorithms to avoid faulty transmission links is permitted. Also, modules 30 have independent clocks and power supplies. These mechanisms are the basis for the present invention's approach to fault tolerance.
|
This is a distributed computing system providing flexible fault tolerance; ease of software design and concurrency specification; and dynamic balance of the loads. The system comprises a plurality of computers each having a first input/output interface and a second input/output interface for interfacing to communications networks each second input/output interface including a bypass for bypassing the associated computer. A global communications network interconnects the first input/output interfaces for providing each computer the ability to broadcast messages simultaneously to the remainder of the computers. A meshwork communications network interconnects the second input/output interfaces providing each computer with the ability to establish a communications link with another of the computers bypassing the remainder of computers. Each computer is controlled by a resident copy of a common operating system. Communications between respective ones of computers is by means of split tokens each having a moving first portion which is sent from computer to computer and a resident second portion which is disposed in the memory of at least one of computer and wherein the location of the second portion is part of the first portion. The split tokens represent both functions to be executed by the computers and data to be employed in the execution of the functions. The first input/output interfaces each include logic for detecting a collision between messages and for terminating the broadcasting of a message whereby collisions between messages are detected and avoided.
| 7
|
CROSS REFERENCE OF RELATED APPLICATIONS
[0001] This application is a divisional application of copending U.S. application Ser. No 09/442,000 filed on Nov. 17, 1999, the content of which is expressly incorporated herein.
FIELD OF THE INVENTION
[0002] This invention relates to a novel, highly efficient and general process for making 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazines class of trisaryl-1,3,5-triazine UV absorbers and their precursors, 2-halo-4,6-bisaryl-1,3,5-triazines, from cyanuric halide. More specifically, the invention relates to a novel process for the synthesis of triazine compounds in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter. The process includes the reaction of a cyanuric halide with substituted or unsubstituted aromatic compounds to produce 2-halo-4,6-bisaryl-1,3,5-triazine compounds. This process produces halo-bisaryl-1,3,5-triazine compounds in higher yields than are possible using present methods. The triazine compounds that are produced are precursors of triazine UV absorbers which are used to stabilize organic materials against damage by light, heat, oxygen, or other environmental forces. The process of producing such UV absorbers can be carried out step-wise or continuously in an one-pot reaction process.
BACKGROUND OF HE INVENTION
[0003] Triazine UV absorbers are an important class of organic compounds which have a wide variety of applications. One of the most important areas of applications is to protect and stabilize organic materials such as plastics, polymers, coating materials, and photographic recording material against damage by light, heat, oxygen, or environmental forces. Other areas of applications include cosmetics, fibers, dyes, etc.
[0004] Triazine derived UV absorbers are a class of compounds that typically include at least one 2-oxyaryl substituent on the 1,3,5-triazine ring. Triazine based UV absorber compounds having aromatic substituents at the 2-, 4-, and 6-positions of the 1,3,5-triazine ring and having at least one of the aromatic rings substituted at the ortho position with a hydroxyl group or blocked hydroxyl group are generally preferred compounds.
[0005] In general this class of triazine UV absorber compounds is well known in the art. Disclosures of a number of such trisaryl-1,3,5-triazines can be found in the following U.S. patents, all of which are incorporated by reference as fully set forth herein: 3,118,887; 3,242,175; 3,244,708; 3,249,608; 3,268,474; 3,423,360; 3,444,164; 3,843,371; 4,619,956; 4,740,542; 4,775,707; 4,826,978; 4,831,068; 4,962,142; 5,030,731; 5,059,647; 5,071,981; 5,084,570; 5,106,891; 5,185,445; 5,189,084; 5,198,498; 5,288,778; 5,298,067; 5,300,414; 5,323,868; 5,354,794; 5,364,749; 5,369,140; 5,410,048; 5,412,008; 5,420,008; 5,420,204; 5,461,151; 5,476,9337; 5,478,935; 5,489,503; 5,543,518; 5,538,840; 5,545,836; 5,563,224; 5,575,958; 5,591,850; 5,597,854; 5,612,084; 5,637,706; 5,648,488; 5,672,704; 5,675,004; 5,681,955; 5,686,233; 5,705,643; 5,726,309; 5,726,310; 5,741,905; and 5,760,111.
[0006] A preferred class of trisaryltriazine UV absorbers (UVAs) are based on 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, i.e., compounds with two non-phenolic aromatic groups and one phenolic aromatic group advantageously derived from resorcinol. The 4-hydroxyl group of the parent compounds, 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, are generally functionalized to make 2-(2-hydroxy-4-alkoxyaryl)-4,6-bisaryl-1,3,5-triazine compounds for end use.
[0007] A number of commercial products exist in which the para-hydroxyl group of the phenolic ring is functionalized and the non-phenolic aromatic rings are either unsubstituted phenyl (e.g., Iinuvin® 1577) or m-xylyl (e.g. Cyasorb® UV-1164, Cyasorb® UV-1164L, Tinuvin® 400, and CCL-1545). These UV absorbers are preferred because they exhibit high inherent light stability and permanence compared to other classes of UV absorbers such as benzotriazole and benzophenone compounds.
[0008] There are several processes known in the literature for the preparation of triazine based UV absorbers. (See, H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, 1972, 55, 1566-1595, S. Tanimoto et al, Senryo to Yakahin, 1995, 40(120), 325-339).
[0009] A majority of the approaches consist of three stages. The first stage, the synthesis of the key intermediate, 2-chloro-4,6-bisaryl-1,3,5-triazine, from commercially available materials can involve single or multi-step processes. Thereafter in the second stage, 2-chloro-4,6-bisaryl-1,3,5-triazine is subsequently arylated with 1,3-dihydroxybenzene (resorcinol) or a substituted 1,3-dihydroxybenzene in the presence of a Lewis acid to form the parent compound 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. The parent compound 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine, as mentioned above, may be further functionalized, e.g., alkylated, to make a final product 2-(2-hydroxy-4-alkoxyaryl)-4,6-bisaryl-1,3,5-triazine.
[0010] There have been several approaches reported in the literature on the synthesis of the key intermediate 2-chloro-4,6-bisaryl-1,3,5-triazine. Many of these approaches utilize cyanuric chloride, a readily available and inexpensive starting material. For example, cyanuric chloride is allowed to react with aromatics (ArH, such as m-xylene) in the presence of aluminum chloride (Friedel-Crafts reaction) to form 2-chloro-4,6-bisaryl-1,3,5-triazine, which is allowed to react in a subsequent step with resorcinol to form 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine (See, U.S. Pat. No. 3,244,708). There are several limitations to this process, viz., the reaction of cyanuric chloride with aromatics is not selective and leads to a mixture of mono-, bis-, and tris-arylated products including unreacted cyanuric chloride (See, Scheme 1). The desired product, 2-chloro-4,6-bisaryl-1,3,5-triazine, must be isolated by crystallization or other purification methods before further reaction.
[0011] Another major drawback of the above mentioned process is that the reaction of cyanuric chloride with aromatics is not generally applicable to all aromatics. It is well known in the literature that the process provides a useful yield of the desired intermediate, 2-chloro-4,6-bisaryl-1,3,5-triazine, only when m-xylene is the aromatic reagent (GB 884802). With other aromatics, an inseparable mixture of mono-, bis-, and trisaryl products are formed with no selectivity for the desired 2-chloro-4,6-bisaryl-1,3,5-triazine (See, H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, 1972, 55, 1575; and S. Tanimoto and M Yamagata, Senryo to Takahin, 1995, 40(12), 325-339). U.S. Pat. No. 5,726,310 describes the synthesis of m-xylene based products 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine is first synthesized and without isolation allowed to react with resorcinol in a one-pot, two-step process to produce 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, which is subsequently purified by crystallization. A one pot process for preparing asymmetric tris-aryl-1,3,5-triazines from cyanuric chloride as well as from mono-aryl-dichloro triazines was earlier described in U.S. Pat. No. 3,268,474.
[0012] Several approaches were developed in an attempt to solve the above mentioned problems related to the formation of the key intermediate 2-chloro-4,6-bisaryl-1,3,5-triazine from cyanuric chloride. For example, cyanuric chloride is allowed to react with an aryl magnesium halide (Grignard reagent), to prepare 2-chloro-4,6-bisaryl-1,3,5 triazine (See, Ostrogovich, Chemiker-Zeitung, 1912, 78, 738; Von R. Hirt, H. Nidecker and R. Berchtold, Helvetica Chimica Acta, 1950, 33, 365; U.S. Pat. No. 4,092,466). This intermediate after isolation can be subsequently reacted in the second step with resorcinol to make a 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine (See, Scheme 2). This approach does not selectively synthesize 2-chloro-4,6-bisaryl-1,3,5-triazine; the mono- and tris-arylated products are formed in significant amounts (See, H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, 1972, 55, 1575). Modifications with better results have been reported (See, U.S. Pat. No. 5,438,138). Additionally, the modified process is not suitable for industrial scale production and is not economically attractive.
[0013] Alternate approaches were developed to solve the selectivity problem when synthesizing 2-chloro-4,6-bisaryl-1,3,5-triazine using either a Friedel-Crafts reaction or Grignard reagents, however, all solutions required additional synthetic steps. One approach, is outlined in Scheme 3. In the first step, cyanuric chloride is allowed to react with 1 equivalent of an aliphatic alcohol to make in high selectivity a monoalkoxy-bischlorotriazine. In the second step, monoalkoxy-bischlorotriazine was allowed to react with aromatics in the presence of aluminum chloride to prepare intermediates monoalkoxy/hydroxy-bisaryltriazines. These intermediates were then converted to 2-chloro-4,6-bisaryl-1,3,5-triazines in the third step by reaction with thionyl chloride or PCl 5 . In the fourth step, 2-chloro-4,6-bisaryl-1,3,5-triazines were allowed to react with resorcinol to synthesize 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazines. In the above process, the desired product was formed with high selectivity. However, the two additional
steps required made the process less attractive economically as an industrial process.
[0014] A similar approach is outlined in Scheme 4 (See, U.S. Pat. Nos. 5,106,972 and 5,084,570). The main difference is that cyanuric chloride was first allowed to react with 1 equivalent of alkanethiol, instead of an alcohol. As with the process summarized in Scheme 3, additional steps were required, making the process neither efficient nor economically feasible.
[0015] Recent improvements are disclosed in European patent application 0,779,280 A1 and Japanese patent application 09-059263.
[0016] Other approaches do not utilize cyanuric chloride as a starting material. For example, the synthesis of 2-chloro-4,6-bisaryl-1,3,5-triazine as disclosed in EP 0497734 A1 and as outlined in Scheme 5. In this process benzamidine hydrochloride is first allow to react with a chloroformate and the resulting product is then dimerized. The resulting 2-hydroxy-4,6-bisaryl-1,3,5-triazine is converted to 2-chloro-4,6-bisaryl-1,3,5-triazine by treatment with thionyl chloride, which is subsequently allowed to react with resorcinol to synthesize 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine, as shown in Scheme 5
[0017] An alternate approach for the preparation of 2-chloro-4,6-bisaryl-1,3,5-triazines is based on the reaction of aryl nitriles with phosgene in the presence of HCl in a sealed tube (S. Yanagida, H. Hayama, M. Yokoe, and S. Komori, J. Org. Chem., 1969, 34, 4125. Another approach is the reaction of N,N-dimethylbenzamide with phosphoryl chloride complex which is then allowed to react with N-cyanobenzamidine to form 2-chloro-4,6-bisaryl-1,3,5-triazine (R. L. N. Harris, Synthesis, 1990, 841). Yet another approach involves the reaction of polychloroazalkenes, obtained from the high temperature of chlorination of amines, with amidines to form 2-chloro-4,6-bisaryl-1,3,5-triazines (H. G. Schmelzer, E. Degener and H. Holtschmidt, Angew. Chem. Internat. Ed., 1966, 5, 960; DE 1178437). None of these approaches are economically attractive, and thus are not commercially feasible.
[0018] Finally, there are at least the approaches which do not require the intermediacy of 2-chloro-4,6-bisaryl-1,3,5-triazine for the preparation of the parent compound, 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. These approaches utilize benzonitriles or benzamidines as starting materials (See U.S. Pat. Nos. 5,705,643 and 5,478,935; WO 96/28431). The benzamidines are condensed with 2,4-dihydroxybenzaldehyde followed by aromatization (Scheme 6) or condensed with phenyl/alkyl 2,4-dihydroxybenzoates (Scheme 7) or 2-aryl-1,3-benzoxazine-4-ones (Scheme 8) to form 2-(2,4,-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. These approaches have the drawback that the starting materials are expensive and may require additional steps to prepare. Moreover, overall yields are not satisfactory and the processes are not economically attractive.
[0019] Based on Benzamidine reactions with 2,4-dihydroxybenzaldehyde:
[0020] Based on Benzamidine reactions with Phenyl 2,4-dihydroxybenzoate
[0021] Based on Benzamidine reactions with substituted 2-aryl-1,3-benzoxazin-4-ones:
[0022] In summary, although direct Lewis acid catalyzed bisarylation of cyanuric chloride to form the desired 2-chloro-4,6-bisaryl-1,3,5-triazine intermediate is the most economically attractive approach, this process has found only limited use due to the following problems:
[0000] 1. Poor selectivity: Almost total lack of selectivity for bisarylation (with the exception of m-xylene where some selectivity is observed). Mono- and tris-arylated triazines are the major by-products.
[0023] 2. Poor reactivity: Typical reaction conditions require high temperatures, long reaction times, and variable temperatures during the course of reaction. Aromatics with electron-withdrawing groups (such as chlorobenzene) fail to react beyond mono-substitution even at elevated temperatures and long reaction times.
[0000] 3. Safety hazards: Temperature and addition rate must be carefully monitored to avoid an uncontrollable exotherm which may result in safety hazards.
[0000] 4. Poor process conditions: The reaction slurry is either thick and difficult to stir or solid thereby making stirring impossible. The process requires various reaction temperatures and addition of reactants in portions over several hours.
[0000] 5. Isolation problem/poor isolated yield: Separation and purification of the desired product is difficult and isolated yields are generally poor and commercially unacceptable
[0000] 6. Not a general process: The reaction cannot be used with different aromatics other than m-xylene.
[0024] Thus, there remains a need for improved methods for synthesizing triazine UV absorbers.
SUMMARY OF THE INVENTION
[0025] It has been now surprisingly discovered after extensive research that 2-halo-4,6-bisaryl-1,3,5-triazine can be prepared with unprecedented selectivity, efficiency, mild conditions, and in high yield by the reaction of cyanuric halide with aromatics in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter. This reaction is also unprecedently general as a variety of aromatics can be used to produce a wide selection of 2-halo-4,6-bisaryl-1,3,5-triazines. The novel approach includes the use of the reaction promoter in combination with at least one Lewis acid under certain reaction conditions to promote the formation of 2-halo-4,6-bisaryl-1,3,5-triazine compounds from cyanuric halide. Preferably, the Lewis acids and reaction promoter's are combined to form a reaction facilitator in the form of a complex.
[0026] The present invention specifically relates to a process for the synthesis of a triazine compound by reacting a cyanuric halide of Formula V:
with at least one substituted or unsubstituted aromatic compound such as a compound of Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, with the reaction being conducted in the presence of at least one reaction facilitator comprising at least one Lewis acid and at least one reaction promoter, optionally in an inert solvent, for a sufficient time at a suitable temperature and pressure to produce a triazine compound of Formula III:
wherein X is a halogen and Ar 1 and Ar 2 are the same or different and each may be the radical of a compound of Formula II:
[0027] In a further embodiment, the triazine compound of Formula III is further reacted with a compound of Formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″wherein R″is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally in the presence of an additional Lewis acid, additional reaction promoter, or additional reaction facilitator; for a sufficient time at a suitable temperature and pressure, optionally in the presence of an inert solvent, to produce a compound of Formula I:
[0028] The reaction to form the compound of Formula III and the reaction to from the compound of Formula I can be carried out without isolating the compound of Formula III.
[0029] Another embodiment relates to a process for synthesizing a triazine compound of Formula I:
wherein Ar 1 and Ar 2 are the same or different, and each independently is a radical of a compound of Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, which comprises:
[0030] simultaneously reacting in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter, sufficient amounts of a cyanuric halide of Formula V:
where each X is independently a halide such as fluorine, chlorine, bromine or iodine, with a compound of Formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and a compound of formula I:
[0031] for a sufficient time, at a suitable temperature and pressure to form the compound of Formula I.
[0032] Another embodiment relates to a process for synthesizing a triazine compound of Formula I:
wherein Ar 1 , and Ar 2 are the same or different, and each independently is a radical of a compound of Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, which comprises:
[0033] reacting in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter, sufficient amounts of a compound of Formula III:
wherein X is independently a halide such as fluorine, chorine, bromine or iodine and Ar 1 and Ar 2 are the same or different and each is a radical of a compound of Formula II; with a compound of Formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, for a sufficient time, at a suitable temperature and pressure to form the compound of Formula I.
DETAILED DESCRIPTION OF THE INVENTION
[0034] The present inventors have found that by using a combination comprising of at least one Lewis acid and at least one reaction promoter; preferably combined to form a reaction facilitator, the reaction of a cyanuric halide with substituted or unsubstituted aromatic compounds can prepare triazine derived 2-halo-4,6-bisaryl-1,3,5-triazine compounds in higher yield with higher selectivity, at a lower reaction temperature, and/or within shorter reaction times than previously known.
[0035] Even more surprising is the fact that the reaction facilitator has been used with excellent results. This approach is in stark contrast to the state of the prior art where the use of anhydrous Lewis acids alone has always been advocated for this reaction step. It has also been discovered that 2-halo-4,6-bisaryl-1,3,5-triazines of this invention can be further reacted, without isolation, with a variety of phenolic derivatives to form 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine. Furthermore, the reaction can be applied to a variety of aromatic compounds. The key reasons for the increase in selectivity and reactivity has been shown to be the use of the reaction promoter.
[0036] As used herein, the cyanuric halide is a compound of the Formula V:
where each X is independently a halide such as fluorine, chlorine, bromine, or iodine.
[0037] The term aromatic compound is to include compounds of the Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′are the same or, different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring.
[0038] Preferred aromatic compounds include benzene, toluene, ethylbenzene, m-xylene, o-xylene, p-xylene, chlorobenzene, dichlorobenzene, mesitylene, isobutylbenzene, isopropylbenzene, m-diisopropyl benzene, tetralin, biphenyl, naphthalene, acetophenone, benzophenone, acetanilide, anisole, thioanisole, resorcinol, bishexyloxy resorcinol, bisoctyloxy resorcinol, m-hexyloxy phenol, m-octyloxy phenol, or a mixture thereof.
[0039] The term “phenolic compound”is to include compounds of the formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or —R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″is hydrogen, alkyl of to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms.
[0040] Preferred phenolic compounds are substituted or unsubstituted monohydroxybenzene, monalkoxybenzene, dihydroxybenzene, dialkoxybenzene, hydroxyalkoxybenzene, trihydroxybenzene, trialkoxybenzene, hydroxybisalkoxybenzene, and bishydroxyalkoxybenzene. More preferred phenolic compounds are: resorcinol (1,3-dihydroxybenzene); C-alkylated resorcinols, e.g, 4-hexylhesorcinol; mono-O-alkylated fresorcinols, e.g, 3-methoxyphenol, 3-octyloxyphenol, 3-hexyloxyphenol, etc.; di-O-alkylated resorcinols, e.g., 1,3-dimethoxybenzene, 1,3-dioctylbenzene, 1,3-dihexyloxybenzene; C-alkylated-di-O-alkylated resorcinols, e.g., 4-hexyl-1,3-dimethoxybenzene; other polyhydroxy, polyalkoxy, hydroxy-alkoxy aromatics, e.g., 1,3,5-trihydroxybenzene, 1,3,5-trialkoxybenzene, 1,4-dihydroxybenzene, 1-hydroxy-4-alkoxybenzene, or mixtures thereof.
[0041] The term “Lewis acid” is intended to include aluminum halides, alkylaluminum halides, boron halides, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halide, copper halides, cadmium halides, mercury halides, antimony halides, thallium halides, zirconium halides, tungsten halides, molybdenum halides, niobium halides, and the like. Preferred Lewis acids include aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, tin dichloride, tin tetrachloride, ferric chloride, or a mixture thereof.
[0042] As used herein the term “reaction promoter” is understood to comprise a compound which is used in combination with the Lewis acid to facilitate the reaction. Thus, triazine compounds are produced at lower reaction temperatures, greater yields, or higher selectivities compared to the use of the Lewis acid alone. Suitable reaction promoters include acids, bases, water, alcohols, aliphatic halides, halide salts, acid halides, halogens, alkenes, alkynes, ester, anhydride, carbonate, urethane, carbonyl, epoxy, ether; acetal compounds, or mixtures thereof.
[0043] Suitable alcohol compounds include carbon compounds of C 1 -C 20 , straight chain or branched, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, which has at least one hydroxyl group and which optionally contains at least one halide, thiol, thiol ether, amines, carbonyl, esters, carboxylic acids, amide, etc. Suitably alcohols include methanol, ethanol, propanol, butanol, isobutanol, t-butanol, 1,2-ethanediol, 3-chloro-1-propanol, 2-hydroxyl-acetic acid, 1-hydroxyl-3-pentanone, cyclohexanol, cyclohexenol, glycerol, phenol, m-hydroxyl-anisole, p-hydroxyl-benzylamine, benzyl alcohol, etc.
[0044] Suitable acid compounds include any inorganic or organic acid that contains at least one acidic proton, which may or may not be dissolved in an aqueous or organic solution. The organic acids include any organic compound that contains at least one acidic functional group including RCO 2 H, RSO 3 H, RSO 2 H, RSH, ROH, RPO 3 H, RPO 2 H, wherein R is as defined above. Preferred protic acids include HCl, HBr, HI, HNO 3 , HNO 2 , H 2 S, H 2 SO 4 , H 3 PO 4 , H 2 CO 3 , acetic acid, formic acid, propionic acid, butanoic acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, methanesulfonic acid, and p-toluenesulfonic acid or mixtures thereof.
[0045] Suitable aliphatic halides include C 1 -C 20 hydrocarbon compounds, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, that are substituted with at least one halide. Optionally, the aliphatic halide may be substituted in one or more positions with an hydroxyl, an ether a polyether, a thiol, a thioether; an amine, such as —NHR, —NR′ 2 —NRR′, a carboxylic acid, an ester, an amide or a carbon structure of C 1 -C 20 group which may be saturated or unsaturated and cyclic or non-cyclic, aromatic and which optionally may be substituted with any of the above preceding groups or mixtures thereof.
[0046] Specific aliphatic halide compounds that are suitable include carbon tetrachloride, chloroform, methylene chloride, chloromethane, carbon tetrabromide, tert-butylchloride, bromoform, dibromomethane, bromomethane, diiodomethane, iodomethane, dichloroethane, dibromoethane, chloroethanol, bromoethanol, benzyl chloride, benzyl bromide, ethanolamine, chloroacetic acid, bromoacetic acid or mixtures thereof.
[0047] The bases that are suitable include inorganic or organic bases dissolved either in water, an organic solvent, or a mixture of solvents. Inorganic bases include LiOH, NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Al(OH) 3 , NH 4 OH, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , MgCO 3 , CaCO 3 , ZnCO 3 , (Al) 3 (CO 3 ) 2 , (NH 4 ) 3 CO 3 , LiNH 2 , Na 2 , K 2 , Mg(2) 2 , CaM 2 ) 2 , Zn(NH 2 ) 2 , Al(NH 2 ) 3 , or a mixture thereof. Organic bases include hydrocarbon compounds with C 1l -C 9 cyclic or non-cyclic that contain at least one alkoxide, amine, amide, carboxylate, or thiolate and which may be substituted in one or more positions with a halide, an hydroxyl, an ether, a polyether, a thiol, a thioether, an amine, such as —NHR, —NR′ 2 , —NRR′, a carboxylic acid, an ester, or an amide. Organic bases include CH 3 O − , CH 3 CH 2 O − , CH 3 CH 2 CH 2 O—, (CH 3 ) 2 CHO − , ((CH 3 ) 2 CH) 2 CHO − , CH 3 CH 2 CH 2 CH 2 O − , (CH 3 ) 3 CO, CH 3 NH 2 , CH 3 C 1 H 2 NH 2 , CH 3 CH 2 CH 2 NH 2 , (CH 3 ) 2 CH 2 , ((CH 3 ) 2 CH) 2 CHNH 2 , CH 3 CH 2 CH 2 CH 2 NH 2 , (CH 3 ) 3 CNH 2 , (CH 3 ) 2 NH, (CH 3 CH 2 ) 2 NH, (CH 3 CH 2 CH 2 ) 2 NH, ((CH 3 ) 2 CH) 2 NH, (((CH 3 ) 2 CH) 2 CH) 2 NH, (CH 3 CH 2 CH 2 CH 2 ) 2 NH, ((CH 3 ) 3 C) 2 NH, (CH 3 ) 3 N, (CH 3 CH 2 ) 3 N, (CH 3 CH 2 CH 2 ) 3 N, ((CH 3 ) 2 CH) 3 N, (((CH 3 ) 2 CH) 2 CH) 3 N, (CH 3 CH 2 CH 2 CH 2 ) 3 N, ((CH 3 ) 3 C) 3 N, CH 3 NH − , CH 3 CH 2 NH − , CH 3 CH 2 CH 2 NH − , (CH 3 ) 2 CHNH − , ((CH 3 ) 2 CH) 2 CHNH − , CH 3 CH 2 CH 2 CH 2 N − ; (CH 3 ) 3 CNH − , (CH 3 ) 2 N − , (CH 3 CH 2 ) 2 N − , (CH 3 CH 2 CH 2 ) 2 N − , ((CH 3 ) 2 CH) 2 N − , (((CH 3 ) 2 CH) 2 CH) 2 N − , (CH 3 CH 2 CH 2 CH 2 ) 2 N − , ((CH 3 ) 3 C) 2 N − , pyriolidine, piperidine, pyrrole, pyridine, aniline, tetramethylenediamine, the corresponding deprotonated amine, and a cation were appropriate. Organic bases also includes salts of deprotonated carboxylic acids such as salts of formate, acetate, propylate, butanoate, benzoate, with Li, Na, K, Mg, Ca, Al, Zn, or any other suitable cation. Organic base includes mixtures of the aforementioned inorganic and organic bases, or a mixture thereof.
[0048] Halogen reaction promoters include fluorine, chlorine, bromine, iodine, or mixed halogens dissolved in either water, an organic solvent, or a mixture of solvents or present as part of an organic or inorganic compound. Halogenated solvents that are suitable include dichloromethane, chloroform, carbon tetrachloride, di-bromomethane, bromoform, iodomethane, diiodomethane, dichloroethane, 1,1,2,2-tetrachloroethane, benzene, toluene, acetone, acetic acid, hexane, or a mixture thereof.
[0049] Additional reaction promoters that are suitable include hydrocarbon compounds of Formula VI:
wherein R 11 and R 12 are either the same or different, may be taken together, hydrogen, hydrocarbon C 1 -C 20 , saturated or unsaturated, aromatic or non-aromatic cyclic or non-cyclic, hydroxyl, ether amine, substituted amine, carboxylate, ester, amide, and may be substituted at least once with a halide, hydroxyl, amine, amide, thiol, thioether, carboxylate, or a carbon structure of C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups, or mixtures thereof.
[0050] Additional compounds of Formula VI include those wherein R 11 and R 12 are either the same or different, may be taken together; hydrocarbon C 1 -C 12 , saturated or unsaturated, cyclic or non-cyclic, hydroxyl, ether, mine, substituted amine, carboxylate, ester, amide, and may be substituted at least once with a halide, hydroxyl, amine, amide, thiol, thioether, carboxylate, or a carbon structure of C 1 -C 7 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups, including hydrocarbon compounds acetaldehyde, butyraldehyde, glutaric dialdehyde, crotonaldehyde, benzaldehyde, acetone, methyl vinyl ketone, acetophenone, cyclohexanone, 2-cyclohexen-1-one, methyl acrylate, acetic anhydride, crotonic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, dimethyl adipate, diethyl phthalate, dimethyl carbonate, ethylene carbonate, diphenyl carbonate, phenyl carbamate, benzyl carbamate, methyl carbamate, urethane, propyl carbamate, or mixtures thereof.
[0051] Suitable ether compounds as reaction promoter's include hydrocarbon compounds C 2 -C 20 , saturated or unsaturated, aromatic or non-aromatic, cyclic or non-cyclic, that have at least one C—O—C bond, and optionally are substituted with at least one halide, hydroxyl, amine, thiol, thioether; carboxylic acid, ester, or a carbon structure of C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups or mixtures thereof.
[0052] Additional ether compounds are hydrocarbon compounds of C 2 -C 12 that have at least one C—O—C bond, saturated or unsaturated, aromatic or non-aromatic, cyclic or non-cyclic, and may be substituted at least once with a halide, hydroxyl, amine, ether, thiol, thioether, carboxylic acid, ester; or a carbon structure of C 1 -C 7 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups including hydrocarbon compounds dimethyl ether; isopropyl ether, dipropyl ether; tert-amyl methyl ether; tert-butyl ethyl ether; allyl phenyl ether; allyl propyl ether, 4-methoxyphenyl ether, 3,3-dimethyl oxetane, dioxane, tetrahydropyran, tetrahydro-4H-pyran-4-ol, ethylene oxide, propylene oxide, styrene oxide, glycidol, glycidyl methyl ether glycidyl butyrate, glycidyl methacrylate, 1,2-epoxy-3-phenoxypropane, 1,2-epoxyhexane, 1-chloro-2,3-epoxypropane, diethyl acetal, 2,2-dimethoxypropane, 1,1-dimethoxycyclohexane, 2-hexenal diethyl acetal, 3-chloropropionaldehyde diethyl acetal, benzaldehyde dimethyl acetal, 1,1,3-trimethoxypropane, or a mixture thereof.
[0053] Alkene reaction promoters include hydrocarbon compounds C 2 -C 20 that include at least one C—C double bond or C—C triple bond, whether the compounds are cyclic, heterocyclic or non-cyclic, and where the compounds are optionally substituted at least once with a halide, hydroxyl, amine, ether; thiol, thioether carboxylic acid, ester; or a carbon structure of C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic and which optionally may be substituted with any of the above preceding groups, or mixtures thereof.
[0054] Additional alkene reaction promoters include hydrocarbon compounds of C 2 -C 12 with at least one C—C double bond or C—C triple bond, cyclic, heterocyclic or non-cyclic, and may be substituted at least once with a halide, hydroxyl, amine, ether, thiol, thioether; carboxylic acid, ester; or a carbon structure of C 1 -C 7 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups including hydrocarbon compounds 2-methylpropene, 1-butene, 2-butene, 2-methyl-2-butene, 1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 2-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-2-pentenoic acid, 3-methyl- 1 -penten-3-ol, 5-chloro-1-pentene, 4-bromo-2-methyl-2-butene, 1,4-pentadiene, 2,6-heptadienoic acid, hexatriene, cyclohexene, cyclohexadiene, cyclopentadiene, 2-cyclopenten-1-one, 2-methylfuran, styrene, methylstyrene, methyl vinyl ketone, acrylic acid, methyl acrylate, 1-pentyne, 2-pentyne, 2-pentyn-1-ol, 6-chloro-1-hexyne, 1,6-heptadiyne, or mixtures thereof;
[0055] Further reaction promoters include compounds of the formula RCOX, RSOX, RSO 2 X, or RPOX wherein at least one carbon, sulfur, or phosphorus atom is double bonded with at least one oxygen atom or phosphorous halides such as PX 3 and PX 5 wherein X is at least one halide from the group F, Cl, Br, and I. R is at least one halide or hydrocarbon C 1 -C 20 saturated or unsaturated, cyclic or non-cyclic, and may be substituted at least once with a halide, hydroxyl, amine, ether; thiol or mixtures thereof.
[0056] Compounds where R includes chloro, bromo, methyl; ethyl, propyl, isopropyl, butyl, phenyl, tolyl, naphthalyl, X includes F, Cl, Br, I, including compounds such as thionyl chloride, thionyl bromide, phosphorus oxybromide, phosphorus oxychloride, phosgene, acetyl chloride, acetyl bromide, benzoyl chloride, benzoyl bromide, toluoyl chloride, toluenesulfonyl chloride, terephthaloyl chloride, terephthaloyl bromide, oxalyl dichloride, oxalyl dibromide, succinyl dichloride, glutaryl dichloride, adipoyl dichloride, pimeloyl dichloride, methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, isopropylsulfonyl chloride, butanesulfonylchloride, benzenesulfonyl chloride, methyl dichlorophosphite, phosphoric acid halides, PCl 3 , PBr 3 , PCl 5 , PBr 5 , or mixtures thereof are suitable.
[0057] Compounds of the formula M a X b are also suitable reaction promoters, wherein the bond dissociation energy of M-X is about less than 145 kcal/mol at 298° Kelvin and where M includes at least one metal or organic cation of the formula NR 4 + , SR 3 + , or PR 4 + where R includes C 1 -C 6 which may be substituted at least one halide hydroxyl, amine, ether, thiol or mixtures thereof and where X is at least one anion.
[0058] Inorganic or organic compounds defined above that are suitable are also soluble in water or organic solvents such as methanol, ethanol, isopropanol, methylene chloride, acetone, diethyl ether, tetrahydrofuran, ethylene glycol, xylene, and chlorobenzene. These compounds include antimony halides, arsenic halides, barium halides, beryllium halides, bismuth halides, boron halides, cadmium halides, calcium halides, cerium halides, cesium halides, cesium tetrachloroaluminates, cobalt halides, copper halides, gold halides, iron halides, lanthanum halides, lithium halides, lithium tetrachloroaluminates, magnesium halides, manganese halides, mercury halides, nickel halides, osmium halides, phosphorus halides, potassium halides, potassium hydrogen fluorides, potassium tetrachloroaluminates, rhodium halides, samarium halides, selenium halides, silver halides, sodium halides, tin halides, lanthanum halides, sodium hydrogen fluorides, sodium tetrachloroaluminates, sodium/potassium tetracloroaurates, sodium/potassium/lithium/zinc/copper tetrafluoroborates, thalium halides, titanium chloride-aluminum chlorides (x:y), titanium halides, yttrium halides, zinc halides, zirconium halides, ammonium halides, tetraalkyl quaternary ammonium halides, aralkyl trialkylquaternary ammonium halides, arayl trialkylammonium halides, alkyl N-alkylimidazolium halides, aralkyl N-alkylimidazolium halides, alkyl N-aralkylimidazolium halides, N-alkylpyridinium halides, N-alkylisoquinolinium halides, N-alkylquinolinium halides, triphenylphosphonium halides, haloalkyl triphenylphosphonium halides, carboxyalkyl triphenylphosphonium halides, carbalkoxyalkyl triphenylphosphonium halides, cycloalkyl triphenylphosphonium halides, alkenyl triphenylphosphonium halides, aralkyltriphenylphosphonium halides, hydroxyaralkyl phosphonium halides, tetraphenylphosphonium halides, trialkylsulphonium halides, including but not limited to, inorganic compounds where M includes Li + , Na + , K + , Mg 2+ , Ca 2+ , S 2+ , Ba 2+ , Ti 4+ , CO 2+ , Ni 2+ , Cu + Cu 2+ , Sn 2+ , Sn 4+ , Pb 2+ , Pb 4+ , Ce 3+ , and Ce 4+ ; organic compounds where M includes + N(CH 3 ) 4 , + N(CH 2 CH 3 ) 4 , + N(CH 2 CH 2 CH 3 ) 4 , + N(CH 2 CH 2 CH 2 CH 3 ) 4 , + NPh 4 , + P(CH 3 ) 4 , + P(CH 2 CH 3 ) 4 , + P(CH 2 CH 2 CH 3 ) 4 , + P(CH 2 CH 2 CH 2 CH 3 ) 4 , + PPh 4 , + S(CH 3 ) 3 , + S(CH 2 CH 3 ) 3 , + S(CH 2 CH 2 CH) 3 , + S(CH 2 CH 2 CH 2 CH 3 ) 3 , + SPh 3 , pyridinium, imidazolium, pyrrolidinium, and pyrrolium, and X includes inorganic X includes Cl − , Br − , I − , S 2− , O 2− , CO 3 2− , SO 3 2− , SO 4 2− , NO 2 − , NO 3 − , BF 4 − , OH − , PO 3 2− , PO 4 2− , ClO 4 − , MnO 4 − ; organic X includes HCO 2 − , CH 3 CO 2 − , CH 3 − , CH 3 CH 2 − , Ph − , CH 3 O − , CH 3 CH 2 O − , PhO − ; CH 3 S − ; CH 3 CH 2 S − , PhS − , CH 3 NH − , CH 3 CH 2 NH − , PhNH − or mixtures thereof.
[0059] The reaction promoter may also be water alone or as an aqueous solution or aqueous suspension, that contains other components therein, such as one or more of the promoters mentioned above.
[0060] Optionally, a combination of at least one Lewis acid and at least one reaction promoter, i.e. a reaction facilitator; is prepared before being added to the reactants.
[0061] The term “solvent” includes hydrocarbon compounds C 1 -C 24 saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, optionally substituted with at least one halide, nitro, or sulfide group. Preferred solvents are hydrocarbons C 1 -C 8 , saturated or unsaturated, such as nitroalkanes, heptane, cyclohexane, benzene, nitrobenzene, dinitrobenzene, toluene, xylene, 1,1,2,2-tetrachloroethane, dichloromethane, dichloroethane, ether, dioxane, tetrahydrofuran, benzonitriles, dimethylsulfoxide, tetramethylene sulfone, carbon disulfide, and benzene rings substituted with at least one halide such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, trifluorobenzene, bromobenzene, dibromobenzene, tribromobenzene, or mixtures thereof.
[0062] The products of the present process include halo-bisaryl-1,3,5-triazine compounds or trisaryl-1,3,5-triazine compounds wherein the aromatic compounds include a C 5 -C 24 unsaturated ring, such as cyclopentadiene, phenyl, biphenyl, indene, naphthalene, tetralin, anthracene, phenanthrene, benzonaphthene, fluorene, which may be substituted in one or more positions with a halide, an hydroxyl, an ether, a polyether, a thiol, a thioether, an amine, such as —NHR, —NR 2 , —NRR′, a carboxylic acid, an ester, an amide or a C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups. A general structure of useful compounds is shown above in Formulas I and III.
[0063] Preferred products include chloro-bisaryl-1,3,5-triazine compounds or trisaryl-1,3,5-triazine compounds wherein the aromatic substituents include phenyl, an ortho, meta, and/or para substituted phenyl ring, a naphthalene ring substituted at one or more positions, substituted or unsubstituted biphenyl, or tetralin ring substituted at one or more positions, wherein the substitution group is a lower alkyl such as methyl, ethyl, propyl, butyl, iso-butyl, t-butyl, pentyl, hexyl, septyl, octyl, nonyl, hydroxy, an ether group such as methoxy, ethoxy, propyloxy, octyloxy, nonyloxy, or a halogen, such as fluoride, chloride, bromide, or iodide.
[0064] Other suitable products include chloro-bisaryl-1,3,5-triazine compounds, trisaryl-1,3,5-triazine compounds, or 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine compounds wherein the aromatic substituted compounds include o-xylene, m-xylene, p-xylene, o-cresol, m-cresol, p-cresol, mesitylene, trimethylbenzene, cumene, anisole, ethoxybenzene, benzene, toloune, ethylbenzene, biphenyl, tert-butylbenzene, propoxybenzene, butoxybenzene, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, o-nonoxyphenol, m-nonoxyphenol, tetralin, 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(4-alkoxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-chloro-4,6-bisphenyl-1,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine; 2-(4-alkoxy-2-hydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine; 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2-(2-hydroxy-4-isooctyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
[0065] The term “step-wise” means a reaction sequence wherein a series of reactions are conducted, the first reaction producing a compound of Formula IV and being carried out to about 50% to about 100% completion prior to addition of a compound of Formula IV to produce a compound of Formula I. Preferably the reaction is carried out to about 70% to about 100% completion prior to addition of compound of Formula IV, and more preferably to about 75% to about 100% completion.
[0066] The term “continuous” means a reaction sequence not defined as “step-wise.”
[0067] The relative amounts of the reactants are as follows. The amount of a cyanuric halide should be in sufficient amounts to react with aromatic compounds of Formula II to produce either 2-halo-4,6-bisaryl-1,3,5-triazine or 2,4,6-trisaryl-1,3,5-triazine. The amount of aromatic compound of Formula II is important to ensure that a sufficient amount of monohalo-bisaryl-triazine is synthesized without excessive amounts of undesired side products such as 2,4-dihalo-6-aryl-1,3,5-triazine or trisaryl triazine. Moreover, excess amounts of aromatic compounds can lead to undesired product distributions enriched in mono- and tris-aryl triazines, thus, making product separation and purification difficult and resource consuming.
[0068] The amount of aromatic compounds should be in sufficient amounts to synthesize 2-halo-4,6-bisaryl-1,3,5-triazine, 2,4,6-trisaryl-1,3,5-triazine, or convert 2-halo-4,6-bisaryl-1,3,5-triazine into 2,4,6-trisaryl-1,3,5-triazine. Preferably, there should be between about 1 to about 5 mol equivalents of aromatic compound of formula II to cyanuric halide. More preferably, the amount of aromatic compound of Formula IV should be between about 0.5 to about 2.5 mol equivalents of aromatic compound of Formula IV to cyanuric halide. In some cases aromatic compounds of Formula II can be used both as a reactant and a solvent.
[0069] The amount of Lewis acid used in the reaction facilitator should be in sufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine to the preferred 2-halo-4,6-bisaryl-1,3,5-triazine or 2,4,6-trisaryl-1,3,5-triazine. The amount of Lewis acid should be between about 0.5 to about 500 mol equivalents. Preferably, the amount of Lewis acid should be between about 1 to about 10 mol equivalents to cyanuric halide.
[0070] The amount of reaction promoter used in the reaction facilitator should be in sufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine, to the preferred 2-halo-4,6-bisaryl-1,3,5-triazine or convert 2-halo-4,6-bisaryl-1,3,5-triazine to the compound of Formula I. Preferably, the amount of reaction promoter should be between about 0.01 to about 5 mol equivalents to cyanuric halide.
[0071] The Lewis acid and reaction promoter preferably combine to form a reaction facilitator complex that can be prepared in situ or pre-formed prior to addition to the reagents. The Lewis acid and/or reaction promoter or reaction facilitator can be combined with either a compound of Formula II or compound of Formula IV or both in any manner. In situ reaction facilitator preparation comprises addition of at least one Lewis acid and at least one reaction promoter to a mixture of cyanuric halide, at least one aromatic compound of Formula II, and optionally solvent without regard to addition order. To prepare the reaction facilitator prior to addition to the reagents, i.e., the pre-formed method, Lewis acid and reaction promoter are combined and allowed to mix prior to addition, optionally in an inert solvent. Thereafter, the reaction facilitator is added to the reagents or vice versa, as desired and in any addition order. As used herein, one or more Lewis acids may be used, the first step and second step Lewis acid may be the same or different. Additionally, one or more reaction promoters may be used, the first step and second step reaction promoter may be the same or different. In the “continuous”process, the use of additional Lewis acid and reaction promoter is optional.
[0072] If the reaction facilitator is prepared using the pre-formed method, preferred mixing time of the Lewis acid and reaction promoter; prior to addition to the reagents, is between about 1 minute to about 10 hours, more preferred is between about 10 minutes to about 5 hours. The preferred mixing temperature of the Lewis acid and reaction promoter combination, prior to addition to the reagents, is between about −50° C. to about 100° C., more preferred is between about −10° C. to about 50° C.
[0073] The reaction should run for sufficient time, at a sufficient temperature and pressure to synthesize the desired triazine compound. The preferred reaction time fort the synthesis of compounds of Formula III, i.e., the first step, is between about 5 minutes and about 48 hours, more preferred between about 15 minutes and about 24 hours. The preferred reaction time for the synthesis of compounds of Formula I, i.e., the second step, is between about 10 minutes and about 24 hours, more preferably between about 30 minutes and about 12 hours. The use of the reaction facilitator reduces the reaction time while improving the selectivity for mono-halo-bis-aryl products in the first step. The preferred reaction temperature for the first step is between about −50° C. and about 150° C., more preferred between about −30° C. and about 50° C. One advantage of using the reaction facilitator is the elimination of the need to heat the reaction mixture to increase the rate of reaction. Additionally, due to the use of the reaction facilitator, the reaction temperature can be maintained at about ambient or lower temperatures, thus increasing product selectivity. The reaction pressure is not critical and can be about 1 atm or higher if desired. An inert gas such as nitrogen or argon is preferred. The preferred reaction temperature for the second step is between about 0° C. and about 120° C., more preferred between about 20° C. and about 100° C.
[0074] The step-wise process comprises mixing cyanuric halide and the reaction facilitator with one or more of the desired aromatic compounds, preferably until the reaction is about 70% to about 100% completed. Thereafter, the product of Formula III is isolated. The second aromatic compound of Formula IV is added to the isolated product of Formula III along with Lewis acid and optionally reaction promoter or reaction facilitator to synthesize the trisaryl-triazine. The step-wise sequence allows for the isolation, purification, and storage of Formula III product prior to subsequent reaction with compounds of Formula IV.
[0075] The continuous reaction comprises allowing a cyanuric halide to react with one or more aromatic compounds of Formula II in the presence of the reaction facilitator preferably until the reaction is about 70% to about 100% complete. Thereafter, without isolating the product of Formula III, the second aromatic compound of Formula IV is allowed to react with the product of Formula III in the presence of optionally at least one second Lewis acid and optionally at least one second reaction promoters, or reaction facilitator preferably until the reaction is about 70% to about 100% complete. The continuous reaction eliminates the need to isolate the intermediate product of Formula III or use of additional reagents such as solvents, and optionally Lewis acids, reaction promoters, or reaction facilitators. Moreover, the one-step process simplifies the synthetic reaction pathway such that no unnecessary handling or processing of the reaction mixture is required until the reaction is completed.
[0076] To synthesize compounds of Formula III using the pre-formed reaction facilitator method, the preferred addition time of the reaction facilitator to a reagent mixture is between about 5 minutes to about 5 hours, more preferred is between about 15 minutes to about 3 hours. The addition temperature of the reaction facilitator to a reagent mixture is between about −50° C. to about 150° C., preferred addition temperature is between about −30° C. to about 50° C., and more preferred addition temperature between about −20° C. to about 30° C.
[0077] To synthesize compounds of Formula I using the pre-formed reaction facilitator, the preferred addition temperature of the reaction facilitator to a reagent mixture is between about 0° C. to about 100° C., preferred addition temperature is between about 20° C. to about 80° C.
[0078] To synthesize compounds of Formula I, the preferred addition time of the compound of Formula IV to the reaction mixture is between about 5 minutes to about 10 hours, more preferred addition time is between about 10 minutes to about 5 hours, and most preferred addition time is between about 15 minutes to about 2 hours. The addition temperature of the compound of Formula IV to the reaction mixture is between about 0° C. to about 150° C., preferred addition temperature is between about 20° C. to about 100° C.
[0079] The reaction facilitator should be present in amounts sufficient to react with the number of halogens being substituted on the triazine compound. A range of between about 1 to about 10 mol equivalents of Lewis acid and a range of between about 0.01 to about 5 mol equivalents of reaction promoter can be used. The preferred Lewis acid is aluminum halide, most preferably aluminum chloride. A preferred amount of Lewis acid is between about 2 to about 4 mol equivalents to halo-triazine. A preferred amount of reaction promoter is between about 0.05 to about 2 mol equivalents to triazine or triazine derived compounds.
[0080] The invention provides several advantages over prior art process such as higher yields, greater selectivity of reaction products, higher reaction rates, and/or applicability of reaction conditions to various aromatic compounds. The present invention consistently provided yields in the range of about 70 to about 98%, based on cyanuric halide conversion, as determined by HPLC analysis. Additionally, the ratio of desired 2-halo-4,6-bisaryl-1,3,5-triazine to trisaryl-1,3,5-triazine consistently averaged about 70:30 or more. The reaction facilitator significantly increased reaction rates in comparison to state of the art with Lewis acids alone. Moreover, the reaction conditions provided high yield and selectivity for a variety of aromatic compounds regardless oft the aromatic substituents.
[0081] The triazine compounds synthesized using the present process can be applied to a variety of applications such as those described in U.S. Pat. No. 5,543,518 to Stevenson et al. Col. 10-19, the content of which, as noted above, is expressly incorporated by reference herein.
[0082] The 2-chloro-4,6-bisaryl-1,3,5-triazines are not only important intermediates for the preparation of trisaryl triazine UV absorbers, but they are also valuable intermediates for a variety of other commercially important products, such as vat dyestuffs (CB 884,802), photographic material (JP 09152701 A2), optical materials (JP 06065217 A2), and polymers (U.S. Pat. No. 706,424; DE 2053414, DE 1246238). These compounds are also of interest for medicinal applications (e.g., see: R. L. N. Harris, Aust. J. Chem., 1981, 34, 623-634; G. S. Trivedi, A. J. Cowper, R. R. Astik, and K. A. Thaker, J. Inst. Chem., 1981, 53(3), 135-138 and 141-144).
EXAMPLES
[0083] Certain embodiments and features of the invention are illustrated, and not limited, by the following working examples.
[0084] The reaction progress can be monitored by HPLC or TLC. Further product characterization may be done by LCMS, MS, NMR, UV, direct comparison with authentic examples, or analytical techniques which are well known in the art. A typical HPLC analysis of the samples is carried out as follows. The reaction mixture may, in some cases be a two-phase system, with a lower, viscous liquid layer which may contain most of the reaction products (as AlCl 3 complexes), and a supernatant, which may contain very little material. This supernatant can be often enriched in unreacted cyanuric chloride. In case of a two-phase system, it is important that both phases are sampled together, in a representative fashion. For example, the mixture can be stirred rapidly and a sample taken from the middle of the mixture using a polyethylene pipette with the tip cut off. When pipetting the sample into a vial for work-up, it is important that the contents of the pipette be completely discharged. Since the two phases will separate into upper and lower layers, partial discharge may result in a sample enriched in the lower layer.
[0085] The reaction sample is discharged into a 4-dram vial containing either chilled 5% HCl, or a mixture of 5% HCl and ice. The precipitate can be extracted with ethyl acetate and the water layer can be pipetted off. The ethyl acetate layer is then washed with water. Finally, an approximately 10% solution of the ethyl acetate layer in acetonitrile is prepared for HPLC analysis.
[0086] Certain embodiments and features of the invention are illustrated, and not limited, by the following working examples.
Example 1
Synthesis of 2-chloro-4,6-bis(2,4-dimethyl phenyl)-135-triazine without a Reaction Promoter
[0087] Cyanuric chloride (11.84 g) was allowed to react with 1.9 eq of m-xylene and 2.5 eq (3.35 g) of AlCl 3 in 25 mL of chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. Analysis by HPLC, after 2.5 h, showed that less than 8% of cyanuric chloride had reacted to form only 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine, no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine were present. The reaction was allowed to continue at room temperature. After 24 hours, HPLC analysis showed about 51% cyanuric chloride conversion and formation of 2,4 dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 95:5, respectively No 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 2
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine without a Reaction Promoter
[0088] Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq of m-xylene and 2.5 eq (3.35 g) of AlCl 3 in chlorobenzene at 5° C. for 2 h and then at 15° C. for 5 h. Analysis by HPLC showed about 5% conversion of cyanuric chloride to 2,4-bischloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine. The reaction was allowed to continue at room temperature. After 22 hours, HPLC analysis showed about 55% cyanuric chloride conversion and formation of 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 96:4, respectively. The reaction was allowed to continue. After 72 hours at room temperature, a final HPLC analysis showed 99% cyanuric chloride conversion, formation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 78:22, and no 2,4-bischloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 3
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.1 eq resorcinol and 2.5 eq AlCl 3
[0089] Cyanuric chloride was allowed to react with 2.05 eq of m-xylene in chlorobenzene, in the presence of 2.5 eq of AlCl 3 and 0.1 eq of resorcinol. The reaction was carried out at about 5° C. for 2 h and then at room temperature for 5 h. Analysis by HPLC showed about 10% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After about 40 h at room temperature, HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine present in a 78:22 ratio respectively, no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 4
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 2.5 eq AlCl 3 and conversion to 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0090] Cyanuric chloride (1.84 g) was allowed to react with 1.9 eq of m-xylene, in the presence of 2.5 eq of AlCl 3 (3.35 g) and 0.2 eq of resorcinol, in 25 mL chlorobenzene at bout 5° C. for 0.5 h and then at room temperature for 3 h. Analysis by HPLC showed about 14% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After about 13 h at room temperature, HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 82:18, respectively. No 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine or resorcinol-containing products were detected.
[0091] To the reaction mixture was added an additional 0.9 eq resorcinol and the reaction mixture was heated at 80° C. for 1 h. HPLC analysis indicated the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 79:21 ratio, with about 1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The process to make 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine was complete within 15 hours.
[0092] The heating was discontinued and the reaction mixture allowed to cool to room temperature. 2% ice-cold aqueous HCl was added with stirring to break the aluminum complexes. A yellow precipitate was formed. The reaction mixture was filtered, washed with water, and dried to give 3.65 g of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 5
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 1 eq resorcinol and 2.5 eq AlCl 3
[0093] Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq of m-xylene, in the presence of 2.5 eq of AlCl 3 (3.35 g) and 1 eq of resorcinol, in 25 mL chlorobenzene at about 5° C. for 2 h and then at 15° C. for 4 h. Analysis by HPLC showed 70% conversion of cyanuric chloride, mainly to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 59:41 ratio. Two minor components were also present, 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine (5%) and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (3%). The reaction mixture was allowed to warm to room temperature, and after about 16 h at room temperature, HPLC analysis showed 92% cyanuric chloride conversion, mainly to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (66%), 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (25%), 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (4.5%), and 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4-(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine (3%).
Example 6
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis( 2 , 4 -dimethylphenyl)-1,3,5-triazine using 0.5 eq resorcinol and 2.5 eq AlCl 3
[0094] Cyanuric chloride was allowed to react with 2 eq of m-xylene, in the presence of 2.5 eq of AlCl 3 and 0.5 eq of resorcinol, in chlorobenzene at room temperature for about 22 h. Analysis of the reaction mixture by HPLC showed about 94% cyanuric chloride conversion, mainly to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 69:27:4.
Example 7
Synthesis of chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3
[0095] A. Absence of a Reaction Promoter
[0096] Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 3 eq of AlCl 3 1 in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. An HPLC analysis showed about 3% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 h at room temperature, HPLC analysis showed about 33% conversion to cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(274-dimethylphenyl)-1,3,5-triazine, formed in a 96:4 ratio respectively.
[0097] B. Effect of 0.2 eq of Resorcinol
[0098] Thereafter, 0.2 eq of resorcinol was added to the above reaction mixture, and the reaction mixture was further stirred at room temperature for 16 h. HPLC analysis showed 97% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 80:20 ratio respectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 8
Synthesis of 2(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5 triazine using 0.2 eq resorcinol and 3 eq AlCl 3
[0099] Cyanuric chloride was allowed to react with 1.9 eq of m-xylene, in the presence of 3 eq of AlCl 3 and 0.2 eq of resorcinol, in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. Am HPLC analysis after 3 h at room temperature showed about 20% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The reaction mixture was stirred overnight at room temperature. After 18 h, an HPLC analysis showed 97% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 81:19 ratio respectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
[0100] To the reaction mixture was then added 0.9 eq of resorcinol, and the mixture was heated in an oil bath to 60° C. (oil bath temperature). After 5 h, analysis by HPLC showed the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (73%) and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (21%), with 3% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 9
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 2.75 eq AlCl 3
[0101] Cyanuric chloride was allowed to react with 2.05 eq of m-xylene in the presence of 2.75 eq of AlCl 3 , and 0.2 eq of resorcinol in chlorobenzene at 5° C. for 0.5 h and then allowed to warm to room temperature. After a total of 18 h at room temperature, analysis by HPLC showed 98% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in an 81:19 ratio respectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected. The reaction mixture was then allowed to react with 0.9 eq of resorcinol at 60° C. for 5 h. HPLC analysis showed the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 77:21 with 1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 10
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 1.8 eq AlCl 3
[0102] Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 1.8 eq of AlCl 3 , and 0.2 eq of resorcinol in chlorobenzene at 5° C. for 0.5 h and then allowed to warm to room temperature. After 18 h at room temperature, HPLC analysis showed 84% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 46:54 ratio. 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was the major product, and about 3% 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was also present.
[0103] The reaction was allowed to continue at room temperature. After 4 days, HPLC analysis showed 93% cyanuric chloride conversion, with the following product distribution: 75% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine; 17% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 4% 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and other resorcinol-containing components as minor products.
Example 11
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.144 eq resorcinol and 1.8 eq AlCl 3
[0104] Cyanuric Chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 1.8 eq of AlCl 3 and 0.144 eq of resorcinol, in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. The ratio of AlCl 3 to resorcinol was thus 12.5:1. An HPLC analysis after 65 hours at room temperature showed 91% cyanuric chloride conversion, with the following product distribution: 79% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine; 10% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 8% 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and other resorcinol-containing compounds as minor products
Example 12
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis( 2 , 4 -dimethylphenyl)-1,3,5-triazine using 0.15 eq resorcinol and 2.5 eq AlCl 3 in a tetrachloroethane solvent
[0105] Cyanuric chloride was allowed to react with 1.9 eq of m-xylene, in the presence of 0.15 eq of resorcinol and 2.5 eq of AlCl 3 , in 1,1,2,2-tetrachloroethane at room temperature for about 26 h. HPLC analysis showed about 95% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 87:13 ratio. The reaction mixture was allowed to react with an additional 0.9 eq of resorcinol for 4 h at 90° C. HPLC analysis showed 98.3% 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine conversion, and the ratio of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 84:16.
Example 13
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 3 eq AlCl 3 in a tetrachloroethane solvent
[0106] Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 3 eq of AlCl 3 and 0.2 of resorcinol, in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. The first step (conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) was completed in less than 16 h, with more than 98% cyanuric chloride conversion as determined by HPLC analysis. 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine were formed in an 86:14 ratio; no other products were detected. The reaction mixture was allowed to react with additional resorcinol at 110° C. for 1.5 h. HPLC analysis showed a product mixture of 82% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, with only 1.5% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 14
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using methyl alcohol with 3 eq AlCl 3
[0107] A two-neck round bottom flask was equipped with a reflux condenser; an argon inlet, a magnetic stirring bar and a glass stopper Cyanuric chloride (3.7 g) and 50 mL of chlorobenzene were added. Next, 3 eq of AlCl 3 (8 g) at ice-bath temperature was added, followed by 0.4 mL of methyl alcohol. After 5 min, 1.9 eq of m-xylene was added. The cooling was removed, and the reaction mixture was stirred at room temperature. The reaction was complete within 20 h at room temperature, as indicated by HPLC which showed the absence of m-xylene and 97% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in an 83:17 ratio.
[0108] To the reaction mixture was added 1.1 eq of resorcinol, and the reaction mixture was heated at 85° C. for 4,5 h. HPLC analysis showed the formation of 78% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 19% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1,4% 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine. The reaction was allowed to cool to room temperature, and 2% ice-cold aqueous HCl was added. A yellow precipitate was formed, separated by filtration, washed with water, and dried to yield 7.7 g of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 15
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 2.5 AlCl 3 at 45° C.
[0109] Cyanuric chloride was allowed to react with 1.9 eq m-xylene, in the presence of 2.5 eq AlCl 3 and 0.2 eq resorcinol, in chlorobenzene at 45° C. HPLC analysis of the reaction after 4 h showed 95% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 67:33 ratio respectively.
Example 16
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 2.5 eq AlCl 3 in a dichlorobenzene solvent
[0110] Cyanuric chloride was allowed to react with 2 eq m-xylene, in the presence of 2.5 eq AlCl 3 and 0.2 eq of resorcinol, in ortho-dichlorobenzene at 24° C. After about 21 h, an exotherm was observed. A sample was immediately taken. HPLC analysis of the sample showed 94% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in an 81:19 ratio. After the exotherm had subsided, the cyanuric chloride conversion had increased to 97.5%, and the 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine ratio was 79:21.
[0111] To this mixture was added 0.9 eq additional resorcinol, and the mixture was heated to 80° C. for 1 h. HPLC analysis of the reaction showed 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, with a 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(xylyl)-1,3,5-triazine ratio of 77:23, and about 2% unreacted bisaryl-chloro-triazine.
Example 17
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,35-triazine using 0.2 eq resorcinol and 2.5 eq AlCl 3 in a dichlorobenzene solvent
[0112] A. No Cooling during Exotherm
[0113] Cyanuric chloride was allowed to react with 2 eq m-xylene, in the presence of 2.5 eq AlCl 3 and 0.2 eq of resorcinol, in ortho-dichlorobenzene at 40° C. A 4° C. exotherm was observed after 4-5 h. HPLC analysis of the reaction at this point showed 96% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 78:22 ratio.
[0114] B. With Cooling to 10° C. after 4 h
[0115] The reaction of part (A) was repeated. The exotherm began after 4 h. A sample was immediately taken, and the reaction was cooled to 10° C. HPLC analysis of the sample showed 96% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 78:22 ratio. There was also some unreacted 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine at this point. After 1 h at 10° C., the cyanuric chloride conversion was 97%, no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected, and the ratio of 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 83:17.
Example 18
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 3 eq AlCl 3 with 6.5% concentrated HCl
[0116] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 and 0.2 eq of resorcinol in chlorobenzene, was added 6.5% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. An immediate reaction with AlCl 3 was observed, leading to its almost complete solvation of AlCl 3 . 1.9 eq of m-xylene was then added. Within 5 min the color changed from light yellow to dark yellow to orange and finally dark red. The cooling bath was removed and the reaction mixture was analyzed at this stage by HPLC. The HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 92:8 ratio. Thereafter, the reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently, heated between 85°-90° C. for 1 h. HPLC analysis of the reaction mixture showed 85.3% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12.8% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 17% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 19
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with 6.5% concentrated HCl
[0117] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 6.5% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. Within 1.5 h, the HPLC analysis showed almost complete conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a ratio of 91:9. Thereafter; the reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated at 85° C. for 1 h. HPLC analysis showed the formation of 83.3% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14.9% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1.7% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. No trisresorcinol-triazine or bisresorcinol-triazine products were detected.
Example 20
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with 13% concentrated HCl
[0118] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 , and 1.9 eq of m-xylene in chlorobenzene, was added 13% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. Within 30 min at room temperature, 97% of the cyanuric chloride had reacted, to produce 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 96:4; no side products were detected. Further stirring gave 99.5% cyanuric chloride conversion, with the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine unchanged and no other products were detected. Thereafter, the reaction mixture was allowed to react with 11.1 eq of resorcinol at 85° C. for 1.5 h. HPLC analysis of the reaction mixture showed the formation of 92.7% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2.3% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
[0119] The product was isolated by treating the reaction mixture with cold 2% aqueous HCl. Precipitate was collected by filtration, washed with water, and dried to give 92% yield of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The actual yield should be even higher than 92%, since some of the product was lost during the sampling for a number of HPLC analyses done during the course of the reaction HPLC analysis of the isolated crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine showed 92.4% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.35% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.25% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 21
Synthesis of 2-chloro-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with 13% concentrated HCl
[0120] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 1.3% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature After addition of 1.9 eq of m-xylene and the reaction of cyanuric chloride with m-xylene was complete, as indicated by the absence of m-xylene, by HPLC analysis, the reaction mixture was quenched with ice-cold 2% aqueous HCl at about 5° C. The reaction mixture was then extracted with methylene chloride. The organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent removed under reduced pressure to give a white solid (quantitative yield based on m-xylene, and 95% yield based on cyanuric chloride) HPLC analysis indicated the isolated white solid to consist of >96% pure 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 22
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl 3 with 13% concentrated HCl
[0121] To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl 3 in chlorobenzene, was added 13% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature HPLC analysis after 1 h at room temperature showed 89% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 82:18. The reaction mixture was left stirring at room temperature overnight after which the complete conversion of cyanuric chloride was detected. The next sample analyzed by HPLC after 22 h at room temperature showed 94% cyanuric chloride conversion, and the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl) 1,3,5-triazine to be 4:3:57.
Example 23
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl 3 with 6.5% concentrated HCl
[0122] To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl 3 in chlorobenzene, was added 6.5% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. After 22 h at room temperature, 98% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 9:10. The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85° C. for, 1.5 h. HPLC analysis of the reaction mixture showed 85.4% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 11.4% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.6% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 24
Synthesis of 2-chloro-4,6-bistetralin-1,3,5-triazine
[0123] To a stirring mixture of 1 eq of cyanuric chloride (5 g, 0.027 mol) in chlorobenzene, maintained at ice bath temperature under nitrogen, was added 3 eq of AlCl 3 (10.87 g, 0.081 mol) over 5-10 min, followed by the addition of conc. HCl (0.54 mL, 0.0065 mol) over 5-10 min, taking care that the reaction temperature did not exceed 5° C. The reaction slurry was stirred at 0-5° C. for another 10 min. The reaction was cooled to −10° C. and tetralin (7.01 mL, 0.0516 mol) was added at −10° C. over 2 h. At the completion of the tetralin addition, the reaction mixture was stirred at −10° C. for 2 h. The reaction was warmed to 0° C. and stirred for 1 h HPLC analysis of the reaction mixture showed 98.5% conversion of cyanuric chloride to 2-chloro-4,6-bistetralin-1,3,5-triazine and 2,4,6-tristetralin-1,3,5-triazine in a 92:8 ratio. The slurry was warmed to 40° C. and resorcinol (3.29 g, 0.0298 mol) was added and the reaction mixture was stirred at 80° C. for 2 h. HPLC analysis showed 100% conversion of 2-chloro-4,6-bistetralin-1,3,5-triazine to 2-(2,4-dihydroxyphenyl)-4,6-bistetralin-1,3,5-triazine.
Comparative Example 24
Synthesis of 2-chloro-4,6-bistetralin-1,3,5-triazine
[0124] To a stirring mixture of 1 eq of cyanuric chloride (5 g, 0.027 mol) in chlorobenzene (50 mL), maintained at ice bath temperature under nitrogen, was added 3 eq of AlCl 3 (10.87 g, 0.081 mol) over 5-10 min. The reaction slurry was stirred at 0-5° C. for another 10 min. The reaction was cooled to −10° C. and tetralin (7.01 mL, 0.0516 mol) was added at −10° C. over 2 h. At the completion of the tetralin addition, the reaction mixture was stirred at −10° C. for 2 h. The reaction was warmed to 0° C. and stirred for 1 h. HPLC analysis of the reaction mixture showed no reaction of cyanuric chloride, and no formation of 2-chloro-4,6-bistetralin-1,3,5-triazine.
Example 25
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with concentrated sulfuric acid
[0125] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of concentrated H 2 SO 4 at ice-bath temperature. After 5 min of stirring 2 eq of m-xylene was added. After another 5 min, the cooling bath was removed and the reaction mixture was stirred at room temperature WIC analysis after 2 h at room temperature showed 100% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 86:14.
Example 26
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.5 eq AlCl 3 with 10% aqueous sulfuric acid
[0126] To a stirring mixture of 1 eq of cyanuric chloride, 3.5 eq of AlCl 3 in chlorobenzene, was added 0.036 eq of sulfuric acid as a 10% aq. solution at ice-bath temperature. After 10 min of stirring 1.9 eq of m-xylene was added. After 5 min at ice bath temperature the reaction mixture was allowed to warm to 10° C. After 1 h 20 min HPLC analysis showed 89% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 89:11 HPLC analysis, after 3 h at 9-11° C., showed 94% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 95:5. HPLC analysis, after 5 h at 9-11° C. and 17 h at room temperature, showed 98.5% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 97:3.
[0127] The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85° C. for 3 h. HPLC analysis of the reaction mixture showed 92.7% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 4% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.4% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.9% 2,4,6-(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 27
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with benzoic acid
[0128] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of benzoic acid as a 4% solution in chlorobenzene at ice-bath temperature. m-Xylene (1.95 eq) was then added. After 5 min at ice bath temperature, the reaction was allowed to warm to room temperature. HPLC analysis after 22 h at room temperature, showed 99.5% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 82:18.
Example 28
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 and 6.5% concentrated HCl
[0129] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of concentrated HCl at ice-bath temperature. After 45 min, 0.95 eq of m-xylene and 0.95 eq of toluene were added. After 45 min at ice bath temperature the reaction was stirred at 9° C. for 1 h and then at room temperature for 2 h. HPLC analysis showed 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product with lesser amounts of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine, and 2-chloro-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine.
[0130] The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85° C. for 2 h HPLC analysis of the reaction mixture showed 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product with lesser amounts of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine.
Example 29
Synthesis of 2-(2,4-dimethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with concentrated HCl
[0131] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of concentrated HCl at ice-bath temperature. After 10 min, 1.9 eq of m-xylene was added. The reaction was stirred at ice bath temperature for 2 h and then at room temperature for 5 h. HPLC analysis showed formation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 91:9 ratio. The reaction mixture was allowed to react with 1.9 eq of 1,3-dimethoxybenzene. The mixture was heated to 59-61° C. and stirred for 2 h, then heated 85° C. and stirred for 5 h. HPLC analysis of the reaction mixture showed 76% 2-(2,4-dimethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 24% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (HPLC area percent at 290 nm) as the only products.
Example 30
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl 3 , and 0.12 eq anhydrous HCl
[0132] To a mixture of cyanuric chloride in chlorobenzene cooled to 5° C. was added 2.5 eq of AlCl 3 , 0.12 eq of anhydrous HCl (as a 0.28 N solution in chlorobenzene), and 1.9 eq of m-xylene. This mixture was warmed to 23° C. with stirring, and the progress of the reaction as monitored by HPLC. The data are given in Table I below.
TABLE I Reaction Profile for Anhydrous HCl Cyanuric Bis-xylyl- Time chloride Mono-xylyl-Bis- monochloro- Tris-xylyl- (h) Conversion (%) chloro-Triazine triazine Triazine 1 3 100 2 6 100 3 9 100 25 65 58 40 2
[0133] The cyanuric chloride conversion is based on area percent at 210 nm. The amounts of the other components are based on area percent at 290 nm.
Example 31
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-tetrazine using 3 eq AlCl 3 and 0.2 eq anhydrous HCl
[0134] To a mixture of cyanuric chloride in chlorobenzene cooled to 5° C. was added 3 eq of AlCl 3 , 0.2 eq of anhydrous HCl (as a 0.156 N solution in chlorobenzene), and 1.9 eq of m-xylene. This mixture was then warmed to 23° C. with stirring and the progress of the reaction was monitored by HPLC The data are given in Table II below.
TABLE II Reaction Profile for Anhydrous HCl (0.20 eq) Cyanuric Bisxylyl- Chloride Monoxylyl- Bis-xylyl- Tris- monochloro: Time Conversion bischloro- monochloro- xylyl- Tris- (h) (%) triazine triazine triazine xylyl* 1 2 100 2.5 6 100 4 15 97 3 5.5 19 97 3 23 59 89 10 1 94:6 48 88 0.5 65.5 34 78:22 *corrected ratio.
Example 32
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.2 eq resorcinol and 3 eq AlCl 3 with 0.55 eq H 2 O
[0135] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 and 0.2 eq of resorcinol in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. An immediate reaction with AlCl 3 was observed. After. 10 min of stirring, 1.9 eq of m-xylene was added. After another 10 min, the cooling bath was removed and the reaction mixture was stirred at room temperature. HPLC analysis of the reaction mixture after 1.5 h at room temperature showed 84% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a 95:5 ratio respectively. After 2.5 h at room temperature HPLC analysis showed 95% conversion of cyanuric chloride, and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 94:6. Thereafter, 1 eq of resorcinol was added and the reaction mixture was stirred at 85° C. for 1 h. HPLC analysis of the reaction mixture showed 89.4% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 7.7% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 1.3% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 33
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis 2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 with 0.55 eq water
[0136] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. After 10 min 1.9 eq of m-xylene was added. HPLC analysis after 30 min at room temperature showed 9:3% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 94:6 respectively. After 1 h at room temperature HPLC analysis showed 98% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 92:8 After 4.5 h at room temperature, HPLC analysis showed conversion of cyanuric chloride had increased to 99%, and the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 93:7.
[0137] Thereafter, 1.1 eq of resorcinol was added and the mixture stirred at 85° C. for 2 h HPLC analysis of the reaction mixture showed 91.1% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 6.3% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.8% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.75% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 34
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 2.5 eq AlCl 3 with 0.55 eq water
[0138] To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl 3 in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. Analysis by HPLC, after 30 min at room temperature, showed 92% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 94:6. After 1 h at room temperature, HPLC analysis of the reaction mixture showed 96% conversion of cyanuric chloride, and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 88:12. After 4.5 h at room temperature, HPLC analysis showed 97% conversion of cyanuric chloride and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 77:23.
Example 35
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 23.25 eq AlCl 3 with 0.55 eq water
[0139] To a stirring mixture of 1 eq of cyanuric chloride, 3.25 eq of AlCl 3 in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. After 10 min 1.9 eq of m-xylene was added. Within 1 h, 98% conversion of cyanuric chloride was detected, based on HPLC analysis. The ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 92:8. A final sample analysis after complete disappearance of m-xylene showed 99% cyanuric chloride conversion, and the ratio of the products, 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, was 89:11.
Example 36
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3 eq AlCl 3 without promoter
[0140] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene was added. After 10 min 1.9 eq of m-xylene was added HPLC analysis after 2 h showed 5% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After 24 h at room temperature HPLC analysis showed 46% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in a 96:4.
Example 37
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.25 eq AlCl 3 without promoter
[0141] The cyanuric chloride was allowed to react with 2 eq of m-xylene in the presence of 3.25 eq of AlCl 3 in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h HPLC analysis. After 4 h, showed about 15% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 h at room temperature, HPLC analysis showed about 51% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 91:9 ratio.
Example 38
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.5 eq AlCl 3 without promoter
[0142] The cyanuric chloride was allowed to react with 2 eq of m-xylene in the presence of 3.5 eq of AlCl 3 in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h HPLC analysis. After 4 h, showed about 6% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 h at room temperature, HPLC analysis showed about 38% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 96:4 ratio.
Example 39
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with dichloromethane and 2.5 eq AlCl 3
[0143] To a stifling mixture of 1 eq of cyanuric chloride 0.4 eq of dichloromethane in chlorobenzene was added 2.5 eq of aluminum chloride at ice-bath temperature, the cooling bath was removed and the reaction mixture stirred at room temperature. The HPLC analysis after 3 h at room temperature showed 14% of cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine formed in a ratio of 93:7 After about 14 h at room temperature, HPLC analysis showed 98.5% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 87:13.
[0144] To the above reaction mixture, 1 eq of resorcinol was added and the mixture stirred at 80-85° C. for 1.1 h. HPLC analysis of the reaction mixture showed 76% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 14% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.
Example 40
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with dichloromethane, resorcinol and 2.5 eq aluminum chloride
[0145] To a stirring mixture of 1 eq of cyanuric chloride, 0.4 eq of dichloromethane, and 0.2 eq of resorcinol in chlorobenzene, was added 2.5 eq of aluminum chloride at ice-bath temperature, the cooling bath was removed and the reaction mixture stirred at room temperature. After 15 min, 10.9 eq of m-xylene was added and after 15 min of stirring at ice-bath temperature, the cooling bath was removed and the reaction mixture stirred at room temperature. HPLC, analysis after 3 h at room temperature showed 95% of cyanuric chloride conversion to 2-chloro-4,6 bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine formed in a ratio of 92:8.
[0146] To the above reaction mixture, 1 eq of resorcinol was added and the mixture stirred at 80-85° C. for 1.5 h. HPLC analysis of the reaction mixture showed 80.5% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 9.9% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.
Example 41
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 2.3 eq of tert-butyl chloride and 2.5 eq aluminum chloride
[0147] To a stirring mixture of 1 eq of cyanuric chloride and 2.5 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 2.3 eq of tert-butyl chloride over 1 h. After 5 min of stilling, 1.95 eq of m-xylene was added over 5 min. The ice bath was replaced with a water bath, and the reaction mixture was allowed to warmed to room temperature. After 5 min at room temperature, HPLC analysis showed 97% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)1,3,5-triazine, present in a ratio of 98:2,
[0148] To the above reaction mixture was added 1.11 eq of resorcinol, and the mixture stirred at 80° C. for 3 h HPLC analysis of the reaction mixture showed 94% of 2-(2,4-dihydroxyphenyl)-4,6 bis(2,4-dimethylphenyl)-1,3-triazine, 3.5% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.5% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 42
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 0.46 eq of tert-butyl chloride with 2.5 eq aluminum chloride
[0149] To a stirring mixture of 1 eq of cyanuric chloride and 2.5 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.46 eq of tert-butyl chloride over 10 min. After 5 min. of stirring, 10.95 eq of m-xylene was added over 5 min. After 5 min, the ice bath was replaced with a water bath, and the reaction mixture warmed to room temperature After stirring at room temperature for 22 h, HPLC analysis showed 98% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris (2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 84:16.
Example 43
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 0.5 eq tert-butylchloride 0.2 resorcinol and 2.5 eq aluminum chloride
[0150] To a stirring mixture of 1 eq of cyanuric chloride 0.2 eq of resorcinol, and 2.5 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.5 eq of tert-butyl chloride over 10 min. After 5 min. of stirring, 1.95 eq of m-xylene was added. The ice bath was replaced with a water bath, and the reaction mixture was allowed to warm to room temperature. After stirring at room temperature for 2 h, HPLC analysis showed 97% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 91:9.
[0151] To the above reaction mixture was added 1 eq of resorcinol, and the mixture stirred at 78-82° C. for 3 h. HPLC analysis of the reaction mixture showed 86% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 44
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using sodium hydroxide and 3 eq of aluminum chloride
[0152] To a stirring mixture of 3.7 g (1 eq) of cyanuric chloride, 8 g (3 eq) of aluminum chloride in 50 mL chlorobenzene, was added 0.4 mL of aqueous sodium hydroxide solution (50%) at ice-bath temperature. After 10 min of stirring, 19 eq of m-xylene was added. The cooling bath was removed and the reaction mixture stirred at room temperature HPLC analysis after 30 min at room temperature showed 91% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 96:4 A second sample analyzed after 1 h at room temperature showed 94% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 92:8. After a total of 4 h at room temperature, HPLC analysis showed 95% conversion of cyanuric chloride and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 89:11.
[0153] To the above reaction mixture, 1.1 eq of resorcinol was added and the mixture heated with stirring at 80° C. for 2 h. HPLC analysis of the reaction mixture showed 80% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 16% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.5% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2.2% of 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.
Example 45
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using aluminum hydroxide with 3 eq aluminum chloride
[0154] To a stirring mixture of 3.7 g (1 eq) of cyanuric chloride, 8 g (3 eq) of aluminum chloride in 50 mL chlorobenzene was added 0.39 g (0.5 eq) of aluminum hydroxide at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. The cooling bath was removed after 10 min and the reaction mixture stirred at room temperature. HPLC analysis after 20 h at room temperature showed 98% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 80:20.
[0155] To the above reaction mixture, 1.1 eq of resorcinol was added and the mixture heated with stirring at 80° C. for 2 h. HPLC analysis of the reaction mixture showed 74% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 22% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.5% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1.4% of 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.
Example 46
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using aq. ammonium hydroxide with 3 eq aluminum chloride
[0156] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.38 eq of aq. ammonium hydroxide over 15 min. After 15 min. of stirring, 1.95 eq of m-xylene was added. The ice bath was replaced with a water bath, and the reaction mixture was allowed to warm to room temperature. After 4 h at room temperature, HPLC analysis showed 97% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 89:11. After an additional 1 h at room temperature, the cyanuric chloride conversion was >99%% and the 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine ratio was at 89:11.
[0157] To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 78-82° C. for 3 h. HPLC analysis of the reaction mixture showed 84% of 2-(2,4-dihydroxylphenyl)-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, 12% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 47
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using sodium methoxide and 3 eq aluminum chloride
[0158] To a stirring mixture of 3 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.5 eq of sodium methoxide over 15 min. The reaction mixture was warmed to room temperature for 0.5 h and then cooled back to ice bath temperature. To the reaction mixture was added 1 eq of cyanuric chloride and 1.95 eq of m-xylene. The ice bach was replaced with a water bath, and the reaction mixture warmed to room temperature. After 7.5 h at room temperature, HPLC analysis showed 98% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 75:25.
[0159] To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 85° C. for 4 h. HPLC analysis of the reaction mixture showed 80% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 18% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine and 2% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 48
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using α-methylstyrene with 3 eq aluminum chloride
[0160] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminum chloride in chlorobenzene was added 0.5 eq of α-methylstyrene at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. After another 10 min, the cooling bath was removed and the reaction mixture was stirred at room temperature HPLC analysis after 16 h at room temperature showed 96% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl) 1,3,5-triazine (tris-xylyl triazine), formed in a ratio of 73:27.
Example 49
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 3 eq aluminum chloride without promoter
[0161] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminum chloride in chlorobenzene was added at ice-bath temperature. After addition of m-xylene, the reaction mixture was allowed to stir at room temperature for a total of 24 h. HPLC analysis of the reaction mixture showed about 46% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 96:4.
Example 50
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with butyryl chloride and 3 eq aluminum chloride
[0162] To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminum chloride in chlorobenzene was added 0.5 eq of butyryl chloride at ice-bath temperature. After 10 min of stirring, 10.9 eq of m-xylene was added. After another 10 min, the cooling bath was removed and the reaction mixture was stirred at room temperature. HPLC analysis after 16 h at room temperature showed 92% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 78:22.
Example 51
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using pyridine hydrochloride with 3.5 eq of aluminum chloride
[0163] To a stirring mixture of 1 eq of cyanuric chloride and 3.5 eq of aluminum chloride in chlorobenzene was added 0.5 eq of pyridine hydrochloride at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. The reaction mixture was stirred for 1 h at ice bath temperature, 3.5 h at 10° C., and 6.5 h at 15-20° C. HPLC analysis showed 98% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 88:12.
[0164] To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 85° C. for 3 h. HPLC analysis of the reaction mixture showed 86% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 13% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 52
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 3.5 eq aluminum chloride
[0165] To a stirring mixture of 1 eq of cyanuric chloride and 3.5 eq of aluminum chloride in chlorobenzene, after 10 min of stirring, 1.9 eq of m-xylene was added. HPLC analysis after 4 h at room temperature showed 6% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine with no formation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The reaction mixture was stirred at room temperature for 24 h. HPLC analysis showed about 38% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, in a 96:4 ratio.
Example 53
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using benzyltriethylammonium chloride and resorcinol and 2.5 eq aluminum chloride
[0166] To a stirring mixture of 1 eq of cyanuric chloride, 0.2 eq benzyltriethylammonium chloride, and 0.2 eq of resorcinol in chlorobenzene was added 2.5 eq of aluminum chloride at ice-bath temperature. After 10 min of stirring, 10.9 eq of m-xylene was added. The reaction mixture was stirred for 1 hour at ice bath temperature, and 3 h at 18-20° C. HPLC analysis showed 72% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 86:14.
Example 54
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using lithium chloride with 3 eq of aluminum chloride
[0167] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene was added 0.5 eq of lithium chloride at ice-bath temperature. After 10 min. of stirring, 1.9 eq of m-xylene was added. The reaction mixture was allowed to stir at room temperature. HPLC analysis of the reaction mixture after 44 h of stirring at room temperature showed 97% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 81:19.
[0168] To the above reaction mixture, 10.1 eq of resorcinol was added and the mixture stirred at 70° C. for 3 hours. HPLC analysis of the reaction mixture showed 76% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 20% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2% of 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.
Example 55
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0169] Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.50 eq of allyl bromide as promoter
[0170] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.5 eq of allyl bromide over 20 min. An immediate reaction with aluminum chloride was observed during the addition. After 10 min at 0-1° C., 1.9 eq of m-xylene was added over 5 nm. After 30 min at 0-1° C., the ice bath was replaced with a cold-water bath, and the reaction mixture was stirred at 17-19° C. for 25.5 h HPLC analysis showed 95% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ration of 86:14. A small amount of by-product was detected, probably arising from the reaction of 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine (CDMPT) with allyl bromide, was observed. If this product is counted along with CDMPT itself, the bis-xylyl-mono-chloro-triazine to tris-xylyl-triazine ratio increases to 89:11.
[0171] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0172] To the above reaction mixture was added 1:1 eq resorcinol and the mixture was stirred at 85° C. for 17 h. HPLC analysis of the reaction mixture showed 87% 2 -(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 1.3% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.
Example 56
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0173] Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; using 0.4 eq. of 3-methyl-2-buten-1-ol as promoter
[0174] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at −13° C. to −15° C. was added 0.4 eq of 3-methyl-2-buten-1-ol over 15 min. An immediate reaction with aluminum chloride was observed during the addition. The mixture was allowed to warm to 0-1° C. and after stirring for 10 min, 1.9 eq of m-xylene was added over 10 min. After stirring for 2 h at 0-1° C., the ice bath was replaced with a cold-water bath and the reaction mixture was stirred at 15-16° C. for 18 h. HPLC analysis showed 94% of cyanuric chloride conversion to 2-chloro-4,6,-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 86:14.
[0175] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0176] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was stirred at 85° C. for 2 h. HPLC analysis of the reaction mixture showed 84% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 57
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0177] Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.5 eq of benzoyl chloride as promoter
[0178] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 1-2° C. was added 0.5 eq of benzoyl chloride over 10 min. After stilling for 10 min, 1.9 eq of m-xylene was added over 6 min. After stirring for 2 h at 0-1° C., the ice bath was replaced with a cold water bath and the reaction mixture was allowed to warm to 15-16° C. and stirred for 19 h. HPLC analysis showed 84% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 86:14.
[0179] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0180] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was stirred at 85° C. for 2 h. HPLC analysis of the reaction mixture showed 80% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 20% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.
Example 58
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0-5 eq of propanesulfonyl chloride as promoter
[0181] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 0-1° C. was added 0.5 eq of propanesulfonyl chloride over 10 min. An immediate reaction with aluminum chloride was observed during the addition. After stirring for 10 min at 1-2° C., 1.9 eq of m-xylene was added over 6 min. After stirring for 2 h at 0-2° C., the ice bath was replaced with a cold water bath, the reaction was allowed to warm to 16-18° C. and was stirred for 20 h. HPLC analysis showed 92% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 90:10.
Example 59
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using 0.5 eq of p-toluenesulfonyl chloride as promoter
[0182] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 0-2° C. was added 0.5 eq of p-toluenensulfonyl chloride over 10 min. After stirring for 10 min, 1.9 eq of m-xylene was added over 6 min. After stirring at 0-1° C., the ice bath was replaced with a cold water bath, the reaction mixture was allowed to warm to 16-17° C. and was stirred for 21 h. The water bath was removed and the temperature was allowed to warm to 23° C. HPLC analysis showed the conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 79:21.
Example 60
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine using 0.5 eq of acetic anhydride as promoter
[0183] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 1-2° C. was added a solution of 0.5 eq of acetic anhydride in chlorobenzene over 10 mm. An immediate reaction with aluminum chloride (exotherm) was observed during addition. After stirring for 10 min, 1.9 eq of m-xylene was added over 6 min. After stirring at 0-1° C. for 2 h, the ice bath was replaced with a cold water bath, the reaction mixture was allowed to warm to 16° C. and was stirred for 19 h. HPLC analysis showed the complete conversion of m-xylene, but only 72% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 84:16.
Example 61
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine
[0184] Part A: Preparation of 2-chloro-4,6-bisphenyl-1,3,5-triazine using concentrated HCl as a Reaction Promoter
[0185] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 1.95 eq of benzene was added and the reaction mixture stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction was allowed to warm to room temperature, and stirred. After 26 h at room temperature, an HPLC analysis indicated about 86% cyanuric chloride conversion to 2-chloro-2,6-bisphenyl-1,3,5-triazine. The stirring was continued for 24 h at room temperature. The HPLC analysis showed the cyanuric chloride conversion to 92% with >96% being 2-chloro-4,6-bisphenyl-1,3,5-triazine and less than 2% of 2,4,6-trisphenyl-1,3,5-triazine. The result was confirmed by LCMS
[0186] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine
[0187] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. Within 2 A, HPLC analysis indicated about 80% of 2-chloro-4,6-bisphenyl-1,3,5-triazine conversion to 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine
Comparative Example 61
Preparation of 2-chloro-4,6-bisphenyl-1,3,5-triazine without concentrated HCl
[0188] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.95 eq of benzene and the reaction mixture was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. After about 26 h, an HPLC analysis indicated almost no cyanuric chloride conversion and no presence of 2-chloro-4,6-bisphenyl-1,3,5-triazine. The stirring was continued for an additional 24 h at room temperature. An HPLC analysis showed almost no cyanuric chloride conversion and no 2-chloro-4,6-bisphenyl-1,3,5-triazine.
Example 62
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine
[0189] Part A: Preparation of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine using concentrated HCl
[0190] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 11 minutes, 1.9 eq of toluene was added and the reaction mixture was stirred at ice bath temperature for 30 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred for 21 h. HPLC analysis indicated about 95% cyanuric chloride conversion to 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine and the isomer 2-chloro-4-(4-methylphenyl)-6-(2-methylphenyl)-1,3,5-triazine
[0191] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine
[0192] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. Within 3 h, an HPLC analysis indicated 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine had converted to 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-,1,3,5-triazine. HPLC analysis of the crude product showed 78% of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 11% of the isomer with probable structure of 2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2-methylphenyl)-1,3,5-triazine
Comparative Example 62
Preparation of 2-chloro-4,6 bis(4-methylphenyl-1,3,5-triazine without concentrated HCl
[0193] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.9 eq of toluene and the reaction mixture was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature. After about 2 h, an HPLC analysis indicated no reaction of cyanuric chloride. The stirring was continued for about 20 h at room temperature. HPLC analysis showed almost no reaction of cyanuric chloride and the absence of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine
Example 63
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine
[0194] Part A: Preparation of 2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine using concentrated HCl
[0195] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 30 minutes, the reaction was further cooled to about −5° C. and 1.9 eq of xylene was added. The reaction mixture was stirred at about 0° C. for 2 h, and then at room temperature for 4 h. HPLC analysis indicated >95% cyanuric chloride conversion to 82% 2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and 6% of its isomer.
[0196] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine
[0197] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. Within 2 h, an HPLC analysis indicated 2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and its isomer had completely reacted to form 8:3% of 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and 6% of its isomer.
Comparative Example 63
Preparation of 2-chloro-4,6-bis(3,4-methylphenyl)-1,3,5-triazine without concentrated HCl
[0198] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.9 eq of o-xylene and the reaction mixture was stirred at ice bath temperature for 1 h. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature. After about 2 h, an HPLC analysis indicated no reaction of cyanuric chloride. The stirring was continued for about 20 h at room temperature. HPLC analysis showed no significant conversion of cyanuric chloride and the absence of 2-chloro-4,6-bis(3,4-methylphenyl)-1,3,5-triazine
Example 64
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine
[0199] Part A: Preparation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine using concentrated HCl
[0200] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 2 eq of biphenyl was added and the reaction was stirred at ice bath temperature for 1 h. HPLC analysis indicated 88% cyanuric chloride conversion to 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine as the major product. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. HPLC analysis after 3 h at room temperature indicated about 93% cyanuric chloride to 2-chloro-4,6-bis(4-biphenyl) as the major product and confirmed by MS.
[0201] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis 4-biphenyl)-1,3,5-triazine
[0202] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 85° C. for 2 h. HPLC and MS analysis indicated the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine.
Comparative Example 64: Preparation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine without concentrated HCl
[0203] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 2 eq of biphenyl and the reaction mixture was stirred at ice bath temperature for 1 h. HPLC analysis indicated almost no cyanuric chloride conversion and the absence of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine. The cooing bath was removed and the reaction mixture was allowed to warm to room temperature. After about 3 h, an HPLC analysis indicated no reaction of cyanuric chloride and no formation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine.
Example 65
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
[0204] Part A: Preparation of 2-chloro-4,6-bis(4-tert-butylphenyl)- 1 , 3 , 5 -triazine using concentrated HCl
[0205] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 1.95 eq of tert-butylbenzene was added and the reaction was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. After 2 h, HPLC analysis indicated 62% cyanuric chloride conversion to 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product (>78%). The reaction mixture was stirred at room temperature for an additional 24 h HPLC analysis showed 83% cyanuric chloride conversion to 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product (>72%), with the isomer.
[0206] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
[0207] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. for 2 h. HPLC analysis indicated 63% formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine.
Comparative Example 65
Preparation of 2-chloro-4,6-bis-4-tert-butylphenyl)-1,3,5-triazine without concentrated HCl
[0208] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.95 eq of tert-butylbenzene. The reaction mixture was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. After about 2 h, an HPLC analysis indicated no reaction of cyanuric chloride and no 2-chloro-4,6-(4-tert-butylphenyl)-1,3,5-triazine formation. The stirring was continued for about 24 h at room temperature. HPLC analysis showed no 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine formation.
Example 66
Preparation of 2-(2,4-dihydroxy-5-hexylphenyl-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
[0209] Part A: Preparation of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine using concentrated HCl
[0210] 2-Chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine was prepared essentially following the procedure described in example 67.
[0211] Part B: Preparation of 2-[2,4-dihydroxy]-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
[0212] To the above reaction mixture was added 1.1 eq of 4-hexylresorcinol and the mixture was heated to 80° C. for 3 h. HPLC analysis indicated conversion of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine to 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product
Example 67
Preparation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0213] Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0214] 2-Chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine was prepared by allowing to react 1 eq of cyanuric chloride with 1.9 eq of m-xylene in the presence of 3 eq of aluminum chloride and concentrated HCl in chlorobenzene as discussed above.
[0215] Part B: Preparation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0216] To the above reaction mixture was added 11 eq of resorcinol monooctyl ether and the mixture was stirred at room temperature for about 20 h. ILC analysis indicated formation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product by a direct comparison with a commercial sample of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Example 68
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0217] Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethyl)-1,3,5-triazine; Simultaneous addition of cyanuric chloride and m-xylene to reaction facilitator prepared from aluminum chloride and concentrated HCl
[0218] To a stirring mixture of 3 eq. of aluminum chloride in chlorobenzene at 0° C. to 5° C. was added concentrated HCl (6 wt % based on aluminum chloride), and the reaction mixture was stirred for 10 minutes to form the reaction facilitator. To the mixture was added a solution of 1 eq of cyanuric chloride and 1.9 eq of m-xylene in chlorobenzene at 0° C. to 5° C. and the reaction was stirred for 10 minutes. HPLC analysis indicated 95% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (99%). The reaction mixture was allowed to stir at 0° C. to 5° C. for 2 b. HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,5,3-triazine (98%).
[0000] Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0219] To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. for 2 h. HPLC analysis indicated 95% of 2-(2,4-dihyroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 69
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine in benzene as solvent and concentrated HCl
[0220] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in benzene at 7° C. was added concentrated HCl (13% wt based on cyanuric chloride), and the mixture was stirred for 10 minutes. To the reaction mixture was added 1.9 eq of m-xylene and the reaction mixture was stirred at 0° C. for 30-35 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred for 3 b. HPLC analysis indicated >97% cyanuric chloride conversion to 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine (85%).
Example 70
Preparation of 2-(2,4-dihydroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0221] Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine complex with reaction facilitator prepared from aluminum chloride and concentrated HCl
[0222] To a stirring mixture of 1 eq of isolated 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 3 eq of aluminum chloride in o-dichlorobenzene was added concentrated HCl (5.9 wt % based on aluminum chloride). After stirring for about 5-6 h at room temperature, the reaction turned orange-red, indicative of a new complex formed between the reaction facilitator, consisting of aluminum chloride and concentrated HCl, and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
[0223] Part B. Preparation of 2-(2,4-dihydroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
[0224] The above complex mixture was heated to about 60° C. To the mixture was added 1 eq of orcinol (5-methylresorcinol), and the reaction mixture was heated to 80° C. to 85° C. for 8 h. HPLC analysis indicated almost complete conversion of 2-chloro-4,6-bis(2,4-, dimethylphenyl)-1,3,5-triazine leading to the formation of 2-(2,4-dihyroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine.
Comparative Example 70
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine complex with aluminum chloride without concentrated HCl
[0225] A mixture of 1 eq of isolated 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 3 eq of aluminum chloride in o-dichlorobenzene was stirred at room temperature for about 5-6 h. The reaction mixture turned slightly yellow and was not orange-red as in the preceding example, indicative of a lack of the new complex formation from 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 71
Preparation of reaction facilitator from aluminum chloride and concentrated HCl
[0226] To a stirring mixture of 3 eq of aluminum chloride in o-dichlorobenzene was added concentrated HCl (6 wt % based on aluminum chloride). The reaction mixture was stirred at room temperature. The formation of a new off-white mixture of the reaction facilitator was observed, which did not change its color even after stirring at room temperature for 2 h.
Example 72
Preparation of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) complex with reaction facilitator prepared from aluminum chloride and concentrated HCl
[0227] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene was added concentrated HCl (13 wt % based on cyanuric chloride). The reaction mixture turned brownish-red after 30 minutes of stirring at room temperature. The reaction became dark brown after an additional 1 h of stirring at room temperature. The color of the reaction mixture indicated the formation of a new complex between cyanuric chloride and the reaction facilitator prepared from aluminum chloride and concentrated
Comparative Example 72
Preparation of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) complex with reaction facilitator prepared from aluminum chloride without concentrated HCl
[0228] A mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene was stirred at room temperature for 3 h. No change in color from original off-white was observed, indicating lack of a similar complex formation of cyanuric chloride as in the preceding example, where cyanuric chloride was treated with the reaction facilitator consisting of aluminum chloride and concentrated HCl.
Example 73
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine using Aliquat-336
[0229] To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in benzene at about 0° C. was added Aliquat-336 (tricaprylylmethylammonium chloride) (50 wt % based on aluminum chloride). A reaction with aluminum chloride was observed with temperature increase. The reaction mixture was stirred at room temperature for 30 minutes, leading to the formation of a clear orange-red solution. To the resulting complex of cyanuric chloride with reaction facilitator was added 1.9 eq of m-xylene and the reaction mixture was stirred at room temperature for 1 h. HPLC analysis indicated almost 90% cyanuric chloride conversion to 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine as the major product and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine as the minor product, formed in a ratio of 3:1.
[0230] The invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed, since these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become 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.
|
It has been now surprisingly discovered after extensive research that 2-halo-4,6-bisaryl-1,3,5-triazine can be prepared with unprecedented selectivity, efficiency, mild conditions, and in high yield by the reaction of cyanuric halide with aromatics in the presence of at least one Lewis acid and at least one reaction promoter. This reaction is also unprecedently general as a variety of aromatics can be used to produce a wide selection of 2-halo-4,6-bisaryl-1,3,5-triazines. The novel approach includes the use of the reaction promoters in combination with at least one Lewis acid under certain reaction conditions to promote the formation of 2-halo-4,6-bisaryl-1,3,5-triazine compounds from cyanuric halide. Preferably, the Lewis acids and reaction promoter's are combined to form a complex 2-Halo-4,6-bisaryl-1,3,5-triazines are key intermediates for making 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine class of UV absorbers.
| 2
|
BACKGROUND
[0001] 1. Technical Field
[0002] The present disclosure relates to heat dissipation devices and, more particularly, to a heat dissipation device thermally contacting with a plurality of electronic components having different height, to dissipate heat of the electronic components, simultaneously.
[0003] 2. Description of Related Art
[0004] Generally, a heat dissipation device thermally contacts with electronic components mounted on a printed circuit board (PCB) to dissipate heat of the electronic components. The heat dissipation device comprises a base contacting with the electronic components and a plurality of fins extending upwardly from a top surface of the base. When the electronic components have different heights, the base of the heat dissipation device is not able to tightly contact with all of the electronic components at the same time; as a result, a large heat resistance will exist between the electronic components and the base, which will adversely affect the heat dissipation of the electronic components.
[0005] What is needed, therefore, is a heat dissipation device which can effectively dissipate heat generated by electronic components on a printed circuit board, wherein the electronic components have different heights.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is an assembly view of a heat dissipation device in accordance with an embodiment of the present disclosure and a printed circuit board separated from the heat dissipation device.
[0007] FIG. 2 is an inverted view of the heat dissipation device of FIG. 1 , but a second base of a second heat sink is taken away from the second heat sink for clarity.
[0008] FIG. 3 is a partly exploded view of the heat dissipation device of FIG. 1 , wherein first fins are separated from a first heat sink of the heat dissipation device.
[0009] FIG. 4 is a partly exploded view of the heat dissipation device of FIG. 1 , wherein the first heat sink is separated from a connecting member of the heat dissipation device.
[0010] FIG. 5 is an exploded view of pins and a first base of the first heat sink of FIG. 4 .
[0011] FIG. 6 is a cross-sectional view of the first heat sink, when the first heat sink is assembled to the connecting member.
DETAILED DESCRIPTION
[0012] FIGS. 1-2 illustrate a heat dissipation device in accordance with the present disclosure. The heat dissipation device thermally contacts a first electronic component 200 and a second electronic component 300 mounted on a printed circuit board (PCB) 100 to dissipate heat generated by the first and second electronic components 200 , 300 at the same time. The first electronic component 200 is shorter than the second electronic component 300 . The heat dissipation device comprises a connecting member 10 , a first heat sink 20 and a second heat sink 30 . The first and second heat sinks 20 , 30 are mounted on the connecting member 10 and thermally contact with the first and second electronic components 200 , 300 of the PCB 100 , respectively.
[0013] Referring to FIGS. 3-4 also, the second heat sink 30 comprises a second base 31 , a number of second pins 32 , a heat pipe 35 and a number of second fins 33 . The second base 31 thermally contacts with the second electronic component 300 and is located at a bottom side of the connecting member 10 . The second pins 32 are secured on the second base 31 and extend through second through holes 13 of the connecting member 10 . The second fins 33 each have a T-shaped configuration and are parallel to and spaced from each other. A number of holes 330 are defined in each of the second fins 33 . The second pins 32 extend through the holes 330 of the second fins 33 and interferentially engage with the second fins 33 . Thus, the second fins 33 are secured on the second pins 32 . The heat pipe 35 is L-shaped and comprises an evaporating section 351 received in a groove 310 of the second base 31 and a condensing section 355 . The heat pipe 35 thermally contacts with the bottom surface of the connecting member 10 on which the second fins 33 are located to transfer heat to the second fins 33 . Two screws 60 extend through the PCB 100 and engage in mounting holes 313 defined two diagonally opposite ends of the second base 31 to mount the second heat sink 30 on the PCB 100 . The bottom surface of the second base 31 intimately and thermally contacts with the second electronic component 300 .
[0014] The connecting member 10 is a metallic plate and has a rectangular configuration. A first end of the connecting member 10 defines an opening 14 to receive a fan (not shown). A second end opposite to the first end defines a number of first through holes 12 . The second through holes 13 are located between the opening 14 and the first through holes 12 . The first and second through holes 12 , 13 are provided for assembly of the first and second heat sinks 20 , 30 to the connecting member 10 . The first through holes 12 are arranged in matrix and located at a corner of the second end. A flange 120 extends upwardly from an edge of the first through hole 12 . The second through holes 13 are located near the opening 14 .
[0015] Referring to FIGS. 5-6 also, the first heat sink 20 comprises a first base 21 , a number of first pins 22 secured on the first base 21 , a number of first fins 23 assembled on the first pins 22 and a number of elastic members 40 enclosing the first pins 22 and sandwiched between the first base 21 and the bottommost first fin 23 . Each of the first base 21 , the first pins 22 and the first fins 23 is made of material having good heat conductivity, such as aluminum or copper. In this embodiment, the elastic member 40 is a helical spring and can be compressed along an axial direction thereof.
[0016] The first base 21 comprises a rectangular bottom plate 211 contacting with the first electronic component 200 and a top cover 215 secured on and covering the bottom plate 211 . A number of columned studs 212 protrude on a top surface of the bottom plate 211 along an edge of the bottom plate 211 . The studs 212 are integrally formed on the bottom plate 211 by punching. Thus, a concave 213 is defined in a bottom surface of the bottom plate 211 corresponding to each of the studs 212 . The top cover 215 is a rectangular plate and defines a number of orifices 218 corresponding to the studs 212 of the bottom plate 211 to receive the studs 212 . A diameter of each orifice 218 is slightly larger than that of each stud 212 . A number of through holes (not labeled) are defied in the top cover 215 . Each through hole has a circular recess 216 defined in a bottom of the top cover 215 and a circular passage 217 defined in a top of the top cover 216 . The recess 216 and a corresponding passage 217 communicate with each other and are coaxial. The recess 216 has a diameter larger than that of the passage 217 . Two sleeves 219 with internal thread extend integrally and downwardly from two diagonally opposite ends of the top cover 215 . When the top cover 215 and the bottom plate 211 are assembled together, the sleeves 219 extend downwardly beyond a bottom face of the bottom plate 211 . Two screws 50 extend through the PCB 100 and engage with the sleeves 219 to fix the first heat sink 20 on the PCB 100 .
[0017] Each of the first pins 22 is columned and comprises a head 28 and a body 29 extending upwardly from a central portion of the head 28 . Understandably the first pin 22 can be square, prism or other shape in alternative embodiments. The head 28 has a diameter larger than that of the body 29 . The first pin 22 has a T-shaped profile in lengthwise cross-section (shown from FIG. 6 ). The head 28 has a height larger than a depth of the recess 216 . The head 28 is received in the recess 216 of the top cover 215 of the first base 21 and beyond the recess 216 . Preferably, the head 28 is 0.05-0.15 mm higher than the recess 21 . The body 29 is slightly smaller than the passage 217 of the top cover 215 . The head 28 is larger than the passage 217 .
[0018] The first fins 23 are parallel to and spaced from each other. A number of holes 230 are defined in the first fins 23 to allow the bodies 29 of the first pins 22 to extend therethrough. The bodies 29 interferantially extend through the holes 230 , thereby securing the first fins 23 on the bodies 29 of the first pins 22 .
[0019] After the second heat sink 30 is assembled on the PCB 100 , the first heat sink 20 is assembled on the PCB 100 too to thermally contact with the first electronic component 200 of the PCB 100 . When the first heat sink is assembled, the bodies 29 of the first pins 22 extend through the passages 217 of the top cover 215 from bottom to top, and top portions of the heads 28 are received in the recesses 216 of the top cover 215 . The bottom plate 211 is pressed upwardly toward the top cover 215 whereby the bottom plate 211 contacts bottom ends of the heads 28 . Each of the heads 28 is pressed to deform and expand to fill a gap between the head 28 and the recess 216 . In this state, a bottom surface of the head 28 is coplanar to the bottom surface of the top cover 215 . Thus, the bottom plate 211 intimately contacts the bottom surface of the top cover 215 and the heads 28 of the first pins 22 . Simultaneously, the studs 22 of the bottom plate 211 are received in the orifices 218 of the top cover 215 . The studs 22 are punched to deform thereby to rivet into the orifices 218 and intimately joint the bottom plate 211 and top cover 215 together. In this state, the first base 21 and the first pins 22 are assembled together. The bodies 29 of the first pins 22 extend through the first holes 12 of the connecting member 10 from bottom to top. The elastic members 40 are positioned around periphery of the flanges 120 of the connecting member 10 and abut against a top surface of the connecting member 10 . The bodies 29 extend through the holes 230 of the first fins 23 and interferentially engaged with the first fins 23 . The elastic members 40 abut against the bottommost first fin 23 . The bottom plate 211 of the first heat sink 20 is arranged on the first electronic component 200 . Two screws 50 extend through the PCB 100 and engage with the sleeves 219 of the bottom plate 211 to fix the first heat sink 20 on the PCB 100 . A distance between the bottom plate 211 and the first electronic component 200 is adjustable by tightening the screws 50 . The elastic members 40 are compressed by the first base 21 and the bottommost fin 23 . Thus, a force afforded by the elastic members 40 pushes the first base 21 and the connecting member 10 toward the first electronic component 200 to make the first base 21 intimately connect with first electronic component 200 .
[0020] It is to be understood, however, that even though numerous characteristics and advantages of the disclosure have been set forth in the foregoing description, together with details of the structure and function of the disclosure, the disclosure is illustrative only, and changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
|
A heat dissipation device is provided for dissipating heat generated by a plurality of electronic components mounted on a printed circuit board and having different heights. The heat dissipation device includes a connecting member and a first base mounted on the connecting member and located at above one of the electronic components. A number of joining members extend through the printed circuit board and engage with the first base to assemble the first base on the one of the electronic components on the printed circuit board. A distance between the first base and the one of the electronic components is adjustable by adjusting the joining members to make the first base intimately contact with the one of the electronic components.
| 7
|
FIELD OF THE INVENTION
[0001] The present invention relates to a technique for adjusting aberration of an optical system.
BACKGROUND OF THE INVENTION
[0002] As described in “T. Yoshihara et al., “Realization of very-small aberration projection lenses”, Proc. SPIE 2000, Vol. 4000-52” and Japanese Patent Laid-Open No. 11-176744, the projection optical system of a semiconductor exposure apparatus is prepared through the first step of measuring optical characteristics, the second step of calculating an adjustment amount for properly correcting various aberrations of the projection optical system on the basis of the measured optical characteristics, and the third step of actually adjusting or processing the projection optical system in accordance with the adjustment amount.
[0003] Most of aberrations to be corrected change in proportion to the adjustment amount of each part. In order to minimize the maximum absolute value of each aberration, the adjustment amount of each part is determined by a method to which linear programming is applied (Japanese Patent Laid-Open No. 2002-367886).
[0004] However, a change in wavefront aberration which is one of important aberrations cannot be expressed as the linear function of the adjustment amount of each part. The method disclosed in Japanese Patent Laid-Open No. 2002-367886 cannot calculate optimal adjustment amounts for various aberrations including the wavefront aberration.
SUMMARY OF THE INVENTION
[0005] The present invention has been made in consideration of the above drawbacks, and an exemplified object thereof is to provide a novel technique concerning aberration adjustment of an optical system.
[0006] According to the first aspect of the present invention, there is provided an optical apparatus including an image forming optical system having a movable optical element, and a driving mechanism which moves the optical element. The apparatus comprises a first block which obtains a linear evaluation value by normalizing, by a first tolerance, an aberration expressed by a linear function of a position of the movable optical element out of aberrations of the optical system, and a quadratic evaluation value by normalizing, by a second tolerance, an aberration expressed by a quadratic function of the position out of the aberrations of the optical system, a second block which obtains a minimum value of a dummy variable by linear programming using an upper limit value of the linear evaluation value as the dummy variable, and a third block which determines a position of the optical element to be moved by the driving mechanism so as to minimize a weighted sum of the quadratic evaluation values with respect to a plurality of image heights by using, as the upper limit value of the linear evaluation value, a value prepared by adding a relaxation amount to the minimum value of the dummy variable that is obtained by the second block. The third block minimizes the weighted sum of the quadratic evaluation values by adjusting the weights assigned to the quadratic evaluation values and the relaxation amount.
[0007] According to the second aspect of the present invention, there is provided an optical apparatus including an optical system having a movable optical element, and a driving mechanism which moves the optical element. The apparatus comprises a first block which obtains a linear evaluation value by normalizing, by a tolerance, an aberration expressed by a linear function of a position of the movable optical element out of aberrations of the optical system, a second block which defines, by a first dummy variable, an upper limit of an absolute value of a Zernike coefficient associated with wavefront aberration of the optical system, and obtains a linear evaluation value that approximates root mean square of the wavefront aberration by a linear function of the first dummy variable, and a third block which defines, by a second dummy variable, an upper limit of the linear evaluation values obtained by the first block and the second block, and determines a position of the optical element to be moved by the driving mechanism so as to minimize the second dummy variable by linear programming.
[0008] According to the third aspect of the present invention, there is provided a method of determining a position of an optical element in an optical apparatus which includes an image forming optical system having the optical element, and a driving mechanism which moves the optical element. The method comprises a first step of obtaining a linear evaluation value by normalizing, by a first tolerance, an aberration expressed by a linear function of a position of the optical element out of aberrations of the optical system, and a quadratic evaluation value by normalizing, by a second tolerance, an aberration expressed by a quadratic function of the position out of the aberrations of the optical system, a second step of obtaining a minimum value of a dummy variable by linear programming using an upper limit value of the linear evaluation values as the dummy variable, and a third step of determining a position of the optical element to be moved by the driving mechanism so as to minimize a weighted sum of the quadratic evaluation values with respect to a plurality of image heights by using, as the upper limit value of the linear evaluation value, a value prepared by adding a relaxation amount to the minimum value of the dummy variable that is obtained in the second step. In the third step, the weighted sum of the quadratic evaluation values is minimized by adjusting the weights assigned to the quadratic evaluation values and the relaxation amount.
[0009] According to the fourth aspect of the present invention, there is provided a method of determining a position of an optical element in an optical apparatus which includes an optical system having the optical element, and a driving mechanism which moves the optical element. The method comprises a first step of obtaining a linear evaluation value by normalizing, by a tolerance, an aberration expressed by a linear function of a position of the optical element out of aberrations of the optical system, a second step of defining, by a first dummy variable, an upper limit of an absolute value of a Zernike coefficient associated with wavefront aberration of the optical system, and obtaining a linear evaluation value which approximates root mean square of the wavefront aberration by a linear function of the first dummy variable, and a third step of defining, by a second dummy variable, an upper limit of the linear evaluation values obtained in the first step and the second step, and determining a position of the optical element to be moved by the driving mechanism so as to minimize the second dummy variable by linear programming.
[0010] According to the preferred embodiment of the present invention, the apparatus can be an exposure apparatus which transfers a pattern to a substrate using the optical system.
[0011] According to the fifth aspect of the present invention, there is provided a device manufacturing method comprising steps of transferring a pattern to a substrate using the above exposure apparatus, and developing the substrate to which the pattern has been transferred.
[0012] According to the sixth aspect of the present invention, there is provided a device manufacturing method comprising steps of moving an optical element in an optical system of an exposure apparatus to a position as determined in accordance with the above method, transferring a pattern to a substrate using the exposure apparatus of which the optical element is moved in the moving step, and developing the substrate to which the pattern has been transferred.
[0013] According to the present invention, a novel technique concerning aberration adjustment of an optical system is provided.
[0014] Other features and advantages of the present invention will be apparent from the following description taken in conjunction with the accompanying drawings, in which like reference characters designate the same or similar parts throughout the figures thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
[0016] FIG. 1 is a view schematically showing an arrangement example of an exposure apparatus according to a preferred embodiment of the present invention;
[0017] FIG. 2 is a view schematically showing the movable directions of a reticle and optical element whose positions are adjustable;
[0018] FIG. 3 is a flowchart for explaining automatic adjustment (configuration or procedures therefor) of a projection optical system according to the first embodiment;
[0019] FIG. 4 is a flowchart for explaining automatic adjustment (configuration or procedures therefor) of a projection optical system according to the second embodiment;
[0020] FIG. 5 is a graph providing an example in which each aberration is shown for each image height;
[0021] FIG. 6 is a graph providing an example in which an evaluation value obtained by normalizing each aberration is shown for each image height;
[0022] FIG. 7 is a flowchart showing the flow of the whole manufacturing process of a semiconductor device; and
[0023] FIG. 8 is a flowchart showing the detailed flow of a wafer process.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Preferred embodiments of the present invention will be described below with reference to the accompanying drawings.
[0025] FIG. 1 is a view schematically showing an arrangement example of an exposure apparatus according to the preferred embodiments of the present invention. An exposure apparatus 100 comprises a reticle stage 10 which holds a reticle 1 , a wafer stage which holds a wafer 2 , a projection optical system 3 which projects the pattern of the reticle 1 onto the wafer 2 , laser interferometers 5 , 6 , and 7 which measure the position of a wafer stage 4 , and a control unit 11 including an adjusting unit which adjusts the characteristics of the optical system including the projection optical system 3 .
[0026] The projection optical system 3 is made up of a plurality of optical elements. Some of the optical elements are arranged so that their postures can be adjusted by the adjusting mechanism. A reticle stage 10 is so arranged as to be able to adjust the posture of the reticle 1 .
[0027] FIG. 2 is a view schematically showing the movable directions of the reticle 1 and optical elements 8 and 9 whose positions are adjustable. The optical elements 8 and 9 are components of the projection optical system 3 . The position of the reticle 1 is adjusted by the reticle stage (reticle driving mechanism) 10 in a direction with six degrees of freedom under the control of the control unit 11 . The positions of the optical elements 8 and 9 are respectively adjusted by driving mechanisms 8 a and 9 a in a direction with six degrees of freedom under the control of the control unit 11 .
[0028] In adjustment of the projection optical system 3 under the control of the control unit 11 , the wavefront aberration (optical characteristic) of the projection optical system 3 is measured by PMI (Phase Measurement Interferometer) or the like. The wavefront aberration is expanded by the Zernike function to obtain a Zernike coefficient for each image height. By this method, the following embodiments can attain a Zernike coefficient for each image height.
[0029] Two methods will be explained as a method of adjusting aberration such as the wavefront aberration of the projection optical system 3 .
[0030] FIG. 3 is a flowchart for explaining automatic adjustment of a projection optical system 3 according to the first embodiment. Automatic adjustment is controlled by a control unit 11 . A block 101 executes a process of measuring the wavefront aberration of the projection optical system 3 . A block 102 expands the wavefront aberration by J Zernike orthogonal functions for image heights at H points to obtain Zernike coefficients Z jh .
[0031] A block 103 calculates aberration amounts from the optical design values of the projection optical system 3 , and obtains main aberration amounts of N types (e.g., coma, curvature of field, astigmatism, distortion, and telecentricity) for evaluating the projection optical system 3 for image heights at H points. A block 104 accumulates pieces of information obtained by the blocks 101 to 103 . As shown in FIG. 5 , the aberration amount can be given as a wavelength value.
[0032] A block 105 divides the aberration amounts by an allowance and normalizes them in order to optimize the aberrations of the projection optical system 3 with good balance in accordance with K adjustment amounts. The normalized aberration amount will be called an evaluation value.
[0033] Suffixes h, i, j, and k to be used below are defined by formulas (1) to (4):
h=1, . . . , H (1)
i=1, . . . , N (2)
j=1, . . . , J (3)
k=1, . . . , K (4)
[0034] A block 106 obtains, out of the evaluation values obtained by the block 105 , an evaluation value (to be referred to as a linear evaluation value) which is expressed by the linear function of the Zernike coefficient. A block 107 obtains, out of the evaluation values obtained by the block 105 , the square (to be referred to as a quadratic evaluation value) of RMS (Root Mean Square) of the wavefront aberration, which is expressed by the quadratic function.
[0035] According to this procedure, each aberration becomes permissible for an evaluation value of 1 or less and impermissible for an evaluation value of more than 1. Thus, a plurality of aberrations can be minimized with good balance.
[0036] FIG. 6 is a graph showing the evaluation values of aberration (1) and aberration (2) shown in FIG. 5 . As given by formula (5), a linear evaluation value y ih can be expressed by the linear sum of Zernike coefficients. When the adjustment amounts of respective components (e.g., optical elements 8 and 9 and a reticle stage 10) are changed, a Zernike coefficient Z jh for each image height can also be expressed by the linear sum of adjustment amounts k of these components, as given by formula (6).
y ih = 1 Y i ∑ j = 1 j a ij z jh ( 5 ) z jh = z 0 jh + ∑ k = 1 J b jhk x k ( 6 )
[0037] Formulas (5) and (6) derive formula (7):
y ih = y 0 ih + ∑ k = 1 J c ihk x k for ( 7 ) y 0 ih = 1 Y i ∑ j = 1 J a ij z 0 jh ( 8 ) c ihk = 1 Y i ∑ j = 1 J a ij b jhk ( 9 )
where
Y i : the allowance of the ith aberration Y ih : the evaluation value of the ith aberration at an image height h Y 0ih : the initial value of the evaluation value of the ith aberration at the image height h z jh : the jth Zernike coefficient at the image height h
z 0jh : the initial value of the jth Zernike coefficient at the image height h
x k : the kth adjustment amount a ij : the degree of influence of the Zernike coefficient z jh on the ith aberration b jhk : the degree of influence of the adjustment amount x k of each part on the Zernike coefficient z jh c ihk : the degree of influence of the adjustment amount x k of each part on the evaluation value y ih of the image performance
[0046] A block 108 minimizes only the linear evaluation value by applying to it linear programming which has been proposed by Japanese Patent Laid-Open No. 2002-367886 and uses a dummy variable. A block 109 minimizes a dummy variable t serving as the upper limit value of the linear evaluation value.
[0047] More specifically, the block 109 uses linear programming given by formulas (10) to (13) to calculate the minimized dummy variable t, and the adjustment amounts x k of respective components (e.g., the optical elements 8 and 9 and the reticle stage 10) that are used to optimize aberrations with good balance.
Minimization: f i =t (10)
[0048] Constraint conditions:
y 0 ih + ∑ k = 1 K c ihk x k ≤ t ( 11 ) - y 0 ih - ∑ k = 1 K c ihk x k ≤ t ( 12 ) t ≥ 0 ( 13 )
[0049] A quadratic evaluation value rms 2 is expressed by the sum of the squares of wavefront aberrations RMS with a weight w h for respective image heights, as given by formula (14):
rms 2 = 1 RMS 2 ∑ h = 1 H w h ∑ j = 1 J α jh z jh 2
= 1 RMS 2 ∑ h = 1 H w h ∑ j = 1 J α jh ( z 0 jh + ∑ k = 1 K b jhk x k ) 2 ( 14 )
where
RMS 2 : the allowance of the square of the wavefront aberration RMS rms 2 : the quadratic evaluation value of the wavefront aberration RMS α jh : the degree of influence of the Zernike coefficient z jh on rms 2 at the image height h
[0053] The quadratic evaluation value is not always smaller than the dummy variable t, and thus aberrations including the quadratic evaluation value must be minimized separately.
[0054] A block 110 sets the value of an allowable error e in order to determine whether the linear evaluation value and quadratic evaluation value have been minimized with good balance. The allowable error e is the allowance of the difference between the linear evaluation value and the quadratic evaluation value.
[0055] A block 111 zeros the initial value of a relaxation amount d. A block 112 executes quadratic programming using the maximum value of the linear evaluation value as the sum of the dummy variable t and relaxation amount d. At this time, an objective function to be minimized is a quadratic evaluation value.
[0056] Quadratic programming having the constraint conditional expressions of formulas (16) to (18) is applied using the quadratic evaluation value given by formula (15) as an objective function and the sum t+d of the minimized dummy variable t and the relaxation amount d as a threshold. A block 113 compares quadratic evaluation values (wavefront aberrations RMS for image heights at a plurality of points) which are obtained by quadratic programming for the adjustment amounts x k of respective components, and adjusts the weight w h to balance the wavefront aberrations RMS of the image heights.
[0057] If the value of the minimized quadratic evaluation value is larger than t+d+e, the quadratic evaluation value is larger than the maximum value of the linear evaluation value. Thus, a block 117 causes a block 115 to increase the relaxation amount d and the block 112 to repeat execution of quadratic programming. To the contrary, if the value of the minimized quadratic evaluation value is smaller than t+d−e, the quadratic evaluation value is much smaller than the maximum value of the linear evaluation value. A block 116 causes a block 114 to decrease the relaxation amount d and the block 112 to repeat execution of quadratic programming.
[0058] At this time, the values w h and d are given proper positive real numbers on the basis of a search algorithm such as the hill-climbing method or genetic algorithm.
[0059] If the difference between the linear evaluation value and the quadratic evaluation value becomes smaller than e, calculation ends, and respective components (e.g., the optical elements 8 and 9 and the reticle stage 10) are adjusted in accordance with the obtained solution.
Minimization: f 2 = 1 RMS 2 ∑ h = 1 H w h ∑ j = 1 J α jh ( z 0 jh + ∑ k = 1 K b jhk x k ) 2 ( 15 )
[0060] Constraint conditions:
y 0 ih + ∑ k = 1 n c ihk x k ≤ t + d ( 16 ) - y 0 ih - ∑ k = 1 n c ihk x k ≤ t + d ( 17 ) x k ≥ 0 ( 18 )
where
w h : weight d: relaxation amount
[0063] When H=1, that is, only one wavefront aberration RMS is to be minimized, only the relaxation amount d is searched for, and this search is easy. To the contrary, it is highly likely that search will take a long time for a large H.
[0064] After the solutions of the adjustment amounts x k of respective components (optical elements 8 and 9 and reticle stage 10) are obtained, these components are driven in accordance with the solutions to adjust the projection optical system 3 .
[0065] FIG. 4 is a flowchart for explaining automatic adjustment of a projection optical system 3 according to the second embodiment. Automatic adjustment is controlled by a control unit 11 . A block 101 executes a process of measuring the wavefront aberration of the projection optical system 3 . A block 102 expands the wavefront aberration by J Zernike orthogonal functions for image heights at H points to obtain Zernike coefficients z jh .
[0066] A block 103 calculates aberration amounts from the optical design values of the projection optical system 3 , and obtains main aberration amounts of N types (e.g., coma, curvature of field, astigmatism, distortion, and telecentricity) for evaluating the projection optical system 3 for image heights at H points. A block 104 accumulates pieces of information obtained by the blocks 101 to 103 .
[0067] A block 105 divides the-aberration amounts by an allowance, normalizes them, and obtains normalized evaluation values (normalized aberration amounts) in order to optimize the aberrations of the projection optical system 3 with good balance in accordance with K adjustment amounts. A block 106 obtains a linear evaluation value from the evaluation values obtained by the block 105 . The above configuration and procedures are the same as those in the first embodiment.
[0068] In the second embodiment, a block 116 defines the upper limit of the absolute value of the Zernike coefficient at the image height h by a dummy variable s jh , as given by formula (19):
|z jh |≦s jh (19)
[0069] A block 117 expresses, by the linear function of the dummy variable s jh , the upper limit of an approximate value calculated by dividing the wavefront aberration RMS by its allowance, as given by formula (20). The resultant value is defined as an RMS approximate evaluation value.
1 RMS ∑ j = 1 J α jh z jh 2 ≈ 1 RMS ∑ j = 1 J α jh z jh ≤ 1 RMS ∑ j = 1 J α jh s jh
α jh ≥ 0 , s jh ≥ 0 ( 20 )
[0070] The RMS approximate evaluation value is the linear function of the dummy variable s jh , and can be processed similarly to other linear evaluation values (their upper limit values are defined by the dummy variable t). Hence, all aberrations including the wavefront aberration RMS can be optimized with good balance by only linear programming which defines, by the dummy variable t, the upper limit values of all linear evaluation values including the linear function (linear evaluation value) of the dummy variable s jh , as given by formulas (21) to (28).
[0071] A block 108 executes linear programming using the dummy variable t in accordance with formulas (21) to (28):
Minimization: f 1 =t (21)
[0072] Constraint conditions:
x k ≥ 0 ( 22 ) s jh ≥ 0 ( 23 ) z jh ≤ s jh ( 24 ) - z jh ≤ s jh ( 25 ) y 0 ih + ∑ k = 1 K c ihk x k ≤ t ( 26 ) - y 0 ih - ∑ k = 1 K c ihk x k ≤ t ( 27 ) 1 RMS ∑ j = 1 J α jh s jh ≤ t ( 28 )
[0073] After the solutions of the adjustment amounts x k of respective components (optical elements 8 and 9 and a reticle stage 10) are obtained, these components are driven in accordance with the solutions to adjust the projection optical system 3 .
[0074] Linear programming using a dummy variable will be explained. Formula (29) shows the relationship between an error e i before adjustment, an error e i after adjustment, an adjustment sensitivity a ij , and an adjustment amount x j .
ei ′ = ei - ∑ j = 1 m a ij x j , ( i = 1 , … , n ) ( 29 )
[0075] A linear programming problem is expressed by the objective function of formula (30) and the conditional expression of formula (31):
Z = ∑ j = 1 m c j x j ( 30 ) ∑ j = 1 m a ij x j ≤ c i , ( i = 1 , … , n ) ( 31 )
[0076] Of these formulas, the objective function is defined by the linear expression of a controlled variable, and is to be minimized or maximized. The conditional expression is an equality or inequality expressed by the linear function of a controlled variable. The solvers of some linear programming problems may process only nonnegative controlled variables. However, nonnegative conditions do not inhibit application of linear programming because variable replacement given by formula (32) makes it possible to express an actual controlled variable x j which does not satisfy a nonnegative condition by two variables x j ′ and x j ″ which satisfy the nonnegative condition.
x j =x j ′−x j ″ (32)
[0077] In practice, it may be required that a controlled variable falls within a predetermined range. This condition can be expressed by the conditional expression formula (31).
[0078] Linear programming using a dummy variable minimizes the maximum absolute value of e i ′, (i=1, . . . , n). For this purpose, the dummy variable t which satisfies |e i ′|≦t, (i=1, . . . , n) is introduced, and a linear programming problem which minimizes t is formulated. That is, an objective function which minimizes the controlled variable t is set, as given by formula (33). A linear programming problem which sets the conditional expressions of formulas (34) and (35) is so defined as to adjust the dummy variable t to the limit value of an error and that of a value prepared by inverting the sign of the error. By solving this problem, the maximum absolute value of a residual after adjustment can be minimized.
z = t ( 33 ) e i - ∑ j = 1 m a ij x j ≤ t , ( i = 1 , … , n ) ( 34 ) - e i - ∑ j = 1 m a ij x j ≤ t , ( i = 1 , … , n ) ( 35 )
[0079] Minimization of the maximum absolute value by linear programming using a dummy variable includes the first to fifth steps. In the first step, the dummy variable t which makes it a condition that the dummy variable t is equal to or larger than an evaluation term (absolute value of an error after adjustment at each point: |e i ′|) is defined by an inequality. In the second step, the range of a controlled variable is expressed by an inequality (see formulas (30) and (31)). In the third step, the variable is so converted as to satisfy a nonnegative condition (see formula (32)). In the fourth step, a linear programming model is formulated. In the fifth step, the optimum solution of the controlled variable is calculated on the basis of linear programming (see formulas (33) to (35)).
[0080] Since a formulated problem always has a solution, the above calculation method can provide the controlled variable x j which strictly minimizes the maximum absolute value of an error. In an exposure apparatus according to the embodiments, the number of controlled variables is not large, and even a general linear programming problem solver can finish calculation in a short time. This method is, therefore, effective for real-time adjustment because a high throughput can be stably maintained.
[0081] A semiconductor device manufacturing process using the above exposure apparatus will be explained. FIG. 7 is a flowchart showing the flow of the whole manufacturing process of a semiconductor device. In step 1 (circuit design), the circuit of a semiconductor device is designed. In step 2 (mask formation), a mask is formed on the basis of the designed circuit pattern. In step 3 (wafer formation), a wafer is formed using a material such as silicon. In step 4 (wafer process) called a pre-process, an actual circuit is formed on the wafer by lithography using the mask and wafer. Step 5 (assembly) called a post-process is the step of forming a semiconductor chip by using the wafer formed in step 4 , and includes an assembly process (dicing and bonding) and packaging process (chip encapsulation). In step 6 (inspection), the semiconductor device manufactured in step 5 undergoes inspections such as an operation confirmation test and durability test. After these steps, the semiconductor device is completed and shipped (step 7 ).
[0082] FIG. 8 is a flowchart showing the detailed flow of the wafer process. In step 11 (oxidation), the wafer surface is oxidized. In step 12 (CVD), an insulating film is formed on the wafer surface. In step 13 (electrode formation), an electrode is formed on the wafer by vapor deposition. In step 14 (ion implantation), ions are implanted in the wafer. In step 15 (resist processing), a photosensitive agent is applied to the wafer. In step 16 (exposure), a circuit pattern is transferred onto the photosensitive agent on the wafer by the above-mentioned exposure apparatus. In step 17 (developing), the exposed wafer is developed. In step 18 (etching), the resist is etched except the developed resist image. In step 19 (resist removal), an unnecessary resist after etching is removed. These steps are repeated to form multiple circuit patterns on the wafer.
[0083] As many apparently widely different embodiments of the present invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the claims.
CLAIM OF PRIORITY
[0084] This application claims priority from Japanese Patent application No. 2004-077044 filed on Mar. 17, 2004, the entire contents of which are hereby incorporated by reference herein.
|
An optical apparatus including an image forming optical system having a movable optical element, and a driving mechanism which moves the optical element is disclosed. The apparatus comprises a first block which obtains a linear evaluation value by normalizing, by a first tolerance, an aberration expressed by a linear function of a position of the movable optical element out of aberrations of the optical system, and a quadratic evaluation value by normalizing, by a second tolerance, an aberration expressed by a quadratic function of the position out of the aberrations of the optical system, a second block which obtains a minimum value of a dummy variable by linear programming using an upper limit value of the linear evaluation value as the dummy variable, and a third block which determines a position of the optical element to be moved by the driving mechanism so as to minimize a weighted sum of the quadratic evaluation values with respect to a plurality of image heights by using, as the upper limit value of the linear evaluation value, a value prepared by adding a relaxation amount to the minimum value of the dummy variable that is obtained by the second block. The third block minimizes the weighted sum of the quadratic evaluation values by adjusting the weights assigned to the quadratic evaluation values and the relaxation amount.
| 6
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and the benefit of U.S. provisional patent application Serial No. 60/170,972, filed Dec. 15, 1999, the disclosure of which application is hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] This invention relates generally to spectral analysis. More particularly, in one embodiment, the invention relates to determining chemically-induced changes of optical spectra.
BACKGROUND OF THE INVENTION
[0003] Direct visual observation alone is often inadequate for identification of abnormalities in a specimen being examined, whether the specimen is a biological specimen or otherwise. Observation of many medical conditions in biological specimens of all kinds is well known. It is common in medical examination to perform visual examinations in disease diagnosis. For example, visual examination of the cervix can discern areas where there is a “suspicion” of pathology. In some instances, filters can be used to improve visual differentiation of normal and abnormal tissues. In other situations, when tissues of the cervix are examined in vivo, chemical agents such as acetic acid can be applied to enhance the differences in appearance between normal and pathological areas. These techniques form an integral part of a colposcopic examination of the cervix. Colposcopists may amplify the difference between normal and cancerous tissue with the application of various “activation” agents, the most common being acetic acid, at approximately 3% to 5% concentration, or an iodine solution, such as Lugol's iodine or Shiller's iodine. Even when the cervical tissues are viewed through a colposcope by an experienced practitioner with the application of acetic acid, correct diagnosis can be affected by subjective analysis. A variety of methods using optical techniques have been directed towards the diagnosis of cancer and other pathologies, particularly involving the cervix. Certain of these systems and methods have limitations that render them unsuitable for use as screening procedures.
[0004] While there have been extensive developments in the field of cancer diagnosis, none of these are well adapted for screening large populations. Currently, disease diagnoses are made predominately from pathological examinations of biopsied tissue. Techniques such as biopsies, while being the definitive determination of the presence of disease, are labor-intensive and operator-dependent, thus unsuitable for screening large populations. As another example, medical imaging techniques, depending on their cost, resource requirements and patient accessibility, may be unsuitable for population screening.
[0005] To be well accepted in the medical community, a screening method should be sufficiently sensitive and specific to identify abnormalities accurately. Furthermore, a screening method ideally is easy to perform so that it can be carried out rapidly on an otherwise healthy patient. In addition, to be cost effective the screening method should not require the use of expensive resources, including a significant time commitment from costly, highly trained medical personnel. Generally, screening settings advantageously employ less skilled operators and more operator-independent technology.
SUMMARY OF THE INVENTION
[0006] The invention provides systems and methods for quickly and efficiently screening samples, especially biological samples. According to the invention, changes in the spectral properties of tissues upon exposure to chemical agents are characteristic of the physiological state of the tissue. In particular, the invention relates to changes in spectral properties of a sample in response to chemical treatment. The sample can be a sample of tissue, and the response can be indicative of a state of health of the tissue or the patient from whom the sample is obtained. Upon exposure to chemical agents, the light emission properties of a sample change. In the case of a sample of tissue, the temporal evolution of these changes is characteristic of the state of health of the tissue generally. When exposed to light, tissues emit light having spectral properties that are characteristic of the physiological and biochemical make-up of the tissue. When exposed to a chemical agent, such as a contrast agent, the spectral properties of the tissue are changed by the interaction of the agent with endogenous molecules in the tissue. As the chemical agent diffuses out of the area of application, or otherwise becomes less abundant in the tissue, the emission spectrum of the tissue returns to pre-exposure levels. According to the invention, changes in tissue produced by endogenous chemical agents provide insight into the sample, such as the clinical health of the tissue as described in detail below. The invention also involves systems and methods of performing the application of one or more chemical agents, including the amount of material dispensed, dispensing patterns, and triggering a measurement relative to the time of dispensing.
[0007] Accordingly, the invention provides methods and systems for diagnosing patient health by exposing a sample to one or more chemical agents, and measuring a change in an optical signal from the sample. A preferred method of the invention comprises dispensing a plurality of chemical agents on a sample, wherein the agents interact to alter an optical signal from the sample and measuring the chemical agents are selected from the group consisting of acetic acid, formic acid, propionic acid, butyric acid, Lugol's iodine, Shiller's iodine, methylene blue, toluidine blue, osmotic agents, ionic agents, and indigo carmine. The chemical agents may be applied substantially simultaneously, or by dispensing at least two of the plurality of chemical agents sequentially.
[0008] The invention is applicable to any sample type. Preferred methods of the invention comprise using a biological sample. In a preferred embodiment, the sample is selected from epithelial tissue, cervical tissue, colorectal tissue, skin, and uterine tissue.
[0009] In another aspect, a preferred embodiment of the invention relates to a method of diagnosing disease comprising dispensing a chemical agent on a sample, providing an automated triggering signal to initiate a measurement period relative to the dispensing, and measuring an optical signal from the sample. The automated triggering signal can be provided prior to, substantially simultaneously with, or after dispensing the chemical agent. In preferred embodiments, the measurement is initiated at a predetermined time relative to the automatic triggering signal. In yet another aspect, methods of the invention comprise of diagnosing the state of health of a applying the chemical agent or agents as a mist onto the sample.
[0010] In a preferred embodiment, the predefined pattern is substantially circular. In another preferred embodiment, the predefined pattern is substantially annular.
[0011] In preferred embodiments, the chemical agent is dispensed at a controlled rate, or a controlled volume of the chemical agent is dispensed, or both.
[0012] In a still further aspect, the invention comprises dispensing a chemical agent on a sample, capturing a plurality of sequential images of the sample during a measurement periods automatically aligning a subset of the plurality of images to spatially correlate the subset of images, measuring an optical signal from the subset of the spatially correlated images, and providing a diagnosis of a state of health of the sample based at least in part on the optical signal.
[0013] In a preferred embodiment, aligning further comprises aligning the subset to compensate for relative motion between the sample and a spectral observation device. In another preferred embodiment, aligning further comprises aligning the subset to compensate for relative motion between a first portion of the sample and a second portion of the sample.
[0014] In a still further aspect, the invention provides methods for determining a tissue response in which a chemical agent is applied to a tissue and an optical property of an endogenous molecule in the tissue is measured. In a preferred embodiment, the endogenous molecule is a chromophore, for example a fluorophore. Method of the invention comprise applying the chemical agent and monitoring an optical signal from the endogenous molecule. The presence, absence, or change in the signal may be indicative of disease when compared to known standards. Such standards may be empirically derived or may be obtained from the art. The endogenous chromophore is preferably hemoglobin, a porphoryin, NADH, a flavin, elastin, or collagen.
[0015] In preferred methods, the optical signal is a light signal, such as a fluorescent or white light spectrum. The optical signal may also be a speetrum produced, at least in part by light-scattering properties of the tissue.
[0016] Also in preferred methods, the optical signal may be a decay function. The optical signal is compared to a standard response associated with healthy or diseased tissue, including tissue at various stages of disease. Such standards may be determined empirically or known in the art. Alteration of an optical signal alone may be indicative of the health of the patient from when a sample was obtained.
[0017] The foregoing and other objects, aspects, features, and advantages of the invention will become more apparent from the following description and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The objects and features of the invention can be better understood with reference to the drawings described below, and the claims. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the drawings, like numerals are used to indicate like parts throughout the various views.
[0019] [0019]FIG. 1 shows an exemplary spectroscopic system that employs a plurality of spectral types according to an illustrative embodiment of the invention;
[0020] [0020]FIG. 2 shows an exemplary operational block diagram of the spectroscopic system of FIG. 1;
[0021] [0021]FIG. 3 is a detailed schematic flow diagram showing exemplary steps of combining a fluorescence spectrum analysis with a reflectance spectrum analysis according to an illustrative embodiment of the invention;
[0022] [0022]FIG. 4 is a schematic diagram of another illustrative system useful for monitoring the effects of a chemical agent on a specimen, and which embodies principles of the invention;
[0023] [0023]FIG. 5 is a graph that shows trend lines of data observed according to principles of the invention;
[0024] FIGS. 6 A- 6 C are diagrams that show razz data observed from various specimens according to principles of the invention;
[0025] [0025]FIG. 7 is a graph showing curves representing averages of data processed according to principles of the invention;
[0026] [0026]FIG. 8 is a graph plotting computed ratios that show a basis for differentiating CIN II/III lesion from CIN I and normal tissue for individual specimens, according to principles of the invention;
[0027] [0027]FIG. 9 is a graph showing responses, normalized at 480 nm, from tissues as function of wavelength, according to principles of the invention;
[0028] [0028]FIG. 10 is a functional block diagram of an embodiment of another illustrative system useful for monitoring the effects of a chemical agent on a specimen according to the invention;
[0029] [0029]FIG. 11 is a functional block diagram of an embodiment of an illustrative hand-held system useful for monitoring the effects of a chemical agent on a specimen according to the invention;
[0030] FIGS. 12 A- 12 C depict schematic arrangements for illustrative filter wheels useful in the system of FIG. 11;
[0031] [0031]FIG. 13 is a functional block diagram of an embodiment of a system useful for monitoring the effects of a chemical agent on a specimen according to the invention;
[0032] [0032]FIG. 14 is a schematic diagram of a filter wheel useful in the system of FIG. 13;
[0033] [0033]FIG. 15 is a functional block diagram of an embodiment of a system useful for monitoring the effects of a chemical agent on a specimen according to the invention,;
[0034] [0034]FIG. 16 shows a schematic diagram of a CCD device for use in the system of FIG. 15;
[0035] [0035]FIG. 17 is a graph showing the time dependence of backscattered responses at 600 nm for various tissue classes (NED, CIN II and CIN III), recorded using systems and methods of the invention;
[0036] FIGS. 18 A- 18 C are diagrams depicting various aspects of a mucosal atomizer device used to spray a chemical agent uniformly onto the surface of a specimen, and to provide a trigger mechanism useful for initiating an optical observation, according to principles of the invention;
[0037] [0037]FIG. 19 is a graph of absorption spectra recorded for NADH using a chemical agent according to the invention;
[0038] [0038]FIG. 20 is a graph of fluorescence spectra as a function of time for specimens treated with a chemical agent according to principles of the invention;
[0039] [0039]FIG. 21 is a graph of flourescence spectra recorded before and after treatment of a specimen with a chemical agent, according to principles of the invention;
[0040] [0040]FIG. 22 is a one-dimensional diagram of watershed segmentation;
[0041] [0041]FIG. 23 is a graph of a signal and its first derivative; and
[0042] [0042]FIG. 24 shows a sigmoidal scaling function used to enhance the contrast between light and dark regions of an image.
DETAILED DESCRIPTION
[0043] Acetowhitening of cervical tissue has long been known to be a qualitative aid to locating lesions during colposcopic examination. However, accurate quantitative measurements of acetowhitening of cervical epithelial tissue, as a function of time and wavelength, have not been reported. Quantitative analysis of the acetowhitening process can significantly increase the sensitivity and specificity of traditional colposcopy.
[0044] The invention will be described in terms of multiple embodiments that relate to the observation of chemically-induced changes in optical spectra, particularly in the area of medical diagnostics, and especially as it relates to the analysis of spectra obtained from human cervical tissue in the detection of cervical cancer. However, the invention has applicability generally in the area of chemically-induced changes in optical spectra.
[0045] [0045]FIG. 1 depicts an exemplary spectroscopic system 100 employing a plurality of spectral data types in methods and systems according to an illustrative embodiment of the invention. The spectroscopic system includes a console 102 connected to a probe 104 by a cable 106 . The cable 106 carries electrical and optical signals between the console 102 and the probe 104 . The probe 104 accommodates a disposable component 108 , which is used only once, and discarded after use. The console 102 and the probe 104 are mechanically connected by an articulating arm 110 , which can also support the cable 106 . The console 102 contains much of the hardware and the software of the system, and the probe 104 contains the necessary hardware for making suitable spectroscopic observations. The details of the system are further explained in conjunction with FIG. 2.
[0046] [0046]FIG. 2 shows an exemplary operational block diagram 200 of a spectroscopic system of the type depicted in FIG. 1. According to an illustrative embodiment, the spectroscopic system of FIGS. 1 and 2 is substantially the same as single-beam spectrometer devices, but is adapted to include the features of the invention. The console 102 includes a computer 202 which executes software that controls the operation of the spectroscopic system 100 . The software includes one or more modules recorded on machine-readable media, which can be any medium such as magnetic disks, magnetic tape, CD-ROM, semiconductor memory, or the like. Preferably, the machine-readable medium is resident within the computer 202 . In alternative embodiments, the machine-readable medium can be connected to the computer 202 by a communication link. In alternative embodiments, one can substitute computer instructions in the form of hardwired logic for software, or one can substitute firmware (i.e., computer instructions recorded on devices such as PROMs, EPROMS or EEPROMs, or the like) for software. The term machine-readable instructions as used herein is intended to encompass software, hardwired logic, firmware and the like.
[0047] The computer 202 is a general purpose computer. The computer 202 can be an embedded computer, or a personal computer such as a laptop or desktop computer, that is capable of running the software, issuing suitable control commands, and recording information in real time. The computer 202 has a display 204 for reporting information to an operator of the spectroscopic system 100 , a keyboard 206 for enabling the operator to enter information and commands, and a printer 208 for providing a print-out, or permanent record, of measurements made by the spectroscopic system 100 and for printing diagnostic results, for example, for inclusion in the chart of a patient. As described below in more detail, in an illustrative embodiment of the invention, some commands entered at the keyboard, enable a user to select a particular spectrum for analysis or to reject a spectrum, and to select particular segments of a spectrum for normalization. Other commands enable a user to select the wavelength range for each particular segment and to specify both wavelength contiguous in non-contiguous segments.
[0048] The console 102 also includes an ultraviolet (UV) source 210 such as a nitrogen laser or a frequency-tripled Nd:YAG laser, a white light source 212 such as one or more Xenon flash lamps, and control electronics 214 for controlling the light sources both as to intensity and as to the time of onset of operation and the duration of operation. One or more power supplies 216 are included in the console 102 , to provide regulated power for the operation of all of the components. The console 102 also includes at least one spectrometer and at least one detector (spectrometer and detector 218 ) suitable for use with each of the light sources. In some embodiments, a single spectrometer can operate with both the UV light source and the white light source. In some embodiments, the same detector can record UV and white light signals, and in some embodiments different detectors are used for each light source.
[0049] The console 102 also includes coupling optics 220 to couple the UV illumination from the UV light source 210 to one or more optical fibers in the cable 106 for transmission to the probe 104 , and for coupling the white light illumination from the white light source 212 to one or more optical fibers in the cable 106 for transmission to the probe 104 . The console 102 also includes coupling optics 222 to couple the spectral response of a specimen to UV illumination from the UV light source 210 observed by the probe 104 and carried by one or more optical fibers in the cable 106 for transmission to the spectrometer and detector 218 , and for coupling the spectral response of a specimen to the white light illumination from the white light source 212 observed by the probe 104 and carried by one or more optical fibers in the cable 106 for transmission to the spectrometer and detector 218 . The console 102 includes a footswitch 224 to enable an operator of the spectroscopic system 100 to signal when it is appropriate to commence a spectral observation by stepping on tie switch. In this manner, the operator has his or her hands free to perform other tasks, for example, aligning the probe 104 .
[0050] The console 102 includes a calibration port 226 for calibrating the optical components of the spectrometer system. The operator places the probe 104 in registry with the calibration port 226 and issues a command that starts the calibration operation. In the calibration operation, a calibrated light source provides illumination of known intensity as a function of wavelength as a calibration signal. The probe 104 detects the calibration signal. The probe 104 transmits the detected signal through the optical fiber in the cable 106 , through the coupling optics 222 to the spectrometer and detector 218 . A test spectral result is obtained. A calibration of the spectral system is computed as the ratio of the amplitude of the known illumination at a particular wavelength divided by the test spectral result at the same wavelength.
[0051] The probe 104 includes probe optics 230 for illuminating a specimen to be analyzed with UV and white light from the UV source 210 and the white light source 212 , and for collecting the fluorescent and backscatter (or reflectance) illumination from the specimen that is being analyzed. The probe includes a scanner assembly 232 that provides illumination from the UV source 210 in a raster pattern over a target area of the specimen of cervical tissue to be analyzed. The probe includes a video camera 234 for observing and recording visual images of the specimen under analysis. The probe 104 includes a targeting source 236 , which can be used to determine where on the surface of the specimen to be analyzed the probe 104 is pointing. The probe 104 also includes a white light illuminator 238 to assist the operator in visualizing the specimen to be analyzed. Once the operator aligns the spectroscopic system and depresses the footswitch 224 the computer 202 controls the actions of the light sources 210 , 212 , the coupling optics 220 , the transmission of light signals and electrical signals through the cable 106 , the operation of the probe optics 230 and the scanner assembly 232 , the retrieval of observed spectra via the cable 106 , the coupling of the observed spectra via the coupling optics 222 into the spectrometer and detector 218 , the operation of the spectrometer and detector 218 , and the subsequent signal processing and analysis of the recorded spectra.
[0052] [0052]FIG. 3 is a detailed schematic flow diagram 300 showing exemplary steps of combining fluorescence spectrum analysis with reflectance spectrum analysis to perform tissue characterization according to an illustrative embodiment of the invention. Step 310 indicates that fluorescence spectra from a test specimen of unknown condition or unknown state of health are available. At step 320 , the computer 202 determines whether the test specimen can be classified as “normal,” or “metaplasia,” or can not be classified by fluorescence spectroscopy alone. As indicated in step 325 , a decision is taken as to whether the test specimen has a definitive state of health, for example that the specimen is “normal.” If the test specimen can be classified, for example as normal, the method ends at step 330 .
[0053] In the event that a definitive condition or state of health cannot be ascribed to a test specimen, the computer 202 further analyses information available from a reflectance spectrum or from a plurality of reflectance spectra taken from the test specimen. At step 335 , the computer 202 provides processed reflectance spectra.
[0054] If the specimen cannot be classified, a mean normalization step is performed by computer 202 , as indicated at step 340 . The mean normalization is carried out using a plurality of reflectance spectra taken from specimens that are known to represent normal squamous tissue. In one embodiment, a single test specimen is examined at multiple locations, each location measuring approximately one millimeter in diameter. If one or more locations of the test specimen provide fluorescence spectra that indicate that those locations can be classified as representing normal squamous tissue, the reflectance spectra recorded from those locations are used to mean normalize the reflectance spectra obtained from locations that are not capable of being classified as “normal” or “metaplasia” solely on the basis of fluorescence spectra.
[0055] As indicated in step 350 , the computer 202 can carry out an analysis using a metric, for example using the Mahalanobis distance as a metric in N-dimensional space. In one embodiment, the test reflectance spectra are truncated to the wavelength regions 391 nm to 484 nm, and 532 nm to 625 nm. In one embodiment, the classifications CIN I and CIN II/II are the classifications that are possible for a test spectrum that is neither classified as “normal” nor “metaplasia” by fluorescence spectral analysis. As indicated at step 350 , the computer 202 classifies the test specimen as having a condition or state of health selected from CIN I and CIN II/III based on the value of the metric computed by the computer 202 , provided that the value of the metric does not exceed a pre-determined maximum value.
[0056] At step 360 , the computer 202 presents the results of the classification of the test specimen, as a condition or state of health corresponding to one of normal, metaplasia, CIN I and CIN II/III.
[0057] [0057]FIG. 4 shows a schematic diagram of an illustrative system 600 embodying principles of the invention. A standard colposcope 610 (Zeiss, Model 1-FC ZMS-506-II) is modified by adding video image capture capability with permanent and electronic storage of data to allow capturing of time-sequenced images during a routine colposcopic examination. The colposcope 610 has magnification capabilities of 4×, 6×, 10×, 16×. and 25×, and is illuminated by a fiber optic-coupled 12 volt/100 watt halogen lamp 620 with 20× eye binoculars. A three-channel charge-coupled device color video camera (DAGE-MTI. Model DC-330) 630 is mounted to the colposcope 610 . The computer 650 includes an integrated video frame-grab board and video display card at 24-bit resolution for capturing images. Images can be captured at a rate of at least about one image per second. The computer 650 also includes image control software (TeleComputing Solutions, ColpoShot™) that interfaces with the video frame grab board for archiving images, for example into patients' medical records. The ColpoShot™ software is modified to allow for intensity measurements at specific sites as a function of time and wavelength (as resolved by four discrete filters in a filter wheel 640 , described in more detail below). The computer 650 also includes control software for controlling the change of filters in the high-speed filter wheel 640 . This software is synchronized with the data collection (image capture) software so each image is associated with a spectral region corresponding to a particular filter. Time-stamping of each image is performed so each image can be placed in proper time sequence.
[0058] In the illustrative system 600 , the filter wheel 640 is from a Ludl Electronics Ltd., with an RS 232 and GPIB 488 computer interface for resolving optical signals with respect to wavelength. Images are measured and recorded at three separate wavelength bands in the visible spectral region. The first wavelength band is near 400 nm, with a bandwidth of about 20 nm to about 30 nm. The second wavelength band is near 525 nm with a bandwidth of about 30 nm. The third wavelength band is near 680 nm with a nominal bandwidth of about 30 nm. In addition to the images taken through the filter wheel 640 , a fourth image using unfiltered illumination is taken as part of the data set. The unfiltered images allow data analysis of red (R), green (G), and blue (B) components for comparison with filtered image data. As described before, crossed polarizers mounted in the optical path, one associated with the light coming from the illumination source 620 , and one associated with the light from the image to be observed and recorded, are used to reduce unwanted glare from the surface of the cervix.
[0059] The illustrative system 600 is controlled by the computer 650 , having capabilities similar to the computer 140 described earlier. The computer 650 has associated with it software to operate the computer 650 , to provide input and output interactions with an instrument user, to control and synchronize the various components of the illustrative system 600 , and to record, analyze, and report data obtained from the illustrative system 600 .
[0060] The illustrative system 600 is configured to capture time-separated images of the specimen during routine colposcopic examinations. Digital images are recorded at a 4× magnification giving a panoramic view of the entire cervical field at maximal acetic whitening. In the illustrative embodiment, images are taken about every second for about 5 minutes after the application of acetic acid. The computer 650 rotates the filter wheel 640 to allow for imaging at different wavelengths.
[0061] In operation, an illustrative embodiment of the process of obtaining images is as follows. The first image following the application of the acetic acid is an unfiltered image. Next, the filter wheel 640 is rotated to bring the short-wavelength (˜400 nm) filter into place and the next image is recorded. Then, the ˜525 nm filter is positioned, and the next image is recorded. Next, the long-wavelength (˜680 nm) filter is positioned and the last image of the sequence is recorded. This process takes four seconds to complete. After this first cycle through the filter wheel 640 , the process repeats with another unfiltered image, followed by the sequence of filtered images. The process of observing and recording images continues without stopping for a duration of 300 seconds. The resulting data are seventy-five unfiltered images of the evolution of an optical signal from a specimen treated with a chemical agent, such as cervical acetowhitening, and a total of seventy-five images in each of the three filtered spectral regions. As will be appreciated by those of skill in the spectroscopic arts, the precise sequence of observing and recording images in the various wavelength bands depends on the sequence of placement of filters within the filter wheel 640 and the sense of rotation of the wheel 640 . Alternative sequences of observation can be employed with substantially equivalent results. The duration of operation can be shortened or extended from the illustrative 300 seconds just described depending on the situation, which can be influenced by the kind of specimen and how it is to be examined (e.g., specimen characteristics, such as cervix, larynx, skin, and the like, specimen in vivo or in vitro, use of different chemical agents, the disease conditions to be investigated, and the like).
[0062] Illustratively, time-stamped images are saved to disk at 20 second intervals. In one embodiment, treatment of a specimen with a chemical agent is accomplished as follows. A solution of 5% acetic acid is applied with solution-soaked cotton balls placed in contact with the surface of the cervix for about 15 seconds. An alternative method of application of a chemical agent is discussed below. In one embodiment, the time sequence image capturing software is run immediately before the application of acetic acid, to obtain baseline measurements.
[0063] In one embodiment, the parameters that are extracted from the observations include the rate of acetowhitening, the maximum intensity of the whitening, and the final rate of decay of the whitening. Once the data is collected, the images are analyzed by the computer 650 with software that calculates four parameters (mean Luminance, and mean red (R), green (G), and blue (B) intensities) within user-defined Regions of Interest (ROI's). The software enables the user to mark with a mouse controlled cross-hair cursor, 5 pixel by 5 pixel ROI's on a location in an image. A biopsy can subsequently be taken by the colposcopist, to permit a comparison of the results obtained from the methods of the invention with the results of the biopsy. Once ROI's have been manually marked on all images in the timed-sequence, mean luminance and mean R. G, B intensities within the 5 pixel by 5 pixel ROI's are calculated and output in tabular form. Also included in the output recorded in the table are the following data elements; image number, ROI location, elapsed time in seconds, and the standard deviation and median of the Luminance and R, G, B values. In one embodiment, the ratio of the mean green intensity to the mean red intensity is found to yield accurate results.
[0064] In this embodiment, to calibrate the utility of the system and method, five (5) biopsy-confirmed CIN II/III lesions are measured, five (5) biopsy-confirmed CIN I lesions are measured, five (5) colposcopy-confirmed normal mature squamous tissue regions are measured and one (1) biopsy-confirmed normal mature squamous tissue region is measured. Data are analyzed by graphing the Green intensity divided by the Red intensity and normalizing by the maximum intensity within each patient.
[0065] [0065]FIG. 5 is a diagram 700 that shows the trend lines of ROIs correlated to CIN II/III lesions (curve 706 ), CIN I lesions (curve 708 ), and normal mature squamous tissue (curve 710 ). The trend lines are plotted using the ratio of mean green intensity to mean red intensity, normalized to maximum intensity, as the vertical axis 702 (expressed in arbitrary units), and using the time after application of acetic acid to the tissue, expressed in seconds, as the horizontal axis 704 .
[0066] FIGS. 6 A- 6 C are diagrams, generally 800 , that show graphs of raw data plotted using the ratio of mean green intensity to mean red intensity, normalized to maximum intensity, as the vertical axis 802 (expressed in arbitrary units), and using the time after application of accetic acid to the tissue, expressed in seconds, as the horizontal axis 804 . FIG. 6A is a diagram that shows the raw data of ROIs correlated to CIN II/III lesions, as curves 810 , 812 , 814 , 816 , 818 representing observations taken from five individuals. FIG. 6B is a diagram that shows the raw data of ROIs correlated to CIN I lesions, as curves 820 , 822 , 824 , 826 , 828 representing observations taken from five individuals. FIG. 6C is a diagram that shows the raw data of ROIs correlated to normal mature squamous tissue, as curves 830 , 832 , 834 , 836 , 838 representing observations taken from five individuals.
[0067] An operator of the illustrative system and method defines a region of interest on an image. The intensity readings of the pixels in this region are averaged to provide a quantitative value of brightness as recorded through the particular filter (or unfiltered). By plotting these values as functions of time, a picture of the evolution of the acetowhitening at the selected location in the image is created.
[0068] A clinically useful tool based on the acetowhitening kinetic characteristics analyzes the data to differentiate CIN II/III lesions from CIN I lesions and normal mature squamous tissue. According to one illustrative embodiment, the technique uses mean values from 100 second segments of individual patient kinetic curves. The curves are processed by calculating the mean of segments along the curve, i.e. the mean value of the data in the temporal range from about 100-200 seconds after application of the chemical agent, the mean value of the data in the temporal range from about 200-300 seconds after application of the chemical agent, and so forth. FIG. 7 is a graph 900 showing curves of the averages of data processed in this manner, in which the average values are plotted along the vertical axis 902 (expressed in normalized units). and using the time after application of acetic acid to the tissue, expressed in seconds, as the horizontal axis 904 . The curve 906 represents data relating to CIN II/III lesions. The curve 908 represents data relating to CIN I lesions. The curve 910 represents data relating to normal mature squamous tissue.
[0069] [0069]FIG. 8 is a scatter plot 1000 generated by taking the ratio of mean values from two time intervals (100-200 seconds) and (200-300 seconds) for data from individual specimens. In FIG. 8, the average values for the time interval 200 seconds to 300 seconds (expressed in normalized units) are plotted along the vertical axis 1002 , and the time interval 100 seconds to 200 seconds (expressed in normalized units), is plotted as the horizontal axis 1004 . The points 1006 represent data relating to CIN II/III lesions. The points 1008 represent data relating to CIN I lesions. The points 1010 represent data relating to normal mature squamous tissue. FIG. 8 shows a basis for differentiating CIN II/III for individual specimens. An illustrative line 1020 is a line of demarcation between the CIN II/III data and the remaining data. A second technique using the first derivative of the curves shown in FIG. 7 is also operative. This technique yields similar results to those shown in FIG. 8.
[0070] According to another illustrative embodiment of the invention, an indication of the presence or lack of cancerous or precancerous tissue is obtained by recording the optical response in two parts of the visible spectrum. In this embodiment, the inventors have observed that at short wavelengths, such as 380 nm, absorption by hemoglobin can reduce signal intensities. Optical responses are recorded in that part of the spectrum where optical response variation can be detected due to morphological changes in tissue which are associated with cancerous and precancerous tissue, such morphological variations having a strong impact on light scattering. At longer wavelengths, beyond 590 nm and to about 750 nm, scattering of light from cancerous tissue was substantially greater than from normal tissue, and thus the reflected responses from cancerous tissue in that spectral range were greater than from normal tissue.
[0071] It is desirable to standardize the responses from the tissue using a signal at a wavelength where both of these influences are relatively weak. In one embodiment, the system of the invention standardizes responses at 480 nm for this purpose. In one embodiment, the response, e.g., the observed reflectance, is recorded at three wavelengths, and the responses obtained at the short wavelength (between 360 and 440 nm) and at the long wavelength (between 590 and 750 nm) are divided by the response at 480 nm. According to one illustrative methodology of the invention, normalized reflections at longer wavelengths indicate cancerous and precancerous tissue, while lower intensity normalized reelections indicate healthy tissue. According to a further illustrative methodology of the invention, reflections in the short wavelength part of the spectrum indicate cancerous and precancerous tissue, while higher intensity reflections indicate healthy tissue.
[0072] An algorithm using the rate of change of white light reflection at some specific wavelength, for instance, at 600 nm, can provide accurate differentiation between pathologic and healthy tissue within the first 60 seconds after the application of a pathology differentiating agent like acetic acid. Other algorithms, using both the aforementioned rate of change, or the time lapsed to reach maximum back scattering after application of a differentiating agent, or the time required to attain specific back scattered (normalized) threshold values, permit the diagnosis of the presence or absence of cancer in the screened cervix.
[0073] As an aspect of the invention, methods are provided that employ specific algorithms to analyze the back-scattered responses obtained at the preselected wavelength or wavelengths either with or without a chemical agent. Algorithms further provide for classifying examined tissues as normal or pathological. In certain embodiments, these systems are characterized by ease of operation, simplicity and ruggedness.
[0074] [0074]FIG. 9 presents a graph 1100 showing two data curves 1102 , 1104 obtained from healthy (no evidence of disease, or NED) and cancerous (CIN) tissue respectively. Normalized intensity is plotted along the vertical axis 1106 and wavelength (in units of nm) is plotted along the horizontal axis 1108 . All received responses (I λ ) are normalized by dividing the intensities received by the intensity obtained at an arbitrary wavelength. Reflections measured at 480 nm are used for this purpose, since it is in a part of the spectrum where the responses' intensities are relatively independent of the tissue state (healthy or pathological). FIG. 9 shows that the received intensities at longer wavelength (between 550 to 750 nm) are consistently higher for cancerous tissue (curve 1104 ) than for healthy tissue (curve 1102 ). The data indicate that the use of three wavelengths from the reflected spectrum of tissue provides correlation between the presence or absence of cancer in the target tissue.
[0075] In one embodiment, an algorithm utilizes the reflected reading from the tissue at the three selected wavelengths to produce an indicator of the presence or absence of a pathology in the target tissue, or to create an artificial pathology image of the tissue observed. In the first step of the algorithm, the responses are collected at three wavelengths for each point observed In one embodiment the following three wavelengths can be used:
[0076] λ 1 =380 nm
[0077] λ 2 =480 nm
[0078] λ 3 =650 nm
[0079] It is understood that one can select wavelength ranges rather than specific narrow bands as illustrated here. Normalized reflected intensities may then be defined:
[0080] R 380 =I(λ 1 )/I(λ 2 )
[0081] R 650 =I(λ 3 )/I(λ 2 )
[0082] where I(λ 1 ), I(λ 2 ) and I(λ 3 ) are the measured reflected intensities at λ 1 , λ 2 and λ 2 respectively. These normalized intensities R 380 and R 650 (which are dimensionless), can vary from about 0.2 to about 6. In one embodiment, the intensity of the reflected light at 380 and 650 nm are normalized, where the normalization parameter is the reflected intensity at 480 nm. It should be evident to those of ordinary skill in the art that while in one embodiment R 380 is defined at λ=380 nm and R 650 at λ=650 nm, one can define R(low λ) and R(high λ) around neighboring wavelengths in the respective ranges as well, using data such as presented in FIG. 9 from a number of subjects and tissue with varying pathologies in those subjects as a “training set” to calibrate the apparatus being employed. The selection of the “bandwidth” around the center wavelength is related to the kind of instrumentation selected for the actual device, as described below in more detail.
[0083] As long as the bandwidths selected during the calibration or training of the device and its subsequent use in the field for screening purposes are the same, good correlation is found between high values of R 650 coupled with low values of R 380 and the presence of cancerous and precancerous, or CIN, tissue. Similarly, good correlation is found between low values of R 650 and high values of R 380 and the presence of healthy, or NED, tissue. Specifically, for cervical tissue that when R 650 <3.1 and R 380 >1.1, the tissue is healthy (NED) and when R 450 >3.3 and R 380 <0.9 the tissue is cancerous or precancerous (CIN of all grades).
[0084] In one embodiment, a grading algorithm is incorporated in a data processing unit employed by these systems and methods. The grading algorithm utilizes the pair (R 650 , R 380 ) and classifies the reflections from each site observed into three groups. In the case of cervical tissue, the algorithm classifies reflections for which the pair obeys R 650 <2.9, R 380 >0.1.1 as “healthy tissue” or NED. Similarly, a second group of sites, for which the pair obeys R 650 >3.5, R 380 <0.9 is classified as cancerous or precancerous tissue or CIN. Finally, a third group of tissue, including those tissues for which the reflections pairs obey the relationships 2.9<R 650 <3.5, 0.9<R 380 <0.1.1, is classified as tissue for which a determination cannot be made. An algorithm according to these systems and methods classifies each point in the observed tissue as healthy or unhealthy. If this classification can not be performed for a particular tissue area, that area is segregated into a third, “unclassifiable” class.
[0085] An algorithm according to these systems and methods maps tissue for the presence or absence of a pathology. In one embodiment, an algorithm utilizes an independently determined set of threshold values for R 380 and R 650 . These threshold values are determined in clinical studies from a large number of patients from which both readings of R 380 and R 650 are compared with biopsies taken from the tissues from which these values are determined. The threshold values as well as the actual wavelengths where the reflections are taken (and the normalizing wavelength utilized to determine from I(λ) the normalized reflection R λ ) can vary from the values presented herein, as long as the short wavelengths reflections correlate well with absorption by hemoglobin and the long wavelengths reflections with variations of scattering between healthy and pathological tissues.
[0086] The wavelengths presented in the example above and shown in FIG. 9 are useful in the diagnosis of cervical tissue abnormalities. It is understood, however, that other wavelengths may be useful, particularly when other tissue areas are studied. Furthermore, the critical threshold values of the short and long wavelengths standardized reflections, R, are subject to determination for each type of tissue targeted.
[0087] In another embodiment of the invention, a tissue integral algorithm is used, where the cervix as a whole is examined to determine if a pathology exists without actually obtaining an image of the location of such pathology within the tissue. This algorithm is used as follows. The computer 650 collects the normalized reflection R 650 for all measured sites on the tissue and determine the minimum R 650 (min) of the set {R 650 56 . The computer 650 determines the maximum value R 650 (max) of the set {R 650 }. In one embodiment, if the condition R 650 (max)<1.2R 650 (min) of the set {R 650 } is true (e.g., if all observed values of R 650 are smaller than 120% of the smallest value of R 650 R 650 (min)), then the tissue is free of pathology. If this condition is not met, pathology of some type is indicated, and the subject should be referred for additional diagnostic tests to identify the type and location of the suspected cervical pathology.
[0088] A similar algorithm involving R 380 can be used, whereby the computer 650 determines the minimum R 380 (min) of the set (R 380 }, for the normalized reflection R 380 observed for all tissue locations. The computer 650 determines the maximum value R 380 (max) of the set {R 380 ). In one embodiment, if the condition R 380 (max)<1.20R 380 (min) of the se {R 380 } is true, (e.g., if all observed values of R 380 are smaller than 120% of the smallest value of R 380 , R 380 (min)), then the tissue is free of pathology. IF this condition is not met, pathology of some type is indicated and the subject should be referred for additional diagnostic tests to identify the type and location of the suspected cervical pathology.
[0089] It is understood that an algorithm in which both of the above conditions are met also results in a valid classification of the subject population into healthy and possibly pathological tissue. It should further be clear that an algorithm based on simultaneously satisfying both conditions can be a useful grading system of tissue for the presence or lack of pathology. Such an algorithm can be expected to result in a greater number of “undetermined” cases. However, the confidence level of correctly grading healthy and pathologic tissue is higher that when using either one of the tissue integral algorithms described above individually.
[0090] It should furthermore be evident to those of ordinary skill in these arts that other algorithms can be constructed without departing from the scope of the systems and methods described above but that nonetheless rely upon the fact that scattering from non-pathological tissue at wavelengths between about 600 nm and about 750 nm is consistently greater for pathological tissue than for healthy tissue, or that rely upon the fact that absorption of light in the range of about 370 nm to about 430 nm is greater for pathological tissue than for healthy tissue. Such algorithms, consistent with these systems and methods, are useful in classifying a subject's cervix for the presence or lack thereof of pathological tissue (e.g., a state of health of a subject's cervix). In other embodiments, algorithms can employ data collected at other wavelengths in order to diagnose pathologies of the cervix or pathologies of other body tissues.
[0091] [0091]FIG. 10 shows an illustrative embodiment of a device for determining the presence or absence of pathology in a tissue of the cervix according to the invention. In this figure, a screening device (shown generally at 1200 ) is an integral part of a colposcope 1202 , and is used to make determinations of tissue pathology point by point. A colposcope 1202 is provide with a high intensity light source and optics to view cervical tissue, all included within the colposcope 1202 . The image viewed by an observer 1203 is recorded with a video camera 1210 and recorded for future reference on magnetic media through a video tape recorder 1211 . The instrument depicted in FIG. 10 is used for determining the presence or absence of pathology point by point. Since it is paired with a colposcope 1202 , this embodiment is suitable for use by highly trained professionals, such as gynecologists. A beam splitter 1212 is used to select a site in the target tissue 1213 which is illuminated with white light 1214 from the light source provided in the colposcope 1202 . The position control of the beam splitter (and thus selection of the point examined in the target tissue) is accomplished with a “joystick” 1215 . The optical head 1216 includes a small laser diode (wavelength at about 635 nm) 1217 , having a beam coaxial with the optical head's detection optics. In operation, the red beam is pointed toward the tissue 1213 . Since the optical axis of the laser diode 1217 and the collection optics in the optical head 1216 are the same, the optical head 1216 measures the light reflected from the point illuminated by the red laser diode beam. In order to maintain the calibration of the optical head's sensor 1218 , a white reflector 1219 is provided within the illumination path of the colposcope, to which the operator directs the seeking beam from the laser diode 1217 . The reflectance from the white reflector 1219 is used as a standard for calibrating the sensor 1218 . Such a white reflector can be made from Spectrolon™, from Labsphere Corporation. Alternatively, high purity BaSO 4 reflecting paint from the Kodak Corporation can be applied to a flat surface and used.
[0092] In some embodiments of the invention, a polarizer is interposed in the back scattered beams which considerably reduces the specular reflection from the target tissues. The specular reflection is understood to comprise the light reflected from the thin film of moisture overlaying the target tissue that has not interacted with the underlying tissue.
[0093] In operation, the physician directs the beam 1214 to a specific site on the suspected tissue 1213 . The reflected light from this site is collected by the optical head 1216 . A spectrometer 1220 (which can be either a refractive or dispersive spectrometer) disperses the light so that the intensity of the reflected light at preselected wave lengths can be measured in the detector 1218 . In one illustrative embodiment, three preselected wavelengths are chosen. In certain embodiments, the sensor 1218 comprises a plurality of sensors corresponding in number to the number of preselected wavelengths, so that one sensor is dedicated to each wavelength. The sensor 1218 can be an ICCD, a standard CCD, or any other detector system known in the art or envisioned by those of ordinary skill in these arts.
[0094] Data from the sensor 1218 is analyzed in a computer processor 1221 by applying an algorithm system as described above, and a score is obtained from the data processing that relates to the presence or absence of pathology at the tissue area being illuminated by the laser diode 1217 . This score is graphically represented on a display 1222 . The digital information corresponding to the score is made available electronically for further processing or representation. In certain embodiments, points for which pathological scores are obtained can be represented on a display 1222 as superimposed upon an image provided by a video camera 1210 . In one embodiment, abnormal points are identified graphically with an artificial color not commonly found in cervical tissue, such as shades of green. It will be seen below that other embodiments provide for creation of artificial images or representations of pathologies. The embodiment illustrated in FIG. 10 is suitable for operation by a gynecologist in conjunction with colposcopy. In this setting, the device is well adapted for use as an assisting device for determining which areas of the cervix may require biopsies.
[0095] In one embodiment, the systems and methods of the invention provide a hand held device adapted for illuminating a target tissue with white light and further adapted for detecting reflections or backscattered responses at three specific wavelengths. FIG. 11 shows an illustrative embodiment suitable for screening applications. This embodiment provides features of a visualization colposcope and features of a screening device according to the present invention. In this embodiment, a superimposition of pathological findings on a cervical image may be produced.
[0096] [0096]FIG. 11 shows a colposcreener 1330 consisting of two orthogonal optical paths 1331 and 1332 . The first optical path 1331 includes a plurality of lenses (for example lenses 1333 , 1334 and 1335 ) to image the tissue 1336 so that it can be viewed by an observer 1303 . The second optical path 1332 includes a distal portion 1331 a of the first optical path 1331 (for example lenses 1334 and 1335 ), a beam splitter, 1338 and additional lenses (for example, lenses 1337 and 1339 ). The beam splitter 1338 couples the two optical paths 1331 and 1332 to the distal portion 1331 a of the first optical path 1331 , directing half of the light reflected back from the tissue 1336 to be viewed by the observer 1303 through the ocular 1333 and directing half to a sensor 1340 . The sensor 1340 is coupled to the optics via a mirror 1341 , as shown in FIG. 11, or the sensor 1340 is positioned in the image plane of the second optical path 1332 . In some embodiments, the sensor 1340 comprises a plurality of sensors corresponding in number to the number of preselected wavelengths, so that one sensor is dedicated to each wavelength. The sensor 1340 can be, for example and 1CCD, a standard CCD, or any other detector system known in the art or envisioned by those of ordinary skill in these arts. A filter wheel 1342 is placed in the optical path of the detected beam 1332 , to allow at any given time only one wavelength to reach the detector 1340 . The filter wheel 1342 is mounted on an appropriate driving mechanism, for instance, a stepper motor 1343 , which sequentially indexes the wheel to the appropriate filter.
[0097] Arrangements of filter wheels are shown in more detail in FIGS. 12A, 12B and 12 C. In one embodiment, as shown in FIG. 12A, the filter wheel 1442 has three filters, 1444 , 1445 and 1446 , each capable of blocking most of the spectrum of the reflected beam except around the three selected wavelengths, 380 nm, 480 nm and 650 nm respectively (for the filters 1444 , 1445 and 1446 ). It will be understood by those of ordinary skill in the art that a number of duplications of these filters can be employed for drive simplicity, in particular when the cross section of the reflected beam is narrowed (at the common focal point of the lens on both sides of the filter wheel 1442 ), so as to allow more than three wavelengths to be determined per rotation of the filter wheel 1442 . In such an arrangement in the illustrated embodiment, the number of filter slots would be a multiple of three. In another embodiment, as shown in FIG. 12B, a different filter wheel, 1447 , is used in place of the previously illustrated filter wheel 1442 . The filter wheel 1447 has four positions (or multiples of four). The first three, positions 1448 , 1449 and 1450 , are filters transmitting at 380 nm, 480 nm and 650 nm respectively, as cited above, and a fourth slot, 1451 , being spectrally neutral, namely it is either a simple open slot in the filter wheel 1447 , or a neutral filter that reduces the transmission of all wavelengths by a constant factor. The latter case simplifies the task of maintaining the signals received by the sensor 1440 , (for instance a CCD) under a given threshold and thus preventing sensor's saturation.
[0098] In one embodiment, the shape of the colposcreener 1330 is similar to the device depicted in FIG. 11. FIG. 11 shows a colposcreener 1330 shaped like a gun, with a trigger 1352 used to initiate the processes of obtaining optical reflection data and viewing the tissue 1336 . In operation of this embodiment, pressing the trigger 1352 switches on a light source in the control console 1353 . This light source is concentrated into an optical fiber bundle (not shown) included in the control cable 1354 which connects the control console 1353 and the colposcreener 1330 . The optical fiber bundle 1354 delivers light to the distal end 1355 of the colposcreener 1330 . In one embodiment, a cone of white light 1357 illuminates the target tissue 1336 homogeneously. It is understood that other shapes and configurations of the colposcreener 1330 may be envisioned by those of ordinary skill in these arts without departing from the scope of the systems and methods disclosed herein. Furthermore, while the colposcreener 1330 is adapted for examination of the cervix, other shapes and embodiments consistent with these systems and methods may be devised that are structurally adapted for other anatomic areas.
[0099] [0099]FIG. 11 further shows that light reflected from the tissue is split by the beam splitter 1338 into a viewing beam carried along the optical path 1331 and a detection beam carried along the optical path 1332 . In that manner, the tissue screened is viewed directly through the ocular 1333 while the detection beam is being sequentially scanned for the three wave length discussed above. The tissue is imaged onto the sensor 1340 . In one embodiment the sensor 1340 comprises a CCD array, whereby the light intensity reflected for each point in the tissue is measured. The data from the sensor 1340 is transmitted through a data cable 1356 to a data processing unit 1358 for further analysis. Synchronization signals generated in the control console 1353 provide correct indexing of the streams of data for each one of the three filters in the filter wheel 1342 . This may he achieved by using the signal sent to the stepper motor 1343 to coordinate with the data stream from the sensor 1340 .
[0100] In one illustrative embodiment, the synchronization task is simplified by using the geometry of the filters in the filter wheel 1342 . In this embodiment, the motor 1343 is used in a continuous rather then a stepping manner, thus the filter wheel 1342 rotates continuously. An embodiment using a filter wheel in this way is shown in FIG. 12C, where the filter wheel 1459 is depicted as having three unequal filters 1460 , 1461 and 1462 , separated by unequal spaces 1463 , 1464 and 1465 . In this embodiment, a CCD or a CCD array is advantageously employed as the sensor 1340 , as previously described. Since the CCD has its highest sensitivity in the red part of the spectrum, and the light source is typically richer in the red part of the spectrum as well, the 650 nm red filter 1460 in FIG. 12C is much shorter, with shorter collection time. The short collection time is used to indicate to the data analysis unit 1358 that the red filter 1460 (transmitting selectively at 650 nm) is being used. To better equilibrate the intensities received, the green filter 1461 (transmitting selectively at 480 nm) is larger than the red filter 1460 . The blue filter 1462 (transmitting selectively at 380 nm where the CCD is least sensitive) occupies the longest segment of the circumference. The signals received at various wavelengths are more homogeneous and easier to analyze. Integration times can be adjusted accordingly. The adjustment of the integration time can be keyed on the “No signal” periods between the filters, represented by the unequal spacings 1463 , 1464 and 1465 between the filters.
[0101] In this illustrative approach, the actual normalized intensities, R 380, R 480 and R 650 as discussed above are modified to account for the time variability of data acquisition between the three different filters. Since these factors depend on the specific integration time selected, the normalized reflections R λ provided above are used, understanding that algorithms based on these findings are devised once a calibration for a specific design is available.
[0102] The data received for each one of the three filters is analyzed for each pixel and is displayed on the display monitor 1322 in a dual fashion. The first display generates a Red/Green/Blue image of the tissue by taking the raw data (normalized for spectral differences in the CCD sensitivity as well as variations of integration times when using the filter wheel 1559 shown in FIG. 12C) from each CCD's pixel and presenting it as a normal full color picture. This is achieved with well known “frame grabbing” electronics readily available commercially.
[0103] Each pixel, P ij , has associated with it three values (residing in the grabbed frame), I ij,380 , I ij,480 and I ij,650, from which are derived normalized intensities R ij,380 and R ij,650. A strongly discriminating algorithm selects all pixels P ij for which both of the conditions R ij,650 >3.3 and R ij,380 <0.9, namely those pixels for which a pathology is identified. These pixels form a group Qij of pathological tissue. A “weaker” discrimination defines as “pathological” only those P ij for which R ij,650 >3.3 and the so defined Q ij are then painted on the total image as a pathology.
[0104] The display superimposes an image of all the pixels Q ij having a “pathological” signature on the natural picture of the tissue. This is achieved by selecting a color uncommon to the tissue (such as green, or blue) and painting said all Q ij (pathological) pixels all in the same color, thus obtaining an artificial-looking image of the extent of the pathology in the tissue. The filter depicted in FIG. 12B wherein one of the positions is a neutral filter uses the image generated by the neutral filter (which will appear on the display having shades of gray) as the background image of the tissue on which the pathology is superimposed in any desired color. To maintain the system of FIG. 11 in calibration, a standard white reflector is used as described above for FIG. 10.
[0105] [0105]FIG. 13 depicts an embodiment in which the apparatus is configured as a screening device 1570 without providing for direct visualization of the tissue being screened by an observer. In the illustrative embodiment, the screening optical head 1571 contains an optical train 1572 , an illuminator 1573 , a CCD array 1574 and a filter wheel 1575 . The filter wheel 1575 is rotated as previously described, either continuously or in a stepping fashion with a stepper motor, 1576 . The light source is within the data processing/control console 1577 , and the data is displayed on a display 1578 . Light from the light source is collected into a bundle of optical fibers 1573 which is an integral part of the cable 1579 , between the console 1577 and the screening device 1571 . While FIG. 13 shows the optical fibers 1573 as nested within the screening device 1571 at one location, it is understood that the fibers within the bundle can be arranged circumferentially or in any other geometric arrangement in order to provide homogeneous illumination of the target tissue 1580 .
[0106] [0106]FIG. 14 shows a filter wheel 1600 suitable for use with the device depicted in FIG. 13. The illustrated filter wheel 1600 is configured to select light at wavelengths of 380 nm, 480 nm and 650 nm, with an open area to facilitate synchronization. It should also be evident to practitioners of ordinary skill that any arrangement of filter wheels understood in the art, including those illustrated in FIGS. 12 A- 12 C above, could be used in the depicted system, with the operation of the apparatus being adjusted accordingly.
[0107] In operation the screening device 1571 may be pointed to the target tissue 1580 . The tissue may be illuminated through the optical fiber bundle 1573 and reflections from the tissue may be recorded by the CCD array 1574 at about 380 nm, about 480 nm and about 650 nm. The data processing unit 1577 analyzes the recorded data using any one of the algorithms described above. Tissues with color enhanced pathologies are represented on the display 1578 . In one embodiment of the invention, visual display is not provided and only a reading or printout of the status of the subject (having or nor having a pathology in the target tissue) is presented. In this embodiment, the instrument advantageously uses the above-mentioned tissue integral algorithm. To use this algorithm, the data processing unit 1577 , after obtaining the values R ij,650 and R ij,380, for each pixel P ij , determines the maximum and minimum values obtained for R 650 and R 380 . If the conditions R 650 (max)<1.2R 6 650 (min) and R 380 (max)<1.2 380 (min) are met, the subject is classified free of pathologies. Otherwise, the subject is referred for additional diagnostic evaluation to determine the nature and the extent of the suspected pathology.
[0108] In another illustrative embodiment, depicted in FIG. 15, the filter wheel is eliminated. Further, in lieu of a standard CCD array a color CCD array may be used. In the illustrated embodiment, a screening device 1700 includes three modules 1701 , 1704 and 1703 . The first module, the screening probe 1701 , is operably connected to the second module 1704 through a cable 1703 . The first module 1701 contains a circumferentially arranged optical fiber bundle 1706 for transmitting light to a target 1710 , and an optical path 1702 comprising optical elements for receiving light emitted from the target 1710 . The second module 1704 contains a light source coupled to an optical fiber bundle 1706 . The fibers in the optical fiber bundle 1706 are distributed circumferentially at the distal end of the probe. Furthermore, the second module 1704 contains a data processing unit, including an electronic frame grabbing submodule to process data received from the color CCD array 1900 in the probe module. Results are displayed on the display module 1705 , which is connected to the second module 1704 by way of cable 1707 .
[0109] The color CCD array 1900 , as used in the illustrated embodiment, may be typically divided into pixels each having four elements. FIG. 16 shows a segment of the surface of such an array 1800 . For illustrative purposes, an array of 10×10 elements organized as an array of 5×5 pixels is shown. However, it is understood that such an array can comprise in excess of 500×500 elements and thus more that 250×250 pixels. Each one of the pixels 1801 has two green filters 1802 and 1803 , overlaying two of the elements of the four elements in pixel 1801 . The other two elements, 1804 and 1805 , have respectively a red and a blue filter overlaid thereupon. While the specific filters employed in standard color CCD devices can vary from the three wavelengths selected above, and can vary from manufacturer to manufacturer, standard color CCDs can be used in the invention.
[0110] The operation of the device 1700 depicted in FIG. 15 is similar to the operation of the system depicted in FIG. 13, except that no filter wheel is employed. In contrast to the embodiment depicted in FIG. 13, in the embodiment of FIG. 16 the whole image in three chroma is taken at once, and the frame grabbing module transfers the intensities received for each one of the three colors to a data processing device which undertakes the normalization of the long and short wavelength reflection with the middle of the spectrum responses and proceeds to apply to the two artificial intensities so derived any of the previously described algorithms.
[0111] In the illustrative embodiment, the system optics 1702 images the target tissue 1710 onto the color CCD 1800 , and the signal from each pixel is captured in a frame grabbing device in module 1704 . The intensities registered for the two green filtered elements are averaged and used as the normalization value for the intensities registered for the red filtered element and for the blue filtered element. In this fashion, normalized values R ij (B) and R ij (R) are obtained for each pixel having a row i and a column j. These normalized values respectively represent the normalized reflected intensities in the blue and red part of the spectrum.
[0112] While the filters used in commercial color CCD do not correspond exactly to the wavelength 380 nm and 650 nm mentioned above, and furthermore the bandwidth of those filters are relatively wide, satisfactory calibration and discrimination between pathological and healthy tissue can be achieved. The threshold values can be changed for R(B) and R(R) relative to those shown above for R 380 and R 650 . These values vary somewhat depending on the source of the color CCD. To alleviate the problem of variability, an array of filters with the appropriate fixed wavelengths of about 380 nm, about 480 nm and about 650 nm can be overlaid over a standard CCD array to obtain a screening device that has no moving parts (such as the filter wheel) in some of the embodiments mentioned above. The general algorithm R λ (Max)<αR λ (min) where α>1 and is a function of the specific λ selected is advantageously employed without undue experimentation by ordinary skilled practitioners in these arts to discriminate between healthy and pathological tissue.
[0113] In another illustrative embodiment, these systems and methods are used in conjunction with an acetic acid delivery system, as shown in FIG. 17. FIG. 17 shows a graph 1900 of measured reflectance I, as normalized by the initial reflectance immediately after the application of the acetic acid, as function of time, beginning with the application of an acetic solution to the cervix, at a wavelength of about 600 nm. The graph 1900 has normalized intensity plotted along the vertical axis 1902 and time expressed in seconds plotted along the horizontal axis 1904 . The data collection is achieved by using a single narrow bandpass filter, transmitting around 600 nm, overlaying a CCD FIG. 17 represents measurements from a number of tissue samples (in vivo, followed by determination of the pathology from biopsies). The time dependence of the reflected responses from tissues fall into three well differentiated zones. Healthy (NED) tissues have a response 1910 which is independent of time. CIN II tissue shows an increasing response 1920 for about 30 to 60 seconds, and then the reflectance slowly fades out and returns to normal within about three minutes or a little longer. CIN III tissue shows a response 1930 that includes a strong change with time for the first 20 to 30 seconds, and then, the response 1930 stays strong for longer than about three minutes. FIG. 17 shows that the optical behavior of the various tissue classes following the application of the amplifying agent differentiates between healthy and pathologic tissue from measurements taken during the first 10 to 20 seconds after the application of the amplifying agent (or chemical agent), in this case acetic acid.
[0114] A useful algorithm employs the rate of change of the normalized intensity I with time, dI/dt at between 10 to 20 seconds after the application of the amplifying agent. According to this algorithm, if dI/dt<0.055 sec −1 , the tissue is classified as healthy (NED). If 0.075 sec −1 <dI/dt<0.11 sec −1 , the tissue is classified as CIN II. If di/dt>0.11 sec −1 , the tissue is classified as CIN III. In one embodiment, the higher dI/dt during the first 10 to 20 seconds after the application of the acetic acid solution, the more severe the pathology is.
[0115] In another embodiment, an algorithm involves the measurement of the normalized reflectance after either 10 or 20 seconds from the application of the acetic acid solution. If I is greater than 1.25 after 10 seconds (or about 1.5 after 20 seconds), the tissue is classified as pathologic, and the patient is directed to have a more detailed analysis of the condition, sometimes, including a biopsy. This embodiment is applied, as an example, when the probe is used in true screening situations rather than in more traditional colposcopic examinations.
[0116] In another embodiment, an algorithm is based on the time required to reach a maximum in the back reflected response of the tissue. According to this embodiment, the longer it takes to reach this maximum the more severe the condition, providing, however, that the maximum is more than about 3.0 times the minimum back scattered response for the same tissue. The disadvantage of this approach is that longer exposure may be required, particularly in the case of CIN III, where back scattered responses continue to increase even after more than 200 seconds.
[0117] To shorten that time interval, another algorithm compares the maximum normalized response at 600 nm during any interval of time greater than 10 seconds from the application of the acetic acid solution, to the initial response, and if that response is more than 30% larger than the initial response, the tissue is classified as CIN in general. This algorithm is used when fast classification of cervixes in a screening environment is desired.
[0118] In yet another embodiment of the invention, a screening algorithm takes an initial reading of responses for each point probed prior to the application of the acetic acid, stores the values as a standard set, and then takes a number of images sequentially. The screening algorithm performs a point by point subtraction of the value of the stored initial responses from the responses obtained after the application of the acetic acid. The time dependence for various classes of tissue results in distributions similar to those shown in FIG. 17, except that the scale of the back scattered intensities is now changed. The algorithm utilizes the differential responses of various classes in a manner as described above.
[0119] Apparatus and methods for controlled delivery amount and delivery pattern of a chemical agent are disclosed below. Apparatus and method for accurately and synchronously triggering the optical measurements with regard to the time of delivery of the chemical agent are disclosed below. Image capture software to record time-stamped images and user-defined regions of interest to be defined on a master image is disclosed below. This analysis software automates the calculation and display of acetowhitening characteristics front a motion corrected time-sequence of patient images. This improves the ability to correlate instrument measurements to the pathological evaluation of biopsied tissue.
[0120] In another embodiment of the invention, when using an amplifying agent such as acetic acid, an automated system delivers the amplifying agent to the target tissue. A triggering mechanism applies the chemical reproducibly and eliminates variability of time delays between the application and the start of obtaining optical responses from the target tissue.
[0121] [0121]FIG. 18A shows an illustrative embodiment of a system with a screening probe 2000 similar in construction to the probe shown in FIG. 11. This apparatus and the associated techniques are used to improve the demarcation of a start time and to guarantee the application of a constant volume of acetic acid. Another embodiment is a mucosal atomizer device comprising a 3 cc syringe and 6″ stylet tubing extension nozzle is used to spray 2 cc of 5% acetic acid uniformly onto the surface of the cervix. The distal part 2013 of the probe 2000 is covered with a composite disposable sheath 2011 having attached at its own distal periphery a hollow toroidal structure 2014 . The hollow toroidal structure 2014 contains the chemical agent or amplifying agent, for example, acetic acid at a 3% to 5% concentration. A retractor 2012 compresses the toroidal structure 2014 when the operator is ready to apply the amplifying agent to the target tissue. When the retractor 2012 is retracted using a trigger like mechanism 2015 the toroidal structure 2014 is compressed and its content is sprayed onto the tissue. Simultaneously with the retraction action, the probe is signaled to start taking measurements, by the actuation of a switch 2016 in the handle of the probe. The chemical or amplifying agent is sprayed through a plurality of perforations 2017 as shown in FIG. 18B, a top view of the distal end of the assembled sheath/retractor assembly. To prevent accidental expulsion of the solution, a covering such as an adhesive tape may be attached to the distal end 2013 , covering the toroidal structure 2014 . In one embodiment, the covering may be removed after mounting the sheath on the probe and just prior to the insertion of the probe into a target area such as the vagina. While FIG. 18A depicts a cylindrical structure, it should be apparent to those of ordinary skill in the art that a conical structure can be utilized to improve packaging and nesting of multiple disposable sheaths, and furthermore, that any other structure may be constructed which is adapted for the functions depicted in FIG. 18A and which is further adapted for the anatomic region in which it will be used.
[0122] In the embodiment shown in FIGS. 18B and 18C, the retractor 2012 is designed to leave an optical window 2018 for the reception of responses from the illuminated tissue. Illumination is achieved through circumferentially distributed optical fibers, as previously described in FIG. 11, and the light is transmitted through a transparent part of the peripheral distal end of the retractor 2012 . The toroidal container 2014 for the amplifying agent is affixed to the sheath 2011 , as shown in FIG. 18C, which shows a cross sectional view of the distal end of the sheath/retractor assembly. The toroidal container 2014 is directly attached to the sheath (as shown at 2019 ) or it is affixed in any other suitable way.
[0123] While in FIG. 18A we show a toroidal container 2014 which discharges its content upon compression, it should be clear that other shapes may be useful in the practice of the invention. For instance, the cross section of the toroidal container 2014 can be oval or rectangular. In certain embodiments, the amplifying agent container is constructed as a side mounted syringe having a plunger that causes discharge of the amplifying agent in a spray form, while providing simultaneously a signal to the probe that amplifying agent is applied, and thus providing a starting point for the temporal measurements of reflections from the target tissue. While this figure shows one embodiment of a system for automating the application of the amplifying agent and for standardizing the time lapse between the application of the amplifying agent and the measurement of back scattered responses from the target tissue, it should be evident to a person trained in the art that other mechanisms achieving the same goal can be devised without deviating from the spirit of the invention. Such other applicators could include, but are not limited to, surgical applicators like sponges, cloths or swabs that are made to be retracted after the application of the amplifying solution so leave open the optical path between the tissue and the probe's distal end 2013 .
[0124] When the algorithms use normalized responses, as normalized against time zero, the trigger actuates a timer within the probe controller that sets up a predetermined time interval for the first measurement (typically within 1 second of amplifying agent application). When the algorithm used normalizes responses relative to the response obtained prior to the application of the amplifying agent, an image of the cervix is taken prior to the application and recorded with the frame grabber in the data processing unit 1704 . After the trigger 2016 signals the probe to start taking responses, the responses are taken and normalized (pixel by pixel) and one of the algorithms described above analyzes the data. The data are presented as either a “positive” or “negative” finding for the whole cervix, or alternatively, an artificial image of the pathology is presented for those pixels where the algorithms returned positive findings. This image is superimposed on a visual image of the cervix and recorded to allow post screening accurate location of tissue requiring subsequent biopsy.
[0125] In some embodiments of the invention, spatial data are averaged over groups of neighboring pixels (between 2×2 to 6×6), and these averages (both for the standardizing measurement, or normalizing measurement) are used as normalized intensities. Other methods for averaging or normalizing spatial data can be used. Different methods of normalizing can be related to the resolution of the CCD used in that specific interest.
[0126] In another embodiment, a plurality of chemical agents are applied to a specimen, either simultaneously or sequentially. The use of multiple chemical agents causes any of a number of different effects. One chemical agent is used to control or change pH (e.g., hydrogen ion concentration), change the concentration of one or more other ionic species, or change an osmotic pressure, while another chemical agent is used to induce another sort of change, for example, staining a material, activating or passivating a material, or otherwise changing a physical property of a material.
[0127] Application of an exogenous contrast agent when combined with the activation of an endogenous contrast agent gives rise to a combined contrast that provides more valuable information than either agent alone. For example, application of acetic acid to epithelial tissue results in time-dependent effects in the fluorescence emission spectrum resulting from activation of endogenous native fluorophores in tissue, such as NADH, collagen, elastin, favins (e.g., FAD) or porphyrins.
[0128] This effect arises from at least two different sources. One source is the penetration of the acetic acid into the tissue followed by the resulting pH change on the spectral properties of the endogenious fluorophore. The effect of pH is shown for NADH in FIG. 19. FIG. 19 shows four absorption spectra recorded over the wavelength range of about 320 nm to about 600 nm. The absorbance is plotted along the vertical axis 2102 and the wavelength in nm is plotted along the horizontal axis 2104 . A baseline spectrum 2110 is taken for a 5% acetic acid solution containing no NADH, and shows little absorption. The spectrum 2120 is taken at pH 4.0 and shows two strong absorption peaks at approximately 350 nm and at approximately 430 nm. The spectrum 2130 is taken at pH 5.0 and shows a strong absorption peak at approximately 350 nm and a much weaker absorption peak at approximately 430 nm as compared to the pH 4.0 spectrum. The spectrum 2140 is taken at pH 7.0 and shows a strong absorption peak at approximately 350 nm and virtually no absorption peak at approximately 430 nm as compared to the pH 4.0 spectrum. The spectral properties of NADH absorption are significantly affected by pH. Since absorption is the first step in fluorescence, it is reasonable to expect that pH will affect the emitted fluorescence as well.
[0129] Acetic acid penetrates into different types of tissues and cells at different rates depending on the type of tissue present. In addition, the amount of NADH in cells typically differs according to the type of cell and its metabolic state. Consequently the kinetics of this pH response can be indicative of the tissue or cell type and its metabolic condition.
[0130] Acetic acid causes acetowhitening when applied to certain tissues, such as epithelial surfaces. The acetowhitening effect is produced by light scattering changes. These changes have further secondary effects on spectral measurements, such as induced fluorescence. Changes in the induced fluorescence result from either of two sources. One source is the direct effect of acetowhitening on the penetration of the UV excitation light. A second effect results from the light scattering on the observed spectral shape of the emitted fluorescence. Since the acetowhitening is time dependent, these secondary effects are time dependent as well.
[0131] Temporal changes observed in fluorescence emission following the application of acetic acid to a cell suspension is shown in FIG. 20. FIG. 20 shows a graph 2200 of spectra measured as a function of time after application of acetic acid. The spectral intensity is plotted along the vertical axis 2202 and the wavelength in nm is plotted along the horizontal axis 2204 . Curve 2210 is recorded at the time of application of the acetic acid solution. Curve 2220 is measured 0.5 minutes after acetic acid application. Curves 2230 , 2240 , 2250 and 2260 are recorded 1, 2, 3, and 7 minutes after acetic acid application, respectively. The fluorescence spectrum originally observed at the time of acetic acid application quickly decreases in intensity, and recovers slowly thereafter.
[0132] Fluorescence spectra in cervical tissue have similar changes over time following application of acetic acid. FIG. 21 is a graph 2300 that shows the changes in fluorescence spectra before (curve 2310 ) and after (curve 2320 ) application of acetic acid to cervical tissue. The spectral intensity is plotted along the vertical axis 2302 and the wavelength in nm is plotted along the horizontal axis 2304 . Note that the fluorescent intensity at some wavelengths below about 450 nm changes more substantially than the intensity at wavelengths above about 450 nm. Since the time-course of those changes is related to the type of tissue being probed (as described above) these spectral differences can differentiate the tripe of tissue under study.
[0133] Relative motion between the patient and the colposcope can cause problems with registration of the different images for that patient during analysis. A robust motion detection and correction technique is disclosed below. This technique uses the cross-correlation of two successive images to determine global motion. The cross-correlation is computed in the Fourier domain using a fast Fourier transform. In one embodiment, the image registration technique is used after the specimen data is collected. In an alternative embodiment, systems according to the invention incorporate the technique on-line, as it does not require excessive processing overhead.
[0134] Image processing is used to extract relevant features from the data observed and recorded using the systems and methods of the invention. Image processing techniques that can be applied include, but are not limited to, color space transformations, filtering, artifact detection and removal, image enhancement, extraction of three-dimensional shape information, manipulations using mathematical morphology, and segmentation.
[0135] A color space transformation is intended to transform the three primary colors, red (R), blue (B), and green (G), into a new set of colors or values using a kinear or non-linear transformation. A number of well-known transformations interconvert R, G, B and luminance/chrominance components, for example, as used in converting light recorded in a camera into broadcast signals, and rendering broadcast signals on a television display.
[0136] Filtering is useful in image processing, and is used to suppress noise and unwanted interfering signals. Many filters and filtering processes are known. Filters can include both hardware filters such as optical filters and electronic filters, as well as filters applied in software, such as digital filters. For example, the median filter replaces every pixel of an image with the median value computed in a given neighborhood of the pixel.
[0137] Artifact detection and removal is used to eliminate spurious information from a set of data to be analyzed. Some artifacts, such as portions of an optical field of view that are extransous, may be eliminated by changing the height and or width of the field of view, or by masking portions of the field of view, for example when a physician observes that the field of view includes material that is not of interest.
[0138] Image enhancement can include processing to improve the visual contrast between adjacent portions of an image. A number of known techniques are available, including applying a weighting function to a range of intensities or gray scale values.
[0139] Extraction of three-dimensional shape information is useful in representing a surface that is non-planar in two-dimensions. An example is computing the three-dimensional features of the cervix to account for the nonuniformities of illuminating a three-dimensional surface.
[0140] Manipulations using mathematical morphology are well-known. Image processing using the principles of mathematical morphology provides a representation of an image in a form that simplifies the computational burden in image processing.
[0141] Morphological operators are based on the mathematics of set theory. A set in mathematical morphology represents the shape of an object in an image. In the case of two-dimensional (binary) images, the sets are members of Z 2 and each element represents the (x,y) coordinates of a black (or white, depending on the convention) pixel in the image. Gray-scale, color, time-varying components, or any vector-valued information can be included by extending the Euclidean space size.
[0142] The basic morphological operators are described in terms of gray-scale images below. Let the input image be described by a function f:Z 2 →R. Gray-scale dilation is defined as:
( f⊕b )( v,w )=max{ f ( v−x,w−y )+ b ( x,y )|( v−x,w−y )ε D f ;( x,y )ε D b ,}
[0143] where b:Z 2 →R is a function called a structuring element. D f is the domain of f and D b is the domain of b. The structuring element has a key role in this operator: it is added morphologically to the image at each pixel location.
[0144] The opposite of dilation is erosion. The erosion operator is defined as:
( f⊕b )( v,w )=min{ f ( v+x,w+y )− b ( x,y )|( v+x,w+y )ε D f ;( x,y )ε D b }
[0145] In this case the structuring element is subtracted morphologically from the image at each pixel location.
[0146] Two important morphological operators are defined using erosion and dilation: opening and closing. They are respectively defined as:
f∘b =( fΘb )⊕ b
f•b =( f⊕b )Θ b.
[0147] The effect of opening is to preserve holes and remove peaks, while closing preserves peaks and closes holes according to the structuring element's shape. The structuring element b is fitted from inside (below an image) in the opening case and fitted from outside (above an image) in the closing case.
[0148] A morphological filter can be defined as any combination of morphological operators. For example (f∘b)•b, opening followed by closing, or (f•b)∘b, closing followed by opening. These operators are neither commutative, no associative or distributive and the filtering operators cited above are not equal. One of the following two filters is used:
f_b = 1 2 [ ( f · b ) + ( f ∘ b ) ] ,
and f_b = 1 2 [ ( f ∘ b ) · b + ( f · b ) ∘ b ]
[0149] where the _ symbol means filtered by b.
[0150] A more elegant way to achieve a morphological filtering with better geometrical characteristics is to use geodesic reconstruction after a morphological opening. The reconstruction process uses geodesic dilation which for gray-scale images is defined by:
( f⊕b ) (1) ( v,w )=min{( f⊕b )( v,w ), f 0 ( v,w )},( v,w )ε D f ,
[0151] where f 0 is the reference image, usually the original image, and g is a small structuring element, usually a four pixel (cross) or eight pixel (square) connected element. Geodesic reconstruction is obtained by repeating the geodesic dilation n times ((f ⊕b) (n) ) until idempotency is reached. The geodesic reconstruction is then written:
Rg =( f⊕b (i) , with ( f⊕b ) (i+1) =( f⊕b ) (i)
[0152] An equivalent operator can be defined for reconstruction after morphological closing which uses geodesic erosion. For gray-scale images it is defined as:
( f — b ) (1) ( v,w )=max{( f — b )( v,w ), f 0 ( v,w )},( v,w )ε D f
[0153] An example of geodesic reconstruction after morphological opening suppresses the square shape deformation introduced by the opening process. These geodesic reconstruction operators significantly improve any filtering process for a modest additional computation time.
[0154] The most natural example of diffusion process is heat transfer inside matter. This physical phenomenon is mathematically expressed by the following partial differential equations:
q = - k ∇ T ,
cp ∂ T ∂ t = - ∇ · q + f ,
[0155] leading to the following second order elliptic equation:
cp ∂ T ∂ t = - ∇ · ( k ∇ T ) + f ,
[0156] Heat transfer involves a thermal flux q. The whole system must obey the law of energy conservation. The symbol ∇ is the differential operator, which is defined as ∇=(∂/∂x I , . . . ∂/∂x d ). The parameter p is the density of the medium, k is the thermal conductivity, c is the specific heat capacity, and f the capacity of internal heat sources. An analogy exists between temperature variation and value variation in images. The basic formulation is obtained when the medium is assumed to be homogeneous, without sources and with constant conductivity.
[0157] In image processing applications the ideal objective is to obtain an image where only strong edges are preserved while noise and small structures are smoothed out. Diffusion is used as an edge preserving filtering method. The thermal conductivity is replaced by a conductivity function which adapts the diffusion to the local gradient: decreasing diffusion for increasing gradient. The above diffusion equation becomes:
∂ v ∂ t = ∇ · ( D ∇ u ) ,
[0158] where v(x,t) is the signal value at time t and position x, and D is a conductivity matrix. The latter defines the type of diffusion:
[0159] if D reduces to a consistent value k then the diffusion is isotropic.
[0160] if D reduces to a nonlinear function g(·) then the diffusion is nonlinear isotropic,
[0161] if D is a tensor whose elements are functions g ij (·) then the diffusion is anisotropic.
[0162] The analysis uses the case where D=g(·), and the following conductivity function:
g ( ∇ υ ) = { 1 if ∇ υ ≤ k o . k o / ∇ υ if ∇ υ > k o . ,
Φ f ( ∇ υ ) = { 1 if ∇ υ ≤ k o . 0 if ∇ υ > k o . ,
[0163] Histogram equalization re-assigns pixel values in order to obtain a uniform distribution. Let υ(x) be the pixel value at location x and P(υ) be the probability density function associated to υ. The following transformation is used:
υ eq (υ)=∫ P ( s ) ds
[0164] where 0 ≦υ≦1. In the discrete case, the uniform distribution is only approximated and the following equation is used:
u k , eq = ∑ j = 0 k n j n ,
[0165] where n is the total number of pixels and n j the number of pixels with value equal to j.
[0166] The fitting technique used is called linear least squares. The idea is to fit a linear combination of arbitrary functions (linear or nonlinear) given by:
l ( x ) = ∑ k = 0 M - 1 α k f k ( x ) ,
[0167] where x is an N-dimensional coordinate vector (N=2 in the case of images), to a set of data l i (x i ), with i=0 . . . , n−1. In one embodiment, the following series of functions are used:
1, x,x 2 ,x 3
[0168] in the 1-D case and:
1, x,y,x 2 ,xy,y 2 ,x 3 ,x 2 y,xy 2 ,y 3
[0169] in the 2-D case.
[0170] The fitting criteria is the minimization of the following least-square error:
x 2 = ∑ i = 0 n - 1 [ l i - ∑ K = 0 M - 1 α k f k ( x i ) σ i ] 2
[0171] where σ i is the measurement variance at location x i . In one embodiment, set σ i −1, ∀i=1, . . . , n−1.
[0172] By defining the n×M matrix A whose elements A ij are given by:
A ij =f j ( x i ),
[0173] and the vector b of length n whose elements b i are given by b i =l i , then the following system must be solved:
a =( A T A ) −1 A T .b,
[0174] where a=[σ 0 . . . σ m−1 ]. Since the A T A product is positive definite, Cholesky decomposition can be used to compute the inverse.
[0175] Segmentation is a morphological technique that splits an image into different regions according to a pre-defined criterion. In the analysis of the state of health of a biological specimen, it is meaningful to compare the properties of different areas of the specimen. Segmentation is a method that directly provides information on how many regions are present in the image of a specimen, and the location of each region.
[0176] In one embodiment colposcopic images are segmented to track regions in a time series of images. Relevant features are extracted from the labeled regions and their evolution is analyzed as a function of time, to measure and localize acetowhitening effects. Colposcopic images are segmented using a watershed based algorithm. An efficient pre-processing scheme is used, as are two region merging techniques. The use of markers to track the segmentation in time-series of images is used, and the problem of global motion and local deformations related to the precise tracking of these markers is discussed.
[0177] A segmentation scheme for colposcopic images separates the image of the cervix into a number of regions according to an intensity criterion. Segmentation techniques are well known in the mathematical morphology arts. In one embodiment, the object (e.g., the cervix) is known and multiple regions with different intensity content within the cervix are to be identified.
[0178] A technique based on the structural and spatial information rather than on the spectral information is suited to analyze colposcopic images. One approach uses the watershed technique. The watershed technique uses structural information. The watershed technique provides a fine to coarse segmentation of an image in combination with region merging techniques. The flooding technique views a gray-level image as a 3-dimensional surface and progressively floods this surface from below. Each local minimum in the surface is thought of as a hole. A rising water level floods a region as soon as a hypothetical water level reaches the associated minimum. FIG. 22 illustrates this concept on a 1-D signal. The arrows 2402 a - 2402 d show the flooding origins and directions and the solid lines 2406 a - 2406 d are the watersheds. The flooded minima are called catchment basins and the borders between neighboring, basins are called watersheds. Only the catchment basins are of interest. They constitute the segmented image. Fast implementations use first-in-first-out (FIFO) queues and sorted data.
[0179] [0179]FIG. 23 is a graph 2500 of a signal 2510 and its first derivative 2520 , both plotted with amplitude as a vertical axis 2502 and position as a horizontal axis 2504 . FIG. 23 shows a signal 2510 used to represent watersheds with three distinct regions (hole 2512 , plateau 2514 , and peak 2516 ) and its derivative function 2520 , or gradient. Image segmentation with the watershed transform is performed on the image gradient 2520 . The signal shows three distinct regions, and the direct watershed transform would produce a one lowest region. The gradient 2520 separates the signal into its three regions. An analogous principle holds for two-dimensional signals, i.e. images.
[0180] [0180]FIG. 24 shows a graph 2600 of a sigmoidal scaling function 2610 used to enhance the contrast between light and dark regions of an image. The sigmoidal scaling function 2610 is plotted as output along a vertical axis 2602 as a function of an input that is indicated along a horizontal axis 2604 . The use of the watershed transform often leads to a severe over-segmentation. Pre-processing is performed to reduce the number of regions in a segmented image. In one embodiment, a pre-processing scheme reduces the number of regions from several thousand to several hundreds:
[0181] An algorithm that treats images to provide a segmented image includes the following steps:
[0182] computing luminance component L*;
[0183] performing 3-D shape compensation;
[0184] performing sigmoidal scaling;
[0185] morphological closing/opening with a cylindrical structural element;
[0186] performing geodesic reconstruction;
[0187] computing image gradient;
[0188] computing threshold gradient;.
[0189] performing closing; and
[0190] performing geodesic reconstruction of the gradient image.
[0191] The uniform luminance component L* is well adapted to the segmentation process, and is computed for an image of interest.
[0192] 3-D shape compensation removes an artifact (e.g., a stair-case effect) in the segmented image. The illumination is non-uniform when falling on a curved surface (e.g., the cervix), which in turn influences the gradient values used for the segmentation.
[0193] A sigmoidal scaling function is used to improve the contrast between light and dark regions. FIG. 24 is a graph of a scaled sigmoid, used in this study. The sigmoid increases contrast in the median intensity range by providing a larger number of quantification levels. Applying a sigmoidal scaling function causes dark and very light areas to exhibit diminished contract, while the limit between light and dark regions is enhanced.
[0194] Closing and opening morphological operators, respectively, are used to suppress small regions corresponding to holes or peaks in the images. The geodesic reconstruction keeps the geometrical aspect of the image as close as possible to that of the original image. A morphological closing with geodesic reconstruction is performed on the gradient of the filtered image to remove plateaus, which are visualized as separate regions in the watershed transform. The diameter of the cylinder used as structuring element defines the minimum size of the regions in the segmented image.
[0195] Finite-element approximations are used to compute derivatives. Alternative approaches involve using a Sobel operator, which is a 3×3 filter. Another alternative is the use of a local cubic polynomial approximation, which is a 5×5 filters. Before processing the gradient for the watershed extraction, application of a threshold removes small values.
[0196] In one embodiment, the gradient is computed using cubic mean-square approximation. In t another embodiment, a morphological closing/opening filter with geodesic reconstruction is first applied and then the gradient is computed. Spurious regions are smoothed out and contrast enhanced in large regions by both methods.
[0197] In one embodiment, the watershed algorithm is modified as follows. The data is represented in floating point, and the interval steps between successive flooded levels is not uniform. Also, each watershed pixel is merged into a neighboring region according to a nearest neighbor criterion.
[0198] The region merging step following the watershed transform step reduces over-segmentation. In one embodiment, neighboring regions are merged if an intensity change along their border is greater than a given threshold. Alternatively, neighboring regions are merged if a difference in mean intensity value is greater than a given threshold.
[0199] In both embodiments, a map of all border pixels is used. For each segment, a computer computes the difference between the mean value of pixels of each of the two regions under consideration. If the absolute value is below a given value, the segment is removed from the
[0200] An alternative merging algorithm uses the same routines. The alternative algorithm uses the mean value image as input in place of the original image. Since all pixels in a region have the same (mean) value, the algorithm works differently, in that border segments are suppressed if the difference in mean value between neighboring regions is smaller than a given threshold. A morphological distance is an approximation of the distance, in pixels, from a pixel to the nearest segment border. A method to use markers to track the segmentation in time series of images is now presented. The extraction of markers is necessary in order to initialize the flooding process in the watershed transform computed in successive images (e.g., in time-series).
[0201] The approach used comprises the steps of finding pixels having minimum value for each region, and selecting the minimum with the largest morphological distance for each region.
[0202] The first step selects the minimum value as an initial marker, since the flooding used in the watersheds start at local minima. The pixel with minimum value and largest morphological distance is used to avoid a small deformation of a region pushing a marker outside of the region.
[0203] A homotopy modification of the gradient image obtained with the markers is used to suppress catchment basins corresponding to minima that have not been marked, in order to speed up the computation. The homotopy modification of v is the geodesic reconstruction of v (mask) from {acute over (υ)} (marker).
υ ~ ( κ , l ) = ( υ ( κ , l ) if ( κ , l ) ∈ M max u υ ( κ , l ) otherwise .
[0204] In one embodiment, more than one marker per region is considered. Pixels having a morphological distance greater than a given value (typically 2-3) or being at least equal to the largest morphological distance within a given region are considered. These markers are used to
[0205] In one embodiment, more than one marker per region is considered. Pixels having a morphological distance greater than a given value (typically 2-3) or being at least equal to the largest morphological distance within a given region are considered. These markers are used to zero out gradient values in the following image, in order to reduce influence of local maxima on the homotopy modification. It is assumed that the borders between neighboring regions are located somewhere between the marked regions.
[0206] Further, the markers are used to initialize the watershed algorithm with the gradient image of the next image. Tracking schemes are employed to take into account global and local motion.
[0207] One illustrative tracking scheme for the detection of patient motion during an acquisition cycle uses the cross-correlation of two sub-images of two successive images to determine the global motion. An alternative algorithm is used to track motion for segmentation tasks.
[0208] Typically, images of specimens exhibit large homogeneous regions which are difficult to track. Structural information is used to improve motion tracking. Derivatives are used instead of the original image. Using the gradient improves the system's sensitivity to glare, while the use of the sum of the gradients in both the x and y directions highlights low-contrast structures. Using the Laplacian operator (the sum of second derivatives) provides similar results. Applying a low-pass filter before computing the derivatives yields results similar to the Laplacian of Gaussian used for edge detection. The low pass filter suppresses noise and smoothes out glare.
[0209] The embodiment further comprises three modifications. The true cross-correlation of successive images is computed in a 512×512 pixels window. The two windows used for each image are different and are of sizes 302×302 and 210×210, respectively. A Hamming window is used to extract these two signals. The two windows have different sizes to make sure that the second signal is completely contained in the first one, and the use of a Hamming window avoids small oscillations, especially at the transition of the selected signals and the zero-padded areas. The equations used for the motion detection are given below.
[0210] Optical flow algorithms are used to measure local motions. In order to save computation time, the optical flow is computed only for the markers. Optical flow is defined as the distribution of apparent velocities of movement of brightness patterns in an image, and is used to reconstruct three-dimensional surfaces in medical imaging applications.
[0211] Additional embodiments of motion detection algorithms include the following steps: implementation of a local deformation tracking system for improving the precision of marker tracking; extraction of feature signals from the series of segmentation results; analysis of feature signals and classification into groups of interest; and use of group information to correlate the evolution with the histology.
[0212] For motion detection, only a single frame is used. The three RGB color components are transformed into a single intensity component using the following relationship:
I= 0.2999· R+ 0.587· G+ 0.114· B
[0213] In order to suppress high-frequencies due to noise and to the interlaced video signals, we apply a Gaussian low-pass filter to the intensity component:
g ( x → ) = 1 2 πσ 2 exp ( ( x → - μ → ) T · ( x → - μ → ) 2 σ 2 )
[0214] Where {right arrow over (μ)} is the center (mean value) of the Gaussian and σ is its standard deviation. Finally, we use only derivative information to compute the translation parameters, either the sum of
derivatives ∂ ∂ x + ∂ ∂ y or the Laplacian ∂ 2 ∂ x 2 + ∂ 2 ∂ y 2 .
[0215] Motion can be detected using a cross-correlation operator applied to two successive images in a sequence.
[0216] The cross-correlation is computed in the Fourier domain using a fast Fourier transform. The following relationship is used:
Φ= X·Y*
[0217] where Φ, X, and Y are the Fourier transform of the cross-correlation function, the first, and the second signal, respectively. The * symbol represents the complex conjugate. Note that the cross-correlation of two signals of length N 1 and N 2 provides N 1 +N 2 −1 values and therefore, in order to avoid aligning problems due to under-sampling, the two signals must be padded with zeros up to N 1 +N 2 −1 samples.
[0218] For discrete signals (i.e. sampled and quantized signals), the discrete Fourier transform (DFT) and the inverse discrete Fourier transform (IDFT) are given respectively by:
v ( k , l ) = ∑ m = 0 N - 1 ∑ n = 0 M - 1 u ( m , n ) exp ( - j2π mk N ) exp ( - j2π nl M ) u ( m , n ) = 1 NM ∑ k = 0 n - 1 ∑ l = 0 M - 1 v ( m , n ) exp ( j2π mk N ) exp ( j2π nl M )
[0219] This transform expands the signal onto an orthonormal basis of exponential functions. Once the inverse discrete transform is computed, the location of the maximum value corresponds to the translation necessary to align both images.
[0220] Different types of windows are used for spectral analysis, when only part of a signal is analyzed. The goal is to avoid oscillation around discontinuities (Gibbs phenomenon). A Hamming window can be used, which is given by the following relationship:
ω h ( k )=½[1+cos (2π k/N )]
[0221] where N is the number of samples, k is the sample index, and −N/2<=k<=−N/2. In the frequency domain, the Fourier transform of the signal is convolved with the Fourier transform of the Hamming window. For the two-dimensional case the Hamming window is constructed as a separable function, i.e. ω h (k,I)=ω h (k)·ω h (k), where (k,I) are the pixel coordinates.
[0222] As mentioned above, in some embodiments, the cross-correlation of the sum-of-derivatives images is the basis of a motion detection algorithm.
[0223] The cross-correlation of two images in a sequence provides information about the translation necessary to obtain the best match in the inner-product sense. However, this does not necessarily mean that the two images are perfectly aligned. A validation method is necessary to measure the “quality” of the matching.
[0224] The Sobel operator is given by:
fs = 1 8 ( - 1 0 1 - 2 0 2 - 1 0 1 )
[0225] This filter is obtained by convolving the finite element approximation to derivatives with a weight matrix:
fs = 1 2 ( 0 0 0 - 1 0 1 0 0 0 ) ** 1 4 ( 0 1 0 0 2 0 0 1 0 )
[0226] where ** is the two-dimensional convolution. The second filter in Equation 2 is a low-pass filter in the direction perpendicular to the derivative operator, which renders the filter less sensitive to noise. The derivative along the y-axis is obtained by using the transposed version of the Sobel operator.
[0227] Another way to compute derivatives is to use a local polynomial approximation by minimizing the mean-square error (MSE) with the underlying image pixels. The approximation is given by:
υ ( κ , t ) ≈ ∑ i = 0 8 b i φ i ( κ , t )
[0228] where (k,I) are the coordinates in the local 5×5 domain centered on the current pixel. The b i coefficients are the optimal weights in the MSE sense and the Φ i are orthogonal polynomials (1, k, l, k 2 −⅔, l 2 −⅔, kl, (k 2 −⅔)l, (l 2 −⅔)k, (k 2 −⅔)(l 2 −⅔)). The minimization of the MSE leads to the following filter for the first derivatives:
f ρ = 1 50 ( - 2 - 1 0 1 2 - 2 - 1 0 1 2 - 2 - 1 0 1 2 - 2 - 1 0 1 2 - 2 - 1 0 1 2 ) - 17 300 ( - 1 2 0 - 2 1 - 1 2 0 - 2 1 - 1 2 0 - 2 1 - 1 2 0 - 2 1 - 1 2 0 - 2 1 ) + 1 144 ( 4 2 0 - 2 - 4 - 2 - 1 0 1 2 - 4 - 2 0 2 4 - 2 - 1 0 1 2 4 2 0 - 2 - 4 )
[0229] The center of each image is divided into an 8×8 array of blocks of size 32×32. The arrays is chosen to avoid the image borders. The borders can contain extraneous material, that is, not part of the cervix. In normal use, the physician attempts to keep the cervix in the middle of the image.
[0230] For each of the blocks the normalized inner product with the corresponding block in the adjacent motion compensated image is computed:
P i , j = ∑ X ∈ B i , j I 2 ( x ) · I 2 ( x ) ∑ x ∈ B i , j I 1 2 ( x ) · ∑ x ∈ B i , j I 2 2 ( x )
[0231] where B ij ⊂ N 2 is the domain of definition of block (ij), and I 1,2 are the two processed images. The absolute value of P ij is used as a quality measure.
[0232] The method is used for series of 28 images and the motion is estimated for each of them, except for the first one. Once the motion parameters are determined, the frame is shifted to its computed “correct” location and the above block-based correlation is computed with the previous shifted image. The result obtained when using the intensity values for each image is plotted with the x-axis corresponding to the different blocks while the y-axis corresponds to the different images. For the example presented above, the shifted images match perfectly and the output is zero intensity everywhere.
[0233] In an alternative embodiment, in which edge information is the only information used in the matching correlation, the intensity images are replaced with sum-of-derivatives images. To date, this embodiment has provided less favorable motion compensation than the other embodiment. However, the sum of derivatives approach appears to provide better identification of sudden or gross motion.
[0234] While the invention has been particularly showing and described with reference to specific preferred embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
|
The invention provides methods and systems for diagnosing disease in a sample by monitoring optical signals produced by samples in response to the chemical agents. Preferred methods comprise application of multiple chemical agents that interact to alter an optical signal from the sample. Methods and systems of the invention also comprise monitoring an optical signal from an endogenous chromophore upon application of a chemical agent to a sample. Methods and systems of the invention also comprise the use of triggers, atomizers and image alignment to enhance the results of methods described herein.
| 0
|
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the filing benefit under 35 U.S.C. §119(e) of provisional U.S. Patent Application Ser. No. 61/197,074 filed on Oct. 23, 2008, as well as International Patent Application No. PCT/US09/61737, both of which are incorporated herein in their entirety.
FIELD OF INVENTION
[0002] The present invention relates to an apparatus for an epicyclic joint. More specifically, the present invention provides a wide angle, constant power, multi-axis joint with epicyclic gearing.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0003] No federal funds were used to develop or create the invention disclosed and described in the patent application.
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISK APPENDIX
[0004] Not Applicable
AUTHORIZATION PURSUANT TO 37 C.F.R. §1.72(d)
[0005] A portion of the disclosure of this patent document contains material which is subject to copyright and trademark protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent file or records, but otherwise reserves all copyrights whatsoever.
BRIEF DESCRIPTION OF THE FIGURES
[0006] In order that the advantages of the invention will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered limited of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings.
[0007] FIG. 1 provides a perspective view of one embodiment of a multi-axis epicyclic joint not rotated about either axis of rotation.
[0008] FIG. 2 provides another perspective view of one embodiment of a multi-axis epicyclic joint at an extreme position about the first axis of rotation and not rotated about the second axis of rotation.
[0009] FIG. 3 provides another perspective view of one embodiment of a multi-axis epicyclic joint not rotated about the first axis of rotation and at an extreme position about the second axis of rotation.
[0010] FIG. 4 provides another perspective view of one embodiment of a multi-axis epicyclic joint at an extreme position about the first axis of rotation and an extreme position about the second axis of rotation.
[0011] FIG. 5A provides a perspective view of one embodiment of a multi-axis epicyclic joint at an intermediate position about the first axis of rotation and an intermediate position about the second axis of rotation.
[0012] FIG. 5B provides another perspective view of one embodiment of a multi-axis epicyclic joint at an intermediate position about the first axis of rotation and an intermediate position about the second axis of rotation.
[0013] FIG. 6A provides a detailed view of one embodiment of a center frame that may be used with a multi-axis epicyclic joint.
[0014] FIG. 6B provides a partial exploded view of one embodiment of a center frame that may be used with a multi-axis epicyclic joint.
[0015] FIG. 7A provides an end view of one embodiment of a planetary gear head that may be used with a multi-axis epicyclic joint.
[0016] FIG. 7B provides a perspective view of one embodiment of a planetary gear head that may be used with a multi-axis epicyclic joint.
DETAILED DESCRIPTION LISTING OF ELEMENTS
[0017]
[0000]
ELEMENT DESCRIPTION
ELEMENT #
Epicyclic joint
10
First axis of rotation
12
Second axis of rotation
14
First frame
20
First frame splitter support
22
Input shaft
23a
Input gear
23b
Right split shaft
24a
First right split gear
24b
Second right split gear
24c
Left split shaft
25a
First left split gear
25b
Second left split gear
25c
Right transfer support
26
Right transfer shaft
27a
First right transfer gear
27b
Second right transfer gear
27c
Left transfer support
28
Left transfer shaft
29a
First left transfer gear
29b
Second left transfer gear
29c
Center frame
30
Right center shaft
31a
First right miter gear
31b
Second right miter gear
31c
Right planetary gear head
32
Right spur gear
33
Left center shaft
35a
First left miter gear
35b
Second left miter gear
35c
Left planetary gear head
36
Left spur gear
37
Center frame journal
38
Top center shaft
41a
First top miter gear
41b
Second top miter gear
41c
Top planetary gear head
42
Top spur gear
43
Bottom center shaft
45a
First bottom miter gear
45b
Second bottom miter gear
45c
Bottom planetary gear head
46
Bottom spur gear
47
First compensation shaft support
52
First compensation shaft
53a
First compensation gear
53b
Second compensation shaft support
54
Second compensation shaft
55a
Second compensation gear
55b
Second frame
60
Second frame splitter support
62
Output shaft
63a
Output gear
63b
Top split shaft
64a
First top split gear
64b
Second top split gear
64c
Bottom split shaft
65a
First bottom split gear
65b
Second bottom split gear
65c
Top transfer support
66
Top transfer shaft
67a
First top transfer gear
67b
Second top transfer gear
67c
Bottom transfer support
68
Bottom transfer shaft
69a
First bottom transfer gear
69b
Second bottom transfer gear
69c
Planetary gear head
70
Input shaft
71
Sun gear
72
Planet carrier
73
Planet gear
74
Annulus
75
Annulus recess
76
DETAILED DESCRIPTION
[0018] Before the various embodiments of the present invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangements of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that phraseology and terminology used herein with reference to device or element orientation (such as, for example, terms like “front”, “back”, “up”, “down”, “top”, “bottom”, and the like) are only used to simplify description of the present invention, and do not alone indicate or imply that the device or element referred to must have a particular orientation. In addition, terms such as “first”, “second”, and “third” are used herein and in the appended claims for purposes of description and are not intended to indicate or imply relative importance or significance.
General Description of the Components
[0019] A description of the several components required for one embodiment of the epicyclic joint follows. A more detailed description of the operation and relation of the several elements are disclosed in the figures and the remainder of the specification.
[0020] It is contemplated that one type of epicyclic gearing system that may be used with the epicyclic joint 10 is a planetary gearing system. Planetary gearing systems typically include one sun gear and a plurality of planet gears. Such gearing systems are well known to those skilled in the art and therefore will not be described in further detail herein for purposes of clarity. U.S. Pat. Nos. 4,644,822, 4,618,022, and 4,727,954, all of which are incorporated by reference herein in their entirties, disclose common uses of planetary gear sets. Another type of epicyclic gearing system that may be used with the epicyclic joint 10 is a common differential with beveled gears. U.S. Pat. Nos. 2,608,261 and 3,400,610, both of which are incorporated by reference herein in their entirties, disclose apparatuses using differentials with beveled gears. Accordingly, the scope of the epicyclic joint 10 is not limited by the type of epicyclic gearing and/or gear sets used, and any such gearing and/or gear sets known to those skilled in the art may be used without departing from the spirit and scope of the epicyclic joint 10 as disclosed herein.
Operation of the Exemplary Embodiment
[0021] Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, FIGS. 1-5 provide perspective views of one embodiment of the epicyclic joint 10 . In the embodiment of the epicyclic joint 10 shown in FIGS. 1-5 , the epicyclic joint 10 operates to allow a rotational energy input from the input shaft 23 a to be rotated about a first axis of rotation 12 and a second axis of rotation 14 to an output shaft 63 a . However, the epicyclic joint 10 may be configured for a single axis of rotation or for more than two axes of rotation within the spirit and scope of the epicyclic joint 10 as disclosed and claimed herein.
[0022] The embodiment of the epicyclic joint 10 pictured herein is comprised of three main portions: (1) a first frame 20 and the elements associated therewith (generally horizontally oriented in FIGS. 1-5 ); (2) a central frame 30 and the elements associated therewith; and, (3) a second frame 60 and the elements associated therewith (generally vertically oriented in FIGS. 1-5 ). The first frame 20 is pivotally mounted to the central frame 30 about the first axis of rotation 12 , and the second frame 60 is pivotally mounted to the central frame 30 about the second axis of rotation 14 . The first axis of rotation 12 and the second axis of rotation 14 are perpendicular to one another in the embodiment of the epicyclic joint 10 pictured herein, although other it may be configured for other orientations without departing from the spirit and scope of the epicyclic joint 10 as disclosed and claimed herein. In an embodiment not pictured herein, the epicylic joint 10 includes only one axis of rotation, and in another embodiment not pictured herein, the epicyclic joint 10 includes more than two axes of rotation.
[0023] The first frame 20 in the embodiment shown is generally U-shaped, and includes a first frame splitter support 22 , which in the embodiment pictured herein is comprised of U-shaped member wherein each surface is perpendicular to the adjacent surface. Right and left transfer supports 26 , 28 , respectively, may be mounted to each side of the first frame 20 . These various elements of the first frame 20 may be separately formed and then joined together, or they may be integrally formed as one continuous structure. Furthermore, the orientations and/or configurations of the various elements of the first frame 20 may be different in other embodiments not pictured herein. The material used to construct the main frame 20 and/or the various components thereof may be any material known to those skilled in the art and suitable for the particular application. Such materials may include metals, alloys, synthetic materials such as polymers, wood, combinations thereof, or any other material known to those skilled in the art.
[0024] As indicated, the first frame 20 may be generally U-shaped, with the first frame splitter support 22 and right and left transfer supports 26 , 28 formed as protrusions thereon. An input shaft 23 a is rotatably mounted to the first frame 20 , as shown in FIG. 1 . Affixed to and rotatable with one end of the input shaft 23 a is an input gear 23 b , which is formed as a miter gear in the embodiment pictured herein. As rotational force is applied to the input shaft 23 a , that force is directly communicated to the input gear 23 b . A miter gear is one type of rotational translator that may be used with the epicyclic joint 10 .
[0025] Intermeshed with the input gear 23 b are a first right split gear 24 b and a first left split gear 25 b The first right and left split gears 24 b , 25 b rotate about an axes that is perpendicular to that of the input gear 23 b . Accordingly, it will be obvious to those skilled in the art that as the input gear 23 b rotates, it causes the right and left first split gears 24 b , 25 b to rotate in opposite directions. The first right split gear 24 b is affixed to and rotatable with a right split shaft 24 a , which may be pivotally mounted to said first frame splitter support 22 in the embodiment pictured herein. The first left split gear 25 b is affixed to and rotatable with a left split shaft 25 a , which also may be pivotally mounted to said first frame splitter support 22 in the embodiment pictured herein. Also affixed to the right split shaft 24 a and rotatable therewith is a second right split gear 24 c , and a second left split gear 25 c is affixed to and rotatable with the left split shaft 25 a . Accordingly, the right split shaft 24 a and associated components and left split shaft 25 a and associated components are one type of symmetrical splitter that may be used with the epicyclic joint 10 to divide the rotational energy of the input shaft 22 and translate that energy by ninety degrees. The first and second right split gears 24 b , 24 c , first and second left split gears 25 b , 25 c are one type of rotational energy dividing member, but other structures and/or methods known to those skilled in the art may be used to divide the rotational energy of the input shaft 22 as described in detail below.
[0026] A right transfer support 26 may be affixed to the first frame 20 , and a complimentary left transfer support 28 may also be affixed to the first frame 20 . A right transfer shaft 27 a may be pivotally mounted to the right transfer support 26 and a left transfer shaft 29 a may be pivotally mounted to the left transfer support 28 , as in the embodiment pictured in FIGS. 1-5 . A first right transfer gear 27 b may be mounted to and rotatable with one end of the right transfer shaft 27 a so that the first right transfer gear 27 b intermeshes with the second right split gear 24 b . A first left transfer gear 29 b may be mounted to and rotatable with one end of the left transfer shaft 29 a so that the first left transfer gear 29 b intermeshed with the second left split gear 25 b . Accordingly, the right transfer shaft 27 a together with the first and second right transfer gears 27 b , 27 c comprise one type of transfer member, as do the left transfer shaft 29 a together with the first and second right transfer gears 29 b , 29 c.
[0027] A center frame 30 may be positioned adjacent the first frame 20 on the end thereof that is opposite the input shaft 23 a . One embodiment of the center frame 30 is shown in detail in FIGS. 6A and 6B , in which embodiment the center frame 30 is generally square in shape. As with the first frame 20 , the components of the center frame 30 may be separately formed and then joined together, or they may be integrally formed as one continuous structure. The material used to construct the center frame 30 and/or the various components thereof may be any material known to those skilled in the art and suitable for the particular application. Such materials may include metals, alloys, synthetic materials such as polymers, wood, combinations thereof, or any other material known to those skilled in the art.
[0028] In the embodiment pictured herein, the first frame 20 is engaged with the center frame 30 via the cooperation of the right center shaft 31 a , left center shaft 35 a , right planetary gearhead 32 , and left planetary gearhead 36 . The right center shaft 31 a may be pivotally supported by the first frame 20 , and a first right miter gear 31 b may be affixed to and rotatable with the right center shaft 31 a . The left center shaft 35 a may be pivotally supported by the first frame 20 , and a first left miter gear 35 b may be affixed to and rotatable with the left center shaft 35 a.
[0029] A right planetary gearhead 32 may be positioned adjacent the first right miter gear 31 b . One type of planetary gearhead 70 that may be used with the epicyclic joint as disclosed herein is shown in FIGS. 7A and 7B . The planetary gearhead 70 shown in FIGS. 7A and 7B includes a sun gear 72 that may be affixed to and rotatable with the input shaft 71 (e.g., the right center shaft 31 a in an embodiment of the right planetary gearhead 32 ). In a typically planetary gearhead 70 , a plurality of planet gears 74 (three in the embodiment shown in FIGS. 7A and 7B , but which may be greater or fewer in other embodiments not pictured herein) are pivotally mounted to a planet carrier 73 , and the planet gears 74 are intermeshed with the sun gear 72 . An annulus 75 may be placed around the planet carrier 73 such that the annulus also is intermeshed with the planet gears 74 . The exterior surface of the annulus 75 includes an annulus recess 76 , which may be fashioned to pivotally engage a center frame journal 38 . In the embodiment of the planetary gearhead 70 shown in FIGS. 7A and 7B , the size and configuration of the sun gear 72 , planet gears 74 , and annulus 75 result in a three-to-one reduction in the rotational speed of the planet carrier 73 with respect to the sun gear 72 (and input shaft 71 , accordingly). However, because the embodiment of the epicyclic joint 10 shown herein transfers rotational energy from an input shaft 71 to a planet carrier 73 , and then from another planet carrier 73 back to an input shaft 71 (via the interaction of the second right miter gear 31 c , second left miter gear 35 c , second top miter gear 41 c , and second bottom miter gear 45 c ), the rotational speed of the output shaft 63 a on the second frame 60 is equal to that of the input shaft 23 a on the first frame 20 . This ratio may be different in other embodiments of the epicyclic joint 10 , and is therefore in no way limiting.
[0030] In the embodiment of the epicyclic joint 10 pictured in FIGS. 1-5 , right planetary gearhead 32 is pivotally mounted to the center frame 30 about the center frame journal 38 formed in the right side of the center frame 30 . The sun gear 72 in the right planetary gearhead 32 may be affixed to and rotatable with the right center shaft 31 a . The planet carrier 73 in the right planetary gearhead 32 may be affixed to and rotable with the second right miter gear 31 c . A right spur gear 33 may be affixed to and rotatable with the annulus 75 of the right planetary gearhead 32 .
[0031] A first compensation shaft support 52 may be affixed to the center frame 30 . A first compensation shaft 53 a may be pivotally supported by the first compensation shaft support 52 . In the embodiment shown in FIGS. 1-5 , two first compensation gears 53 b are affixed to and rotatable with the first compensation shaft 53 a . One first compensation gear 53 b may be intermeshed with the right spur gear 33 and the other first compensation gear 53 b may be intermeshed with the left spur gear 37 , which is explained in detail below. The first compensation shaft support 52 may be affixed elsewhere on the epicyclic joint 10 in other embodiments thereof not pictured herein. The first compensation shaft support 52 may have any convenient orientation or configuration as long as it does not interfere with the other components of the epicyclic joint 10 and allows the appropriate components to engage one another
[0032] In a manner analogous to the right planetary gearhead 32 , a left planetary gearhead 36 may be positioned adjacent the first left miter gear 35 b . The left planetary gearhead 36 may be pivotally mounted to the center frame 30 about the center frame journal 38 formed in the right side of the center frame 30 . The sun gear 72 in the right planetary gearhead 36 may be affixed to and rotatable with the left center shaft 35 a . The planet carrier 73 in the left planetary gearhead 36 may be affixed to and rotable with the second left miter gear 35 c . A left spur gear 37 may be affixed to and rotatable with the annulus 75 of the left planetary gearhead 36 .
[0033] Because the planet carrier 73 in the right planetary gearhead 32 rotates in the opposite direction of the planet carrier 73 in the left planetary gearhead 36 , the first compensation shaft 53 a and first compensation gears 53 b bind the right and left planetary gearheads 32 , 36 together. As is apparent from the description and various figures included herein, the right center shaft 31 a , right planetary gearhead 32 , left center shaft 35 a , and left planetary gearhead 36 cooperate to engage the first frame 20 with the center frame 30 about a first axis of rotation 12 . The first frame 20 is allowed to rotate with respect to the center frame 30 about the first axis of rotation 12 through the cooperation of the right and left planetary gearheads 32 , 36 with the first compensation shaft 53 a and first compensation gears 53 b.
[0034] More specifically, because the right spur gear 33 (which is affixed to and rotatable with the annulus 75 of the right planetary gearhead 32 ) may rotate independently from the second right miter gear 31 c (which is affixed to and rotatable with the planet carrier 73 of the right planetary gearhead 32 ), and because the left spur gear 37 (which is affixed to and rotatable with the annulus 75 of the left planetary gearhead 36 ) may rotate independently from the second left miter gear 35 c (which is affixed to and rotatable with the planet carrier 73 of the left planetary gearhead 36 ), both by virtue of the epicyclic qualities of the planetary gearhead 70 , the first frame 20 may pivot with respect to the center frame 30 about the first axis of rotation 12 (which also causes the annuluses 75 of the right and left planetary gearheads 32 , 36 to rotate about their respective center frame journals 38 ) without lashing of any of the gears in the epicylic joint 10 . During rotation of the first frame 20 with respect to the center frame 30 , the first compensation shaft 53 a does not rotate, but instead requires that the right and left spur gears 33 , 37 rotate in the same direction by the same magnitude, even though the second right miter gear 31 c and second left miter gear 35 c are counter rotating. Accordingly, a stationary gear may be positioned to intermesh with either the right or left spur gear 33 , 37 to achieve the same functionality as that of the epicyclic joint 10 pictured herein.
[0035] In an embodiment not pictured herein, a single output gear (not shown) is pivotally supported by the center frame 30 and arranged to intermesh with both the second right and left miter gears 31 c , 35 c . The single output gear may be affixed and rotatable with an output shaft (not shown), such that the arrangement creates a single-axis epicyclic joint 10 . In light of the present disclosure it will become apparent to those skilled in the art that in an embodiment not pictured herein, the right spur gear 33 may be affixed to and rotatable with the planet carrier 73 of the right planetary gearhead 32 , and the second right miter gear 31 c may be affixed to and rotatable with the annulus 75 of the right planetary gearhead 32 with an analogous configuration for the elements on the left side of the epicyclyic joint 10 to yield a similarly functional first axis of rotation 12 . Furthermore, it will also become apparent to those skilled in the art in light of the present disclosure that the right and left planetary gearheads 32 , 36 and first compensation shaft and gears 53 a , 53 b may be positioned adjacent the first frame splitter support 22 if spur transfer gears (not shown) are employed in lieu of the right and left transfer shafts and gears 27 a , 29 a , and 27 b , 27 c , 29 b , 29 c , respectively.
[0036] As is apparent from the detailed description and several figures included herein, the various elements of the first frame 20 may cooperate to divide a single rotational input into two counter-rotating rotational energy sources with axes of rotation perpendicular to that of the rotational input. Each counter-rotating rotational energy source may then be transferred to an epicyclic gearhead (which is shown as a planetary gearhead 70 in the embodiment pictured herein) and eventually combined to produce an output rotational energy source with an axis of rotation parallel to that of the rotational input.
[0037] To yield a second axis of rotation 14 as in the embodiment of the epicyclic joint 10 shown herein, a top and bottom planetary gearhead 42 , 46 may be pivotally mounted to the center frame 30 about respective center frame journals 38 . The top and bottom portions of the center frame 30 and second frame 60 are analogous to the right and left portions of the center frame 30 and first frame 20 , respectively. The top and bottom portions of the center frame 30 and second frame 60 are mirror images of the right and left portions of the center frame 30 and first frame 20 rotated along a horizontal axis by negative ninety degrees. Accordingly, the second top miter gear 41 c may be affixed to the planet carrier 73 of the top planetary gearhead 42 and the top spur gear 43 may be affixed to the annulus 75 of the top planetary gearhead 42 . The second bottom miter gear 45 c may be affixed to the planet carrier 73 of the bottom planetary gearhead 46 and the bottom spur gear 47 may be affixed to the annulus 75 of the bottom planetary gearhead 46 . The second top and bottom miter gears 41 c , 45 c may be intermeshed with both the second right miter gear 31 c and second left miter gear 35 c , such that the counter-rotating second right and left miter gears 31 c , 35 c cause the second top and bottom miter gears 41 c , 45 c to counter rotate. Accordingly, the configuration of the second right and left miter gears 31 c , 35 c and second top and bottom miter gears 41 c , 45 c translate the axis of rotation of the rotational energy by negative ninety degrees (i.e., from horizontal to vertical as shown in the orientation pictured in FIG. 5A ).
[0038] The rotation of the second top and bottom miter gears 41 c , 45 c causes the rotation of planet carriers 73 in the top and bottom planetary gearheads 42 , 46 , respectively. A second compensation shaft support 54 may be affixed to the center frame 30 to pivotally support a second compensation shaft 55 a , which second compensation shaft may have two second compensation gears affixed thereto and rotatable therewith. The second compensation shaft support 54 may be affixed elsewhere on the epicyclic joint 10 in other embodiments thereof not pictured herein. The second compensation shaft support 54 may have any convenient orientation or configuration as long as it does not interfere with the other components of the epicyclic joint 10 and allows the appropriate components to engage one another
[0039] The second compensation gears 55 b may be intermeshed with the top and bottom spur gears 43 , 47 , respectively. Because the top and bottom spur gears 43 , 47 may be affixed to and rotatable with the annuluses 75 of the top and bottom planetary gearheads 42 , 46 , respectively, the configuration of the second compensation shaft and gears 55 a , 55 b require that the rotation of the planet carrier 73 results in rotation of the sun gear 72 and top and bottom center shafts 41 a , 45 a. In a manner completely analogous to that explained in detail above for the first frame 20 and center frame 30 , the top center shaft 41 a (which may be pivotally supported by the second frame 60 ), top planetary gearhead 42 , bottom center shaft 45 a (which may be pivotally supported by the second frame 60 ), and bottom planetary gearhead 46 cooperate to engage the second frame 60 with the center frame 30 about a second axis of rotation 14 , which in the embodiment of the epicyclic joint 10 shown herein is perpendicular to the first axis of rotation 12 . The second frame 60 is allowed to rotate with respect to the center frame 30 about the second axis of rotation 14 through the cooperation of the top and bottom planetary gearheads 42 , 46 with the second compensation shaft 55 a and second compensation gears 55 b.
[0040] The first top miter gear 41 b , which may be affixed to and rotatable with the top center shaft 41 a (i.e., input shaft 71 ) and sun gear 72 in the top planetary gearhead 42 , may be intermeshed with the second top transfer gear 67 c . The first bottom miter gear 45 b , which may be affixed to and rotatable with the bottom center shaft 45 a (i.e., input shaft 71 ) and sun gear 72 in the bottom planetary gearhead 46 , may be intermeshed with a second bottom transfer gear 69 c . This engagement translates the rotational energy with axes of rotation in two primarily vertical directions (in the orientation shown in FIG. 1 ) to rotational energy with axes of rotation in two primarily horizontal directions (in the orientation shown in FIG. 1 ).
[0041] In a manner analogous to that of the first frame 20 , the second top and bottom transfer gears 67 c , 69 c , may be affixed to and rotatable with top and bottom transfer shafts 67 a , 69 a , respectively, and first top and bottom transfer gears 67 b , 69 b , may also be affixed to and rotatable with the top and bottom transfer shafts 67 a , 69 a , respectively. As in a manner similar to that described above for the first frame 20 , the top transfer shaft 67 a is pivotally supported by the top transfer support 66 , and the bottom transfer shaft 69 a is pivotally supported by the bottom transfer support 68 . Furthermore, the first top and bottom transfer gears 67 b , 69 b may be intermeshed with a second top and bottom split gear 64 c , 65 c respectively. As is readily apparent from FIG. 1 , this engagement translates the rotational energy with axes or rotation in two primarily horizontal directions (in the orientation shown in FIG. 1 ) to rotational energy with axes of rotation in two primarily vertical directions (in the orientation shown in FIG. 1 ).
[0042] The second top and bottom split gears 64 c , 65 c may be affixed to and rotatable with top and bottom split shafts 64 a , 65 a , respectively. In the embodiment pictured herein, the top and bottom split shafts 64 a , 65 a are each pivotally supported by the second frame 60 adjacent the second frame splitter support 62 , all of which is completely analogous to the first frame 20 . First top and bottom split gears 64 b , 65 b may be affixed to and rotatable with the top and bottom split shafts 64 a , 65 a , respectively. The first top and bottom split gears 64 b , 65 b , in turn, may be intermeshed with an output gear 63 b , which in the embodiment pictured herein combines two rotational energy sources into one single source transferred to the output shaft 63 a , to which the output gear 63 b may be affixed and with which the output gear 63 b may be rotatable. The first and second top split gears 64 b , 64 c , first and second left split gears 65 b , 65 c are one type of rotational energy combing member, but other structures and/or methods known to those skilled in the art may be used to divide the rotational energy of the output shaft 62 .
[0043] As with the first frame 20 and center frame 30 , the components of the second frame 60 may be separately formed and then joined together, or they may be integrally formed as one continuous structure. The material used to construct the second frame 60 and/or the various components thereof may be any material known to those skilled in the art and suitable for the particular application. Such materials may include metals, alloys, synthetic materials such as polymers, wood, combinations thereof, or any other material known to those skilled in the art.
[0044] In the embodiment of the epicyclic joint 10 pictured herein, the center frame 30 in combination with the second right, left, top, and bottom miter gears 31 c , 35 c , 41 c , 45 c , respectively serves as a type of translator. That is, the various elements associated with these components of the center frame 30 function to translate the axis of rotation for rotational energy into a different orientation, which in the embodiment pictured herein is from an axis that is generally horizontal to one that is generally vertical.
[0045] The epicyclic joint 10 is not limited by the number of planet gears 74 used for any of the planetary gear sets. Accordingly, any type of planetary gear set may be used with the epicyclic joint 10 without departing from the spirit and scope of the present invention. Furthermore, as previously mentioned, in light of the preceding disclosure, it will be apparent to those skilled in the art that a differential gear set may be used with the epicyclic joint 10 in place of a planetary gear set. Therefore, the specific type of epicyclic gear set used with the epicyclic joint 10 in no way limits the scope of the epicyclic joint 10 , and any type of epicyclic gear set known to those skilled in the art may be used with epicyclic joint 10 without departing from the spirit and scope thereof.
[0046] In other embodiments of the epicyclic joint 10 not pictured herein, other structures and/or methods other than the right transfer shaft 27 a and associated right transfer gears 27 b , 27 c , left transfer shaft 29 a and associated left transfer gears 29 b , 29 , top transfer shaft 67 a and associated top transfer gears 67 b , 67 c , and bottom transfer shaft 69 a and associated bottom transfer gears 69 b , 69 c may be used to transport the rotational energy from a rotating member positioned on the first frame 20 to the center frame 30 and/or from the center frame 30 to the second frame 60 . For example, large spur gears (not shown) may be used, as may chains with sprockets, or any other structure and/or method known to those skilled in the art. In light of the present disclosure, it will be obvious to those skilled in the art that the symmetry associated with the embodiment of the epicyclic joint 10 shown in the various figures herein possesses certain inherent advantages. The input rotational energy is symmetrically divided about the first frame 20 , which rotational energy is then symmetrically translated by ninety degrees about the center frame 30 , which rotational energy is then transmitted along the second frame 60 before being combined into one rotational energy output at the output shaft 63 a.
[0047] Other embodiments of the epicyclic joint 10 may not require the level of symmetry contained in the embodiment pictured herein. In fact, in other applications it is contemplated that non-symmetrical configurations may be advantageous. For example, in another embodiment of the epicyclic joint not pictured herein, the rotational energy is not symmetrically divided about the first frame 20 and/or not symmetrically translated about the center frame 30 . Furthermore, the rotational energy may be transferred along the second frame 60 and combined adjacent thereto in a non-symmetrical fashion. Such non-symmetrical embodiments of the epicyclic joint 10 may employ torque vectoring apparatuses, such as that disclosed in U.S. Pat. No. 7,491,147, which is incorporated herein in its entirety.
[0048] As will be obvious to those skilled in the art in light of the present disclosure and accompanying drawings, the length of the first frame 20 with respect to the size of the center frame 30 and second frame 60 is an important factor in determining how far the first frame may rotate with respect to the center frame 30 about the first axis of rotation 12 . For example, if the first frame 20 is sufficiently lengthened with respect to the second frame 60 , but the center frame 30 remains in proportion to the second frame 60 as shown in the various figures contained herein, the epicyclic joint 10 may be configured to allow the first frame 20 to rotate three hundred and sixty degrees with respect to the center frame 30 about the first axis of rotation 12 . In a similar manner, the epicyclic joint 10 may be configured to allow the second frame 60 to rotate three hundred and sixty degrees with respect to the center frame 30 about the second axis of rotation 14 . Accordingly, the degree of freedom of motion for either the first frame 20 or second frame 60 with respect to one another or the center frame 30 in no way limits the scope of the epicyclic joint 10 as disclosed and claimed herein.
[0049] It will be apparent to those skilled in the art in light of the present disclosure that the epicyclic joint 10 may be configured with more than two axes of rotation. In such an embodiment, another frame similar to the center frame 30 would be positioned adjacent the second frame 60 for engagement therewith. The output shaft 63 a could be affixed to and rotatable with a miter gear (not shown), the cooperated with two other miter gears (not shown) to divide the rotational energy of the output shaft 63 a into corresponding phases. The orientation of various axes of rotation of such an epicyclic joint 10 may be configured differently depending on the specific application, as may the maximum angle or rotation of any component about such an axis. The fact that the first and second axes of rotation 12 , 14 are perpendicular to one another and that both are perpendicular to the longitudinal axis of the input shaft 23 a in the embodiment pictured herein is in no way limiting. Accordingly, the epicyclic joint 10 may be used with any number of rotational axes in any number of orientations within the spirit and scope of the epicyclic joint 10 as disclosed and claimed herein.
[0050] The various advantages of the epicyclic joint 10 as disclosed and described herein will be apparent to those skilled in the art in light of the present disclosure. For example, one advantage the epicyclic joint 10 is increased range of motion about the first and second axes of rotation 12 , 14 . In the embodiment pictured herein, the range of motion for each axis of rotation 12 , 14 may greater than two hundred and seventy degrees. As explained above, in other embodiments not pictured herein the range of motion for one axis 12 , 14 may be as large as 360 degrees. Another advantage of the epicyclic joint 10 is the lack of rotating frame members. In the epicyclic joint 10 , the first frame 20 , central frame 30 , and second frame 60 do not rotate in a manner dependent on the rotational energy of any of the components thereof. Instead, the first, center, and second frames 20 , 30 , 60 rotate about either the first axis of rotation 12 and/or the second axis of rotation 14 so that the epicyclic joint 10 may be oriented in the most advantageous direction for the specific application. The compensators (first compensation shaft and gears 53 a , 53 b and second compensation shaft and gears 55 a , 55 b in the embodiment pictured herein) allow the epicyclic joint 10 to be configured in an infinite number of orientations without additional shock, vibrations, or other perturbations imparted to the other components of the epicyclic joint 10 as rotational energy is being transmitted through the epicyclic joint 10 .
[0051] The epicyclic joint 10 and various elements thereof may be constructed of any suitable material known to those skilled in the art. In the embodiment as pictured herein, it is contemplated that various frame elements, shaft elements, and gear elements will be constructed of metal, aluminum, metallic or aluminum alloys, polymers, or combinations thereof. However, other suitable materials may be used.
[0052] Other methods of using the epicyclic joint 10 will become apparent to those skilled in the art in light of the present disclosure. Accordingly, the methods and embodiments pictured and described herein are for exemplary purposes only, and are not intended to limit the scope of the epicyclic joint 10 in any way. The scope of the epicyclic joint 10 is not limited by the embodiments pictured and described herein, but is intended to apply to all similar apparatuses and methods for allowing a rotational energy to be transmitted about one or more axes or rotation, which one or more axes or rotation are distinct from the axis of rotation of the rotational energy source. Modifications and alterations from the described embodiments will occur to those skilled in the art without departure from the spirit and scope of the epicyclic joint 10 .
[0053] It is understood that the epicyclic joint 10 as disclosed and defined herein extends to all alternative combinations of two or more of the individual features mentioned or evident from the text and/or drawings. All of these different combinations constitute various alternative aspects of the epicyclic joint 10 . The embodiments described herein explain the best modes known for practicing the epicyclic joint 10 and will enable others skilled in the art to utilize the same. The claims are to be construed to include alternative embodiments to the extent permitted by the prior art.
|
The various embodiments disclosed and pictured herein are directed to an epicyclic joint with at least one axis of rotation. The epicyclic joint includes rotational members mounted to frame members in such a manner that rotational energy may be transposed along multiple axes of rotation without the need for the frame members to rotate. Epicyclic gear sets and compensation gears and shafts are employed to mitigate vibration, stress, and perturbation of the rotating members when the orientation of the epicyclic joint is varied along any of the axes of rotation. Planetary gear sets or differential gear sets may be used with the epicyclic joint, as may spur gears and miter gears.
| 5
|
This application claims the benefit of U.S. Provisional Patent Application No. 60/411,367, filed Sep. 18, 2002, the contents of which is hereby incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel fluorinated dendrons and to a method for producing functional fluorinated dendrons programmed to self-assemble into supramolecular nanocylinder compositions containing p-stacks of high electron or hole mobility donors (D), acceptors (A), or D-A complexes in the core. Such nanocylinder compositions are uniquely useful in devices such as transistors, photovoltaics, photoconductors, photorefractives, light emissives, and optoelectronics.
2. Background
Self-organized organic nanostructures with controlled optoelectronic properties that facilitate ultrahigh density nanopatterning have been attempted to be developed for molecular electronics. In this regard, charge carrier mobility (μ) in organic materials appears to be mediated by p-stacking of conjugated groups, a principle resembling that of base pairs in DNA. Examples are disc- and rod-like molecules stacked in discotic hexagonal and calamitic liquid crystals (LCs), and acenes in single crystals. The development of these structures has required the synthesis of novel complex molecules and the elaboration of new processing techniques for LCs and single crystals.
The discovery of the first organic conducting polymer, polyacetylene, initiated early work relating to molecular optoelectronics. However, further work has required the development of new organic systems that exhibit higher processability, efficiency, μ, density of active elements per square centimeter, mechanical integrity, and lower costs than inorganic analogues. For example, amorphous organic polymers like poly(-vinyl-carbazole) have good mechanical properties, but their μ is very low (10 −8 -10 −6 cm 2 ·V −1 ·s −1 ). Single crystals have high μ (10 −1 cm 2 ·V −1 ·s −1 ) but are difficult to fabricate. In 1994, discotic hexagonal LCs based on aromatic molecules such as triphenylene were shown to exhibit u approaching those of single crystals. However, their effectiveness has been hindered by the multistep synthesis of each disc, their different phase behavior, and their complex processability.
The general state of the art relating to dendritic polymers and their uses, and compounds having electron-accepting or electron-donating systems, is described in the following U.S. Patents.
U.S. Pat. No. 5,731,095 to Milco, et al., issued Mar. 24, 1998, discloses water-soluble or water-dispersible fluorine-containing dendritic polymer surfactants.
U.S. Pat. No. 5,872,255 to Attias, et al. issued Feb. 16, 1999, discloses conjugated compounds having electron-withdrawing or electron-donating systems, and the use of said compounds or of any material which includes them in electronic, optoelectronic, nonlinear optical, and electrooptical devices.
U.S. Pat. No. 5,886,110 to Gozzini, et al. issued Mar. 23, 1999, discloses branched, dendrimeric macromolecules having a central nucleus and a series of polyoxaalkylene chains that radiate from the nucleus and spread into the surrounding space, branching in a cascade fashion until the desired size results.
U.S. Pat. No. 6,020,457 to Klimash, et al. issued Feb. 1, 2000, discloses dendritic polymers containing disulfide functional groups which are essentially inert under non-reducing conditions, but which form sulfhydryl groups upon being subjected to a reducing agent, and their uses in the formation of differentiated dendrimers, formation of binding reagents for diagnostics, drug delivery, gene therapy and magnetic resins imaging, and in the preparation of self-assembled dendrimer monolayers on quartz crystal resonators to provide dendrimer-modified electrodes which are useful for detecting various ions or molecules.
U.S. Pat. No. 6,051,669 to Attias, et al., issued Apr. 18, 2000, discloses conjugated polymer compounds having electron-withdrawing or electron-donating systems, and the use of said compounds or of any material which includes them in electronic, optoelectronic, nonlinear optical, and electrooptical devices.
U.S. Pat. No. 6,077,500 to Dvornic, et al., issued Jun. 20, 2000, discloses higher generation radially layered copolymeric dendrimers having a hydrophilic poly(amidoamine) or a hydrophilic poly(propyleneimine) interior and a hydrophobic organosilicon exterior, and their uses for delivering active species for use in catalysis, pharmaceutical applications, drug delivery, gene therapy, personal care, and agricultural products.
U.S. Pat. No. 6,136,921 to Hsieh, et al., issued Oct. 24, 2000, discloses a coupled polymer which is prepared by reacting a living alkali metal-terminated polymer with a coupling agent, having good rubbery physical properties, transparency, and wear resistance.
U.S. Pat. No. 6,312,809 to Crooks, et al., issued Nov. 6, 2001, discloses a substrate having a dendrimer monolayer film covalently bonded to the surface, and uses as a chemically sensitive surface, such as in chemical sensors.
The prior art has been ineffective in formulating effective structures that have higher processability, efficiency, μ, density of active elements per square centimeter, mechanical integrity, and lower costs than inorganic analogues. Surprisingly, the present inventive subject matter overcomes these deficiencies in the prior art and is directed to the production of novel functional fluorinated dendrons which are programmed to self-assemble into supramolecular nanocylinder compositions containing p-stacks of high electron (μ e ) or hole (μ h ) mobility donors (D), acceptors (A), or D-A complexes in the core. The co-assembly of D- or A-dendrons with amorphous polymers containing A or D side groups, respectively, incorporates the polymer backbone in the center of the cylinder via p-stacks of D-A interactions and enhances u of the resulting polymer. These supramolecular cylinders self-process into homeotropically aligned hexagonal and rectangular columnar LCs that pattern ultrahigh density arrays (up to 4.5×10 12 cylinders per square centimeter) between electrodes. Below glass transition temperature, a complex and organized optoelectronic matter of cylinders composed of helical dendrons jacketing stacks of aromatic groups with even higher, essentially insensitive to ionic impurities, is produced. Such arrays are uniquely applicable to devices having a broad range of sizes. In particular, such compositions are used in devices spanning the range from single supramolecule, to nanoscopic, to macroscopic. Useful devices for including said compositions are transistors, photovoltaics, photoconductors, photorefractives, light emissives, and optoelectronics, which has not heretofore been possible.
SUMMARY OF THE INVENTION
The present invention relates to a compound of formula I
wherein:
X is Z—(CH 2 CH 2 O) n , where n is 1-6, or Z—(CH 2 ) m O, where m is 1-9;
Y is selected from the group consisting of pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthrcene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, and naphthacene,
wherein said Y is optionally substituted with 1-6 substituents selected from the group consisting of nitro, nitroso, carbonyl, carboxy, oxo, hydroxy, fluoro, perfluoro, chloro, perchloro, bromo, perbromo, phospho, phosphono, phosphinyl, sulfo, sulfonyl, sulfinyl, trifluoromethyl, trifluoromethylsulfonyl, and trimethylsulfonyl,
and wherein 1-4 carbon atom(s) of said Y is/are optionally replaced by N, NH, O, or S; and
Z is selected from the group consisting of a direct bond, —C(O)O—, (C 1 -C 6 alkyl)—C(O)O—, (C 2 -C 6 alkenyl)—C(O)O—, and (C 2 -C 6 alkynyl)—C(O)O—.
The present invention further relates to a process for making a stacked nanocylinder composition having a mobility donor complex, a mobility acceptor complex, or a mobility donor-acceptor complex in its core, which comprises:
(a) heating semi-fluorinated dendrons incorporating selected dendron apex moiety(ies) and side group(s) having donor, acceptor, or donor-acceptor characteristics to an isotropic phase temperature;
(b) filling a substrate with said isotropic phase dendrons; and
(c) cooling said dendrons to a liquid crystalline phase temperature.
The present invention further relates to the stacked nanocylinder composition described above, made by the process which comprises the steps of:
(a) heating semi-fluorinated dendrons incorporating selected dendron apex moiety(ies) and side group(s) having donor, acceptor, or donor-acceptor characteristics to an isotropic phase temperature;
(b) filling an indium tin oxide coated glass substrate with said isotropic phase dendrons; and
(c) cooling said dendrons to a liquid crystalline phase temperature at a rate of about 0.1° C. per minute, in the presence of a magnetic field of about 1 tesla.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 ( a ) is a drawing which depicts the spacial correlation between elements of compound A1 in a supramolecular cylinder.
FIG. 1 ( b ) is a photograph which depicts thermal optical polarized microscopy (TOPM) of the texture of compound D4 in the liquid crystalline state after cooling at 20° C./minute from the isotropic phase, showing defect characteristics.
FIG. 1 ( c ) is a photograph which depicts TOPM of a homeotropically aligned compound D4 after cooling at 0.1° C./minute.
FIG. 2 ( a ) is a graph which depicts the 1 H NMR spectra of compound A1 at 22° C.
FIG. 2 ( b ) is a graph which depicts the 1 H NMR spectra of compound A1 in the isotropic melt state at 120° C.
FIG. 2 ( c ) is a graph which depicts the 1 H NMR spectra of compound A1 in the LC state at 75° C.
FIG. 2 ( d ) is a graph which depicts the 1 H NMR spectra of compound A1 in the glassy state at 25° C.
FIG. 2 ( e ) is a drawing which depicts sandwich-type stacking of nitro-fluorenone moieties.
FIG. 2 ( f ) is a drawing which depicts the structure of supramolecular cylinders of the present invention, with stacks of fluorenone sandwiches in the center, jacketed by helical dendrons.
FIGS. 3 ( a ) and 3 ( b ) are graphs which depict hole photocurrent transients plotted on (a) linear and (b) double logarithmic scales for compound D4 at 70° C.
FIGS. 4 ( a ) and 4 ( b ) are graphs which depict (a) electric field and (b) temperature dependence of the carrier mobility of compound D4 in the Φ h phase.
FIG. 5 is a photograph which depicts the electron diffraction (ED) of compound D4.
FIG. 6 is a drawing which depicts self-assembly, co-assembly, and self-organization of dendrons containing donor (D) and acceptor (A) groups with amorphous polymers containing D and A groups.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
The term “replaced” as used herein refers to the situation wherein an atom takes the place of another atom in the chemical formula of a compound. For example, replacement of the carbon atom at the 9-position of fluorene with a nitrogen atom produces carbazole.
The term “substituent” as used herein refers to an atom or group which is added to a chemical entity by replacing one or more hydrogen atom(s); monovalent groups replace one hydrogen atom, bivalent groups replace two hydrogen atoms, and so forth.
The term “μ” as used herein refers to charge carrier mobility, or velocity, in an electric field.
The term “μ e ” as used herein refers to electron mobility in an electric field.
The term “μ h ” as used herein refers to hole mobility in an electric field.
The term “p-stack” or “π-stack” as used herein refers to the hydrophobic interaction which occurs between aromatic or aromatic heterocyclic side chains and produces a cloud of free electrons from the pi-orbitals of atoms composing the stacked structure.
The term “donor” or “D” as used herein refers to a substance which produces an increase in the electron density in a material, and a corresponding decrease in the hole concentration. Similarly, the term “acceptor” or “A” as used herein refers to a substance which produces an decrease in the electron density in a material, and a corresponding increase in the hole concentration. “D-A complexes” refers to a material in which both donor and acceptor substances are present.
The term “isotropic phase” as used herein refers to the phase of matter in which the molecules are randomly aligned, exhibit no long range order, and have a low viscosity. The characteristic lack of orientational order of the isotropic phase is that of a traditional liquid phase.
The term “liquid crystalline phase” as used herein refers to a phase of matter in which the molecules tend to point along a common axis, exhibit long range orientational order, and wherein the average orientation may be manipulated with an electric field. The characteristic orientational order of the liquid crystal state is between the traditional solid and liquid phases.
COMPOUNDS OF THE PRESENT INVENTION
The present invention relates to a compound of formula I
wherein:
X is Z—(CH 2 CH 2 O) n , where n is 1-6, or Z—(CH 2 ) m O, where m is 1-9;
Y is selected from the group consisting of pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthrcene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, and naphthacene,
wherein said Y is optionally substituted with 1-6 substituents selected from the group consisting of nitro, nitroso, carbonyl, carboxy, oxo, hydroxy, fluoro, perfluoro, chloro, perchloro, bromo, perbromo, phospho, phosphono, phosphinyl, sulfo, sulfonyl, sulfinyl, trifluoromethyl, trifluoromethylsulfonyl, and trimethylsulfonyl,
and wherein 1-4 carbon atom(s) of said Y is/are optionally replaced by N, NH, O, or S; and
Z is selected from the group consisting of a direct bond, —C(O)O—, (C 1 -C 6 alkyl)—C(O)O—, (C 2 -C 6 alkenyl)—C(O)O—, and (C 2 -C 6 alkynyl)—C(O)O—.
In a preferred embodiment of the compound of Formula I:
X is Z—(CH 2 CH 2 O) n , where n is 1-3, or Z—(CH 2 ) m O, where m is 2-4;
Y is selected from the group consisting of naphthalene, indacene, fluorene, phenanthrene, anthrcene, and pyrene,
wherein said Y is optionally substituted with 1-4 substituents selected from the group consisting of nitro, carboxy, oxo, phospho, and sulfo,
and wherein one carbon atom of said Y is optionally replaced by N or NH; and
Z is selected from the group consisting of a direct bond, —C(O)O—, or (C 1 -C 6 alkyl)—C(O)O—.
In a more preferred embodiment of the compound of Formula I:
X is selected from the group consisting of diethylene glycol and tetraethylene glycol;
Y is selected from the group consisting of carbazole, naphthalene, pyrene, and 4,5,7-trinitrofluorenone-2-carboxylic acid; and
Z is selected from the group consisting of a direct bond, —C(O)O—, and —CH 2 —C(O)O—.
In the most preferred embodiment of the compounds of Formula I, said compound is selected from the group consisting of:
SYNTHESIS OF COMPOUNDS OF THE INVENTION
A representative mobility donor fluorinated dendron of the present invention may be readily prepared by standard techniques of chemistry, utilizing the general synthetic pathway depicted below in Scheme I.
Utilizing the general pathway to a representative mobility donor fluorinated dendron of the present invention as shown in Scheme I, compounds may be prepared using 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoic acid as a starting material. These intermediates are then reacted with, for example, an alcohol of the desired apex moiety, such as 2-(2-carbazol-9yl-ethoxy)-ethanol, to obtain the compounds of the invention.
In the preparation of the compounds of the invention, one skilled in the art will understand that one may need to protect or block various reactive functionalities on the starting compounds or intermediates while a desired reaction is carried out on other portions of the molecule. After the desired reactions are complete, or at any desired time, normally such protecting groups will be removed by, for example, hydrolytic or hydrogenolytic means. Such protection and deprotection steps are conventional in organic chemistry. One skilled in the art is referred to “Protective Groups in Organic Chemistry,” McOmie, ed., Plenum Press, New York, N.Y.; and “Protective Groups in Organic Synthesis,” Greene, ed., John Wiley & Sons, New York, N.Y. (1981) for the teaching of protective groups which may be useful in the preparation of compounds of the present invention.
The product and intermediates may be isolated or purified using one or more standard purification techniques, including, for example, one or more of simple solvent evaporation, recrystallization, distillation, sublimation, filtration, chromatography, including thin-layer chromatography, HPLC (e.g. reverse phase HPLC), column chromatography, flash chromatography, radial chromatography, trituration, and the like.
PROCESSES AND PRODUCTS OF THE PRESENT INVENTION
The present invention further relates to a process for making a stacked nanocylinder composition having a mobility donor complex, a mobility acceptor complex, or a mobility donor-acceptor complex in its core, which comprises:
(a) heating semi-fluorinated dendrons incorporating selected dendron apex moiety(ies) and side group(s) having donor, acceptor, or donor-acceptor characteristics to an isotropic phase temperature;
(b) filling a substrate with said isotropic phase dendrons; and
(c) cooling said dendrons to a liquid crystalline phase temperature.
In a preferred embodiment, said cooling step is in the presence of a magnetic field of about 1 tesla.
In another preferred embodiment, said cooling is at a rate of about 0.1° C. per minute.
In another preferred embodiment, said substrate is an indium tin oxide coated glass substrate.
In another preferred embodiment, the substrate cell size of said nanocylinder composition is controlled by mylar spacers.
The present invention further relates to the stacked nanocylinder composition described above, made by the process which comprises the steps of:
(a) heating semi-fluorinated dendrons incorporating selected dendron apex moiety(ies) and side group(s) having donor, acceptor, or donor-acceptor characteristics to an isotropic phase temperature;
(b) filling an indium tin oxide coated glass substrate with said isotropic phase dendrons; and
(c) cooling said dendrons to a liquid crystalline phase temperature at a rate of about 0.1° C. per minute, in the presence of a magnetic field of about 1 tesla.
In order to address the need for self-organized organic nanostructures with controlled optoelectronic properties which facilitate ultrahigh density nanopatterning, we have elaborated a library based on a semifluorinated dendron that is functionalized at its apex with a diversity of D and A groups. The resulting functional dendrons are programmed to self-assemble into cylinders containing the optoelectronic element in their core. The supramolecular cylinders self-organize into homeotropically aligned hexagonal (Φ h ) or rectangular (Φ r-c and Φ r-s ) LCs.
The combination of self-assembly, insensitivity to ionic impurities, ease of processability, and high charge carrier mobility is unexpected, resulting in an unprecedented, simple, and practical strategy to increase the μ values of conventional D, A, and EDA low molar mass and macromolecular systems to levels previously obtained only by complex discotic molecules. The new supramolecular cylindrical architecture, and the universal self-processability of these programmed dendrons into large homeotropic domains (100 μm to cm size) (FIGS. 1 b, c ), create new frameworks for dendritic molecules and open new perspectives in the world of nanoscience and nanotechnology. In addition to the utility described above in relation to optoelectronic devices employing LCs, such nanocylinder compositions are expected to be uniquely useful in devices such as transistors, photovoltaics, photoconductors, photorefractives, and light emissives because of their uniquely high charge carrier mobility and relative ease of synthesis and handling.
EXAMPLES
The following examples are illustrative of the present invention and are not intended to be limitations thereon. Unless otherwise indicated, all percentages are based upon 100% by weight of the final composition. All starting materials, reagents, and solvents were commercially available and were used either as obtained from chemical suppliers, synthesized according to known literature procedures, and/or washed, dried, distilled, recrystallized, and/or purified before use.
Example 1
Preparation of {2-[2-(Carbazol-9-yl)-ethoxy]-ethyl}3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D1)
The synthesis of a mobility donor fluorinated dendron D1 of the present invention is as shown in the Scheme below. D1 is prepared using 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoic acid as a starting material. The intermediate is then reacted with an alcohol of the desired apex moiety, 2-(2-carbazol-9yl-ethoxy)-ethanol, to obtain the compound of the invention.
More particularly, compound D1 is synthesized as follows:
2-(2-Carbazol-9-yl-ethoxy)-ethanol (4): To a flask containing 100 ml benzene, 100 ml 50% NaOH, was added carbazole (2) (20 g, 0.12 mmol), 4 g benzyltriethylammonium chloride (TEBA), 1 g of NaI and 2-[2-(2-chloroethoxy)-ethoxy]-tetrahydropyran (3) (38 g, 0.12 mmol) under N 2 . The mixture was refluxed for 6 h.
The reaction mixture was diluted with 100 ml of benzene and the organic phase was separated, washed with H 2 O, dried over anhydrous MgSO 4 , and filtered through acidic Al 2 O 3 . After the removal of benzene, the crude product was suspended in 400 ml MeOH followed by addition of 2 ml of concentrated HBr. After the reaction mixture was stirred at 20° C. for 16 h, it was neutralized by 10% aqueous NaOH and MeOH was distilled. The crude product was washed with H 2 O several times, dried under vacuum and was further purified by recrystallization from MeOH twice to yield 23 g (75%) of 4 as white crystals. Purity: 99% (HPLC). TLC: R f =0.18 (hexanes/EtOAc: 3/1). mp 80-81° C. 1 H NMR (200 MHz, CD 3 COCD 3 , 20° C.): d 8.1 (d, 2H, J=7.8 Hz), 7.4 (m, 4H), 7.25 (m, 2H), 4.4 (t, 2H, J=5.7 Hz), 3.8 (t, 2H, J=5.7 Hz), 3.5 (t, 2H, J=5.0 Hz), 3.4 (t, 2H, J=5.0 Hz). 13 C NMR (50 MHz, CD 3 COCD 3 , 20° C.): d 140.9, 125.8, 123.0, 120.3, 119.1, 109.5, 72.8, 69.4, 61.1, 43.1.
{2-[2-(Carbazol-9-yl)-ethoxy]-ethyl}3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D1): A mixture containing 1 (1.0 g, 0.63 mmol) and 4 (0.17 g, 0.66 mmol) was dissolved in α,α,α-trifluorotoluene (10 ml) and stirred over 1 g of molecular sieves (4 Å) for 1 h under N 2 . DCC (0.260 g, 1.26 mmol) and DPTS (40 mg, 0.13 mmol) were added to the reaction mixture. The reaction mixture was stirred at 45° C. for 24 h under N 2 . The progress of the reaction was monitored by TLC. The reaction mixture was filtered through a sintered filter to remove the molecular sieves which were subsequently washed several times with CH 2 Cl 2 . The organic solution was concentrated and precipitated in MeOH four times from CH 2 Cl 2 solution. Purification of the crude product was performed by column chromatography (SiO 2 /CH 2 Cl 2 ), followed by precipitation in MeOH from CH 2 Cl 2 solution to yield 0.92 g (82%) of D1 as white crystals. 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 8.1 (d, 2H J=7.7 Hz), 7.4 (m, 4H), 7.2 (m, 6H), 4.5 (t, 4H, J=5.9 Hz), 4.4 (t, 2H, J=4.7 Hz), 4.2-4.0 (overlapped t, 8H), 3.7 (t, 2H J=4.7 Hz), 2.3-2.1 (m, 6H), 1.8 (m, 12H); 13 C NMR (CDCl 3 , 125 MHz, 20° C.): d 166.7, 152.6, 142.1, 140.8, 125.7, 125.2, 121.9, 120.5-108.2 (several CF multipletts), 119.6, 119.2, 108.8, 108.3, 72.7, 69.6, 69.4, 68.5, 64.1, 43.3, 30.6 (t, J CF =22 Hz), 29.8, 28.8, 17.4, 17.2. Anal. Calcd. for C 57 H 42 NF 51 O 6 : C, 38.73; H, 2.31; F, 52.95; N, 0.77. Found: C, 38.68; H, 2.12; N, 0.79. DSC: 1 st Heating k 39 (2.3) k 53 (9.6) Φ h 75 (1.0) i, 1 st cooling i 71 (0.8) Φ h 13 (4.9) k 6 g, 2 nd heating g 13 k 21 (5.0) Φ h 75 (0.8) i.
Example 2
Preparation of {2-[2-((1-Naphthyl)-acetoxy)-ethoxy]-ethyl}3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D2)
As depicted in the Scheme below, (2-hydroxyethoxy)-ethyl (1-naphthyl)-acetate is reacted with 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoic acid to produce a second representative mobility donor fluorinated dendron of the present invention, compound D2.
More particularly, compound D2 is synthesized as follows:
(2-Hydroxyethoxy)-ethyl (1-naphthyl)-acetate (7): A mixture of 1-naphthylacetic acid (5) (2.0 g, 0.011 mol), PTSA (200 mg, 1.1 mmol), and diethylene glycol (6) (8 ml, 72.8 mmol) was stirred at 120° C. under N 2 . The reaction mixture became homogeneous after 1 h, and the stirring was continued for 15 h. After the reaction was completed (confirmed by TLC), the reaction mixture was poured into 50 ml of icewater mixture. The aqueous reaction mixture was extracted by EtOAc (3×50 ml) and dried over anhydrous MgSO 4 . The crude product was purified by column chromatography (SiO 2 , EtOAc/hexanes: 8/2) to yield 2.25 g (76%) of 7 as a colorless oil. 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 7.83 (d, 1H, J=7.1 Hz ), 7.72-7.64 (m, 2H), 7.40-7.26 (m, 4H), 4.11 (t, 2H, J=4.7Hz), 3.96 (s, 2H), 3.46 (overlapped m, 4H), 3.26 (t, 2H, J=4.4 Hz), 1.90 (s, 1H). 13 C NMR (CDCl 3 , 90 MHz, 20° C.): d 171.7, 134.0, 132.2, 130.6, 128.9, 128.2, 126.5, 126.0, 125.7, 123.9, 72.4, 65.8, 64.2, 61.2, 39.3.
{2-[2-((1-Naphthyl)-acetoxy)-ethoxy]-ethyl}3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D2): To a solution of 1 (1 g, 0.63 mmol), 7 (0.68 g, 2.5 mmol), and DPTS (50 mg, 0.17 mmol) in α,α,α-trifluorotoluene (15 ml) under N 2 was added DCC (300 mg, 1.5 mmol), and the reaction mixture was stirred at 45° C. for 24 h. The mixture was diluted with CH 2 Cl 2 and precipitated in MeOH four times. The crude product was purified by flash column chromatography (SiO 2 , CH 2 Cl 2 ) and precipitated in EtOH from CH 2 Cl 2 solution to yield 0.81 g (68%) of D2 as white solid. TLC: R f =0.81 (EtOAc). Purity: 99%+(HPLC). 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 7.87-7.78 (overlapped d, 2H), 7.76 (d, 1H, J=6.8 Hz), 7.48-7.38 (m, 4H), 7.26 (s, 2H), 4.37 (t, 2H, J=4.4 Hz), 4.28 (t, 2H, J=4.5 Hz), 4.07 (s, 2H), 4.01 (m, 6H), 3.69 (m, 4H), 2.13 (m, 6H), 1.82 (m, 12H), 13 C NMR (CDCl 3 , 90 MHz, 20° C.): d 172.0, 166.3, 152.7, 142.1, 134.0, 130.5, 128.9, 128.3, 128.2, 126.6, 126.0, 125.6, 125.3, 123.9, 120.5-108.2 (several CF multipletts), 108.3, 72.8, 69.3, 69.1, 68.6, 64.2, 39.2, 30.8 (t, J CF =22 Hz), 29.9, 28.9, 17.5, 17.3. FAB-MS for C 59 H 43 F 51 O 8 m/z: 1871.2 [M+Na] + . Anal. Calcd. for C 59 H 43 F 51 O 8 C, 38.33, H, 2.34, found C, 38.42, H, 2.20. DSC: 1 st heating k 24 (0.7) k 48 (8.9) Φ h 75 (0.4) i, 1 st cooling i 70 (0.4) Φ h 1 6 (3.2) k. 2 nd heating g 11 k 24 (3.0) Φ h 74 (0.4) i.
Example 3
Preparation of {2-[2-((1-Pyrenyl)-acetoxy)-ethoxy]-ethyl}3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D3)
As depicted in the Scheme below, 2-(2-Hydroxyethoxy)-ethyl (1-pyrenyl)-acetate is reacted with 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoic acid to produce compound D3.
More particularly, compound D3 is synthesized as follows:
2-(2-Hydroxyethoxy)-ethyl (1-pyrenyl)-acetate (15): 1-Pyreneacetic acid (1 g, 3.85 mmol), diethylene glycol (10 ml, 91.0 mmol) and p-toluenesulfonic acid (100 mg, 0.58 mmol) were mixed and heated to 130° C. for 16 h with stirring under N 2 . After the reaction was completed (confirmed by TLC), the reaction mixture was cooled to 20° C. and poured into 50 ml ice-water drop-wise. The aqueous reaction mixture was extracted with EtOAc (3×100 ml) and the combined organic solutions were washed with 5% aqueous KOH (2×50 ml), H 2 O (2×50 ml) and brine (1×50 ml), and were subsequently dried over anhydrous MgSO 4 . The crude product was purified by column chromatography (silica gel, EtOAc/hexanes: 1/1) to yield 1.12 g (83.59%) 15 as a light green oil. Purity: 99+% (HPLC). TLC: R f =0.17 (EtOAc/hexanes: 1/1). 1 H NMR (250 MHz, CDCl 3 , 20° C.): δ 8.26-7.94 (m, 9H), 4.38 (s, 2H), 4.27 (m, 2H), 3.63 (m, 2H), 3.53 (m, 2H), 3.39 (m, 2H), 2.82 (s broad, 1H). 13 C NMR (125 MHz, CDCl 3 , 20° C.): δ 171.5, 131.3, 130.8, 130.7, 129.4, 128.3, 127.9, 127.4, 127.3, 126.0, 125.3, 125.1, 125.0, 124.8, 124.7, 123.2, 72.2, 68.9, 64.1, 61.6, 39.4.
{2-[2-((1-Pyrenyl)-acetoxy)-ethoxy]-ethyl}3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D3): 15 (0.40 g, 1.15 mmol), 1 (1.46 g, 0.92 mmol), DCC (0.57 g, 2.75 mmol) and DPTS (14 mg, 45.7 μmol) were dissolved in α,α,α-trifluorotoluene (20 ml) and stirred for 16 h at 55° C. under N 2 . The solvent was evaporated and the residue was dissolved in CH 2 Cl 2 (10 ml) and precipitated in MeOH (50 ml) 4 times. The crude product was further purified by column chromatography (silica gel, EtOAc/hexanes: 3/7) to yield 1.33 g (60.0%) of D3 as a white powder. Purity: 99+% (HPLC). TLC: R f =0.37 (EtOAc/hexanes: 3/7). 1 H NMR (250 MHz, CDCl 3 , 20° C.): δ 8.21-7.89 (m, 9H), 7.22 (s, 2H), 4.35-4.28 (m overlapping, 6H), 3.95-3.93 (m, 6H), 3.72-3.67 (m, 4H), 2.20-2.05 (m, 6H), 1.90-1.70 (m, 12H). 13 C NMR (125 MHz, CDCl 3 , 20° C.): 171.5, 166.1, 152.5, 141.9, 131.3, 130.8, 130.7, 129.4, 128.3, 128.0, 127.9, 127.3, 126.0, 125.3, 125.1, 125.1, 125.0, 124.8, 124.6, 123.2, 120.5-108.2 (several CF multipletts), 108.1, 72.6, 69.1, 69.0, 68.4, 64.1, 64.0, 39.3, 30.6 (t, J CF =22 Hz), 29.7, 28.6, 17.3, 17.1. MALDI: 1923.11 (M+H + ); 1946.22 (M+Na + +H + ); 1962.20 (M+K + +H + ). DSC: 1 st heating: k 49 (11.0) Φ h 97 (0.5) i, 2 nd heating: g −2 k 19 (2.3) Φ h 97 (0.5) i, 1 st cooling: i 92 (−0.4) Φ h 7 g.
Example 4
Preparation of [4-(1-Pyrenyl)-butyl]3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D4)
As depicted in the Scheme below, 1-pyrenebutanol is reacted with 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoic acid to produce a fourth representative mobility donor fluorinated dendron of the present invention, D4.
More particularly, compound D4 is synthesized as follows:
[4-(1-Pyrenyl)-butyl]3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoate (D4): To a solution of 1 (0.5 g, 0.31 mmol), 1-pyrenebutanol 16 (95 mg, 0.34 mmol) and DPTS (20 mg, 65.4 μmol) in α,α,α-trifluorotoluene (20 ml) under N 2 was added DCC (140 mg, 0.68 mmol), and the reaction mixture was stirred at 45° C. for 24 h. The reaction mixture was cooled to 20° C. and the product was precipitated in MeOH which was subsequently precipitated in MeOH three times from CH 2 Cl 2 solution. The crude product was purified by column chromatography (SiO 2 , CH 2 Cl 2 ) and followed by precipitating in EtOH from CH 2 Cl 2 solution yielded 320 mg (55%) of D4 as white solid. TLC: R f =0.52 (CH 2 Cl 2 /hexanes: 2/1). Purity: 99%+: (HPLC). 1 H NMR (CDCl 3 , 200 MHz, 20° C.): d 8.26 (d, 1H, J=7.6 Hz), 8.18-7.98 (m, 7H), 7.89 (d, 1H, J=7.8 Hz), 7.24 (s, 2H), 4.4 (t, 2H, J=6.0 Hz), 3.98 (m, 6H), 3.44 (t, 2H, J=7.3 Hz), 2.13 (m, 8H), 1.81 (m, 14H). 13 C NMR (CDCl 3 , 90 MHz, 20° C.): d 166.2, 152.5, 141.8, 131.7, 131.1, 130.2, 128.8, 127.8, 127.7, 127.5, 127.1, 126.1, 125.8, 125.2, 125.0, 123.5, 120.5-108.2 (several CF multipletts), 107.9, 72.6, 68.2, 64.9, 33.0, 30.7 (t, J CF =22 Hz), 30.4, 28.7, 28.6, 28.2, 17.3, 17.1. FAB-MS (m/z): 1871.2 [M+Na] + . Anal. Calcd. for C 63 H 43 F 31 O 3 C, 41.19; H 2.58; found C, 41.04; H, 2.08. DSC: 1 st heating k 59 (8.2) k 63 (−11.0) k 83(11.7), k 90 (11.2) i, 1 st cooling i 78 (0.5) Φ h 2 g. 2nd heating g −1.0 k 13 (1.3) Φ h 82 (0.6) i.
Example 5
Preparation of 2-[2-(4,5,7-Trinitro-9-fluorenone-2-carboxy)-ethoxy]-ethyl 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-Heptadecafluoro-n-dodecan-1-yloxy)benzoate (A1)
As depicted in the Scheme below, [2-(2-Hydroxyethoxy)-ethyl](4,5,7-trinitro-9-fluorenone)-2-carboxylate is reacted with 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-heptadecafluoro-n-dodecan-1-yloxy)-benzoic acid to produce a representative mobility acceptor fluorinated dendron of the present invention, compound A1.
More particularly, compound A1 is synthesized as follows:
[2-(2-Hydroxyethoxy)-ethyl](4,5,7-trinitro-9-fluorenone)-2-carboxylate (18): A mixture of 4,5,7-trinitro-9-fluorenone-2-carboxylic acid 17 (2.0 g, 5.6 mmol), diethylene glycol (4 ml, 36.4 mmol) and 100 mg (0.58 mmol) of PTSA was stirred at 120° C. under N 2 . The reaction mixture became homogeneous after 1 h and the stirring was continued overnight (12 h). The reaction mixture was cooled to 20° C. and poured into a mixture of ice and H 2 O (50 ml) drop-wise. The crude product was separated from H 2 O as a light brown solid. Column chromatography (SiO 2 , hexanes/EtOAc: 60/40) followed by recrystallization from ethanol yielded 1.6 g (65%) of 18 as brown crystals. Purity: 99% (HPLC). TLC: R f =0.1 (hexanes/EtOAc: 3/1). mp 140° C. 1 H NMR (200 MHz, CDCl 3 , 20° C.): d 8.99 (d, 1H, J=2 Hz), 8.89 (t, 2H, J=2 Hz), 8.75 (d, 1H, J=2 Hz), 4.60-4.64 (q, J=4Hz, 2H), 3.91-3.89 (q, 2H, J=4 Hz), 3.81-3.77 (q, 2H, J=4.1 Hz), 3.65-3.69 (q, 2H, J=4 Hz). 13 C NMR (50 MHz, CDCl 3 , 20° C.) d 186.43, 162.03, 149.96, 147.08, 146.81, 138.70, 138.63, 137.95, 135.75, 131.95, 129.56, 125.70, 122.19, 72.82, 69.09, 65.90, 62.04.
2-[2-(4,5,7-trinitro-9-fluorenone-2-carboxy)-ethoxy]-ethyl 3,4,5-tris-(12,12,12,11,11,10,10,9,9,8,8,7,7,6,6,5,5-Heptadecafluoro-n-dodecan-1-yloxy) benzoate (A1): A mixture containing 1 (1.0 g, 0.63 mmol) and 18 (0.295 g, 0.65 mmol) was dissolved in α,α,α-trifluorotoluene (10 ml) and stirred over molecular sieves (4 Å) for 1 h under N 2 . DCC (0.260 g, 1.26 mmol) and DPTS (40 mg, 0.13 mmol) were added to the reaction mixture. The reaction mixture was stirred at 45° C. for 24 h under N 2 . The progress of the reaction was monitored by TLC (hexanes/EtOAc: 75/25) (R f =0.75). The reaction mixture was filtered through a sintered funnel and the molecular sieves were washed several times with CH 2 Cl 2 . The organic solution was concentrated and precipitated in MeOH four times from CH 2 Cl 2 solution. The crude product was purified by column chromatography (SiO 2 /CH 2 Cl 2 ) to yield 1.08 g (85%) orange crystals. 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 9.09-9.10 (d, 1H, J=2 Hz), 8.93-8.85 (t, 2H, J=2 Hz), 8.71-8.70 (d, 1H, J=2 Hz), 7.39 (s, 2H), 4.76-4.71 (q, 2H, J=4 Hz), 4.62-4.58 (q, 2H, J=4 Hz), 4.12-4.09 (m, 6H) 4.03-4.01 (m, 4H), 2.33-2.20 (m, 6H), 1.99-1.85, 1.70-1.38 (m, 12H). 13 C NMR (CDCl 3 , 90 MHz, 20° C.): d 184.78, 165.91, 162.73, 152.51, 149.70, 146.73, 146.53, 140.42, 138.58, 137.65, 135.25, 131.48, 128.96, 125.25, 125.1, 122.52, 120.5-108.2 (several CF multipletts), 108.03, 105.73, 72.67, 69.18, 68.48, 65.36, 63.75, 31.17 (t, J CF =22 Hz), 29.75, 28.83, 17.3-17.17. Anal. Calcd for C 61 H 38 N 3 F 51 O 15 : C, 36.24; H, 1.89; F, 47.92; N, 2.08. Found: C, 36.41; H, 1.79; N, 1.92. DSC: 1 st heating k 50 (2.0) Φ r-c 121 (0.4) i, 1 st cooling i 115 (0.4) Φ r-c 33 g. 2 nd heating g 34 Φ r-c 121 (0.4) i.
Example 6
Preparation of Poly([2-(2-carbazol-9-yl-ethoxy)-ethyl]methacrylate) (DP2)
[2-(2-Carbazol-9-yl-ethoxy)-ethyl]methacrylate (20): 1.05 g (4.12 mmol) 4 and 0.65 g (6.22 mmol) methacryloyl chloride were dissolved in 15 ml of carbon tetrachloride. After the addition of 2.6 g activated molecular sieves (3 Å), the mixture was heated to reflux for 24 h. After cooling down to room temperature, it was filtered over basic alumina using 20% THF in CCl 4 . Evaporating the solvent yielded 0.8 g (60.1%) of a viscous yellow oil. R f =0.44 (EtOAc/hexanes: 2/8). 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 8.10 (t, 2H, J=7.76 Hz), 7.44 (m, 4H), 7.23 (m, 2H), 5.99 (s, 1H), 5.51 (s, 1H), 4.49 (t, 2H, 5.95 Hz), 4.19 (t, 2H, J=4.75 Hz), 3.88 (t, 2H, J=5.95 Hz), 3.59 (t, 2H, J=4.75 Hz), 1.88 (s, 3H). 13 C NMR (CDCl 3 , 125 MHz, 20° C.): d 167.3, 140.6, 136.0, 125.8, 125.7, 122.9, 120.3, 119.0, 108.8, 69.5, 69.3, 63.7, 43.2, 18.2.
Poly([2-(2-Carbazol-9-yl-ethoxy)-ethyl]methacrylate) (DP2): A Schlenk tube was charged with 2.1 ml 1,4-dioxane, 0.5 g (1.55 mmol; 23.8% w/v) 20 and 30.0 mg AIBN (6%). The reaction mixture was degassed six times and the polymerization was carried out at 60° C. for 48 h. The polymer was purified by precipitation of the crude polymer from THF solution three times into methanol. The molecular weights related to poly (styrene) standards were determined in THF. M n =11,400. M w /M n =1.96. 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 7.91 (br, 2H), 7.29-7.04 (br, 6H), 4.15 (br, 2H), 3.82 (br, 2H), 3.48 (br, 2H), 3.20 (br, 2H), 1.94-1.87 (br, 2H), 1.20-0.90 (br, 3H).
Example 7
Preparation of Poly(2-{2-[2-(2-methacryloyloxyethoxy)-ethoxy]-ethoxy}-ethyl 4,5,7-Trinitrofluoren-9-one-2-carboxylate) (AP1)
2-{2-[2-(2-hydroxyethoxy)-ethoxy]-ethoxy}-ethyl 4,5,7-trinitro-fluoren-9-one-2-carboxylate (22): 1 g (2.78 mmol) 17, 15 ml (86.6 mmol) dry tetraethylene glycol and 100 mg (0.58 mmol) p-toluenesulfonic acid were dissolved in toluene (100 ml). The flask was equipped with a water receiver and the reaction mixture was heated to reflux for 16 h. After removing the toluene, ethyl acetate was added and extracted with water for two times. The ethyl acetate was evaporated and the product was filtered over a short silica gel column using 30% hexanes in ethyl acetate as eluent. The solvent was removed and the product was precipitated from CH 2 Cl 2 into hexanes to yield 0.83 g (55.8%) of a highly viscous dark red oil. R f =0.29 (EtOAc). 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 8.98 (s, 1H), 8.85 (s, 2H), 8.76 (s, 1H), 4.61 (t, 2H, J=4.6 Hz), 3.89 (t, 2H, J=4.7 Hz), 3.70 (m, 10H), 3.59 (t, 2H, J=4.7 Hz), 2.30 (s br, 1H). 13 C NMR (CDCl 3 , 125 MHz, 20° C.): d 184.9, 162.7, 149.6, 146.8, 146.5, 138.5, 138.4, 137.6, 136.1, 135.6, 131.8, 129.4, 125.4, 122.6, 72.5, 70.7, 70.6, 70.5, 70.3, 68.8, 65.7, 61.7.
2-{2-[2-(2-methacryloyloxyethoxy)-ethoxy]-ethoxy}-ethyl 4,5,7-trinitrofluoren-9-one-2-carboxylate (23): 0.7 g (1.3 mmol) 22, 0.15 g (1.44 mmol) 19 and 0.5 g activated molecular sieves (4 Å) were added to dry THF (10 ml). After the mixture was cooled to 0° C., 0.15 g (1.44 mmol) triethylamine was added. Then it was allowed to reach room temperature and was stirred for three hours. Ammonium salts were filtered off, the THF was evaporated and the crude product was redissolved in chloroform. The solution was extracted three times with diluted potassium hydroxide solution, two times with water, one time with brine and was then dried over magnesium sulfate. After the chloroform was evaporated, the monomer was purified by column chromatography on silica gel using 50% ethyl acetate in hexanes as eluent. The evaporation of the solvent yielded 0.4 g (51%) of a viscous dark orange oil. R f =0.37 (EtOAc/hexanes: 1/1). 1 H NMR (CDCl 3 , 500 MHz, 20° C.): d 8.99 (s, 1H), 8.85 (m, 2H), 8.74 (s, 1H), 6.10 (s, 1H), 5.56 (s, 1H), 4.60 (m, 2H), 4.28 (m, 2H), 3.88 (m, 2H), 3.71 (m, 10H), 1.93 (s, 3H). 13 C NMR (CDCl 3 , 125 MHz, 20° C.): d 184.9, 162.6, 149.6, 146.8, 138.5, 138.4, 137.6, 136.2, 136.1, 135.5, 131.7, 129.3, 125.7, 125.3, 122.6, 70.7, 69.1, 68.8, 65.7, 63.8, 18.3.
Poly(2-{2-[2-(2-methacryloyloxyethoxy)-ethoxy]-ethoxy}-ethyl 4,5,7-trinitrofluoren-9-one-2-carboxylate) (AP1): A Schlenk tube was charged with 0.8 ml 1,4-dioxane, 0.3 g (1.55 mmol; 37.5% w/v) 23 and 55.0 mg AIBN (18.3%). The reaction mixture was degassed six times and the polymerization was carried out at 60° C. for 36 h. The polymer was purified by precipitation of the crude polymer from THF solution three times into methanol. The molecular weights related to poly(styrene) standards were determined in THF. M n =11,000. M w /M n =2.07. 1 H NMR (CDCl 3 , 500 MHz, 20° C.): 8.94-8.56 (m br, 4H), 4.58 (s br, 2H), 4.27-3.70 (m br, 14H), 1.86 (s br, 3H), 1.4-0.7 (m, br, 2H).
Example 8
Preparation of Poly(-vinyl Carbazole) (DP1)
Poly(-vinyl carbazole) (DP1): The polymerization of vinyl carbazole was carried out in benzene (50%, w/v) under N 2 at 60° C. AIBN (5%) was used as a radical initiator. The polymerization was terminated by diluting the polymerization mixture with CH 2 Cl 2 and by precipitating in MeOH. The polymer was fractionated using CH 2 Cl 2 as solvent (1%, w/v) and MeOH as nonsolvent at 20° C. into following fractions. Fraction 1: M n =6,450 (M w /M n : 1.47). Fraction 2: M n =12,100 (M w /M n : 1.75). Fraction 3: M n =28,600 (M w /M n : 1.38). Fraction 4: M n =57,450 (M w /M n : 1.49). Fraction 5: M n =67,350 (M n /M w : 1.28).
Example 9
Preparation of Nanocylinder Compositions
Carbazole derivatives (D1), naphthalene derivatives (D2) and pyrene derivatives (D3 and D4) have been introduced at the apex as D, and 4,5,7-trinitrofluorenone-2-carboxylic acid (TNF) as A (A1), as discussed above, to produce fluorinated dendrons of the present invention having desired D, A, or D-A characteristics. A diethylene glycol or tetraethylene glycol spacer between the dendron and the D or A groups decouples their motion and facilitates fast self-assembly dynamics. In addition to this extraordinary simplicity, and diversity in synthesis, the self-assembled D and A groups are protected from moisture by the internal compartmentalization of the cylinder and external jacketing with the fluorinated coat.
Co-assembling a D-dendron with an A-dendron incorporates an electron donor-acceptor (EDA) complex in the center of the cylinder (for example, A1+D1). Amorphous polymers with A and D side groups form EDA complexes when the D-dendron (for example, D1) is mixed with an A-polymer (for example, AP1) and when an A-dendron (for example, A1) is mixed with a D-polymer (for example, DP1 or DP2). Surprisingly, these EDA complexes self-assemble into cylinders that are self-organized into Φ h or Φ r LCs. We expect that the driving force of the fluorophobic effect is so strong that the complexed polymer is forced to reside in the center of the cylinder. EDA interactions, rather than the previously reported covalent bonding, are generating a supramolecular polymer with dendritic side groups. Nevertheless, as in the previous case, the random-coil conformation of the backbone becomes organized by jacketing with its dendritic side groups. The self-assembly and self-organization into Φ h (D1, D2, D3, D4, D1+A1, A1+DP1, A1+DP2), Φ r-s (D1+AP1) and Φ r-c (A1) LCs was demonstrated by a combination of techniques, including differential scanning calorimetry (DSC), thermal optical polarized microscopy (TOPM), X-ray diffraction (XRD), and electron diffraction (ED). Calculations based on density and XRD measurements indicate that between 3.8 and 4.6 dendrons self-assemble into a 4.8 Å stratum of the cylinder. These self-processed systems consist of 4.5×10 12 to 5.8×10 12 cylinders per square centimeter. Accordingly, these systems are about two orders of magnitude denser than previously reported examples.
Table 1 summarizes the structures and the field and temperature independent μ e and μ h values of the supramolecular assemblies determined by the time of flight (TOF) method. D-dendrons lead to μ h ranging from 10 −4 to 10 −3 cm 2 ·V −1 ·s −1 in the LC state whereas the A-dendron (A1) has an μ e of 10 −3 cm 2 ·V −1 ·s −1 . The μ of the EDA polymer complexes are in the same range. All these values are from two to five orders of magnitude higher than those of the related D and A compounds in the amorphous state (see Table 1). We expect that this enhancement is due to the p-stacked one-dimensional ordered structure of D, A or EDA complex in the center of the supramolecular column. The charge migration through the columns is not well understood, but we believe that it involves a polaron hopping process. XRD and 1 H-NMR studies demonstrate p-p-interactions between the D or A groups. The μ of these very simple D-dendrons is similar to those of more complex discotic LCs. Higher μ reported on these discotic molecules was obtained either in the Φ ho crystal phase or was measured by contactless pulse-radiolysis time-resolved microwave conductivity (PR-TRMC) that provides the one-dimensional intracolumnar mobility. TOF data are inherently lower, accounting for the structural imperfections within the inter-electrode gap but are more relevant for technical applications than the higher values obtained by PR-TRMC.
Cooling the LC state leads to crystallization in the case of D2, whereas the 2-D order of D1, D3 and A1 is enhanced in the glassy state, showing helical short-range order. For example, the XRD of a fiber of A1 in the glassy ordered state cooled from the LC phase exhibits, in the small-angle region, the pattern of the Φ h order (FIG. 1 ). This demonstrates that the LC order is frozen into a glassy Φ h state. In addition, at wide-angle the XRD pattern reveals diffuse spots arranged in an x-like fashion that indicates short-range helical correlation along the column axis with an average repeat distance of 4.8±0.3 Å (“E” in FIG. 1 ). We expect that this value arises from the packing of the aromatic regions of the dendron near the aliphatic tails. This XRD also shows diffuse spots assigned to disordered p-stacks of TNF units in the core of the column with an average separation of 3.44 Å (“C” in FIG. 1 ). Consequently, μ of this glassy LC state increases since the motion of the D groups from the core of the supramolecular cylinder is decreased, leading to reduced dynamic disorder (Table 1). Furthermore, the motion of ionic impurities is frozen in the ordered state, whereas the photo-generated charges continue to migrate within the system. Therefore, the glassy ordered state is essentially insensitive to ionic impurities.
FIG. 2 depicts 1 H NMR spectra of A1 in CDCl 3 solution at 22° C., in the isotropic melt at 120° C., in the Φ h LC state at 75° C. and in the Φ h glassy state at 25° C. In this sequence, the loss of molecular mobility is reflected by the increase of the line widths. As fast magic-angle spinning is applied (except for the solution), four groups of 1 H resonances can be distinguished in all spectra: aromatic fluorenone (9-8 ppm), dendron phenyl (7-6 ppm), OCH 2 (4.5-3 ppm), and alkyl (2.5-1 ppm). In the glass, the LC phase and the melt, the lines are shifted to high field by 0.5-0.7 ppm relative to the solution-state values except for the alkyl resonances. This effect is due to aromatic p-electrons situated above or below the respective protons, and thus provides direct evidence for p-p packing of the fluorenones and the dendron phenyls. Analogous effects are observed in the 1 H spectra of the other materials. Moreover, in A1 a distance of 3.5 Å was determined between the protons in adjacent fluorenone moieties by 1 H— 1 H double-quantum NMR spectroscopy, which leads to the expectation of a sandwich-type packing of pairs of nitro-fluorenone groups (FIG. 2 e ). Combining the NMR information with the XRD data, it can be concluded that, in the glassy Φ h phase, the cylinder adopts a supramolecular structure of the form schematically depicted in FIG. 2 f . In the center, the fluorenone sandwiches are stacked in a column surrounded by dendrons whose phenyl groups are arranged in a helical fashion around the central column. Furthermore, NMR data provides evidence for the separation of the fluorenones (center), dendron phenyls (inner ring) and alkyl chains (outer ring) from each other, as there are no proton-proton distances detectable between the different units on a length scale of less than 4 Å. This separation, however, is not completely achieved when the material is precipitated from solution, but only when the system is enabled to self-organize in the course of a cooling process from the melt into the LC and glassy Φ h phases. Prior to this process the supramolecular column contains errors introduced by intramolecular backfolded A1 dendrons. A self-repair process occurs during cooling from the isotropic melt. The supramolecular structure from FIG. 2 f in some ways resembles that of base-pairs in DNA.
Tables 2-5 summarize the structural analysis of A and D dendrons and of their EDA complexes, as well as the EDA complexes of A and D dendrons with amorphous polymers containing D and A side groups by XRD experiments. The charge carrier mobilities of amorphous polymers and the acceptor compound available in the literature are reported in Tables 4 and 5. Charge carrier mobilities determined by TOF are reported in Tables 2 and 5.
TABLE 1
μ h and μ e values of D, A and EDA dendrons in the LC and glassy LC state at selected temperatures (° C.). Values of related amorphous structures are also reported.
μ (cm 2 · V −1 · s −1 )
(h) 1.3 · 10 −3 (Φ h /65)
(h) 3.5 · 10 −3 (Φ h /50)
(h) 9.4 · 10 −4 (Φ h /60)
(h) 1.5 · 10 −3 (Φ h /50)
(n) 2.3 · 10 −3 (Φ r-c /50)
(h) 5.0 · 10 −3 (gΦ h /18)
(h) 1.3 · 10 −3 (gΦ h /18)
(n) 7.5 · 10 −3 (gΦ r-c /10)
EDA Complexes
D1 + A1
molor ratio
95/5
50/50
50/50
50/50
μ (cm 2 · V −1 · s −1 )
(h) 1.6 · 10 −3 (Φ h /70)
(h) 10 −4 (Φ h /70)
(h) 2.3 · 10 −4 (Φ h /70)
(h) 2.3 · 10 −4 (Φ h /60)
(h) 1.5 · 10 −4 (Φ h /70)
(n) 7.5 · 10 −4 (Φ r-s /60)
Related systems (all at 25° C.)
DP1 + A2
μ (cm 2 · V −1 · s −1 )
(h) 1.5 · 10 −7 (g)*
(h) 1.5 · 10 −6 (g)*
(n) 6 · 10 −5 (g) †
(n) 2.8 · 10 −8 (g) ‡
(h) 2.0 · 10 −8 (g) §
(n) 2.0 · 10 −6 (g) §
*ref. 25.
† Emerald, R. L., Mort, J. J. Appl. Phys. 45, 3943-3945 (1974).
‡ Turner, S. R. Synthesis, Macromolecules 13, 782-785 (1980).
§ Gill, W. D. J. Appl. Phys. 43, 5033-5040 (1972).
TABLE 2
Thermal transitions, X-ray results, and charge
carrier mobilities (μ h and μ e ) of compounds D1-D4 and A1.
Transition temperatures (° C.) and
d-spacings and lattice dimensions
μ h and μ s (cm 2 .V −1 .s −1 )
Compound
enthalpy changes (kcal-mol −1 )
(Å) at T (° C.)
Phase and T (° C.)
D1
k 39 (2.3) k 53 (9.6) Φ h 75 (1.O) i
Φ h :d 10 (39.0) d 11 (22.4) d 20 (19.5)
1.3 · 10 −3 (Φ h , 65, h)
g 13 k 21 (5.0) Φ h 75 (0.8) i
<a> (44.9)
5.0 · 10 −3 (g, 18, h)
i 71 (−0.8) Φ h 13 (−4.9) k 6 g
T (61)
D2
k 24 (0.7) k 48 (8.9) Φ h 74 (0.4) i
Φ h :d 10 (40.8) d 20 (20.1) <a> (46.8)
3.5 · 10 −3 (Φ h , 50, h)
g 11 k 24 (3.0) Φ h 74 (0.4) i
T (36)
i 70 (−0.4) Φ h 16 (−3.2) k
D3
k 49 (11.0) Φ h 97 (0.5) i
Φ h :d 10 (42.5) d 11 (24.2) d 20 (20.9)
9.4 · 10 −4 (Φ h , 60, h)
g −2 k 19 (2.3) Φ h 97 (0.5) i
<a> (48.6) T (30)
1.3 · 10 −3 (g, 18, h)
i 92 (−0.4) Φ h 7 g
D4
k 59 (8.2) k 63 (−11.0) k 83 (11.7)
Φ h :d 10 (39.0) d 11 (22.3) d 20 (19.2)
1.5 · 10 −3 (Φ h , 55, h)
k 90 (11.2) i
<a> (44.6) T (60)
g −1 k 13 (1.3) Φ h 82 (0.6) i
i 78 (−0.5) Φ h 2 g
A1
k 50 (2.O) Φ r-c 121 (0.4) i
Φ r-c *:d 11 (44.3) d 02 (41.3) d 20 (25.5)
2.0 · 10 −3 (Φ r-c , 50, e)
g 34 Φ rc 121 (0.4) i
d 22 (21.8) d 04 (20.5) a (51.4)
7.5 · 10 −3 (g, 10, e)
i 115 (−0.4) Φ r-c 33 g
b (82.0)
b/a = 1.60 T (25)
*In the centered rectangular lattice (Φ r-c ), the columns with elliptical cross-section are centered at the corners as well as the center of the rectangular unit cell.
TABLE 3
Densities ρ of compounds D1-D4 and A1,
number of molecules per cylinder stratum of 4.8 Å (N m ),
and number of columns per cm 2 (N c ).
Density ρ
N c
Compound
(g · cm −3 )
N m *
(cm −2 )
D1
1.62
4.54
5.73 · 10 12
D2
1.49
4.42
5.27 · 10 12
D3
1.49
4.58
4.89 · 10 12
D4
1.53
4.12
5.81 · 10 12
A1
1.25
3.76
4.75 · 10 12
*
For
the
Φ
h
lattice
:
N
m
=
ρ
·
3
·
a
2
·
l
·
N
A
2
M
w
;
for
the
Φ
r
-
c
lattice
:
N
m
=
ρ
·
a
·
b
·
l
·
N
A
2
M
w
with
:
a, b = lattice dimensions, I = 4.8 Å (thickness of the stratum), N A = Avogadro's number, M w = molecular weight.
†For
the
Φ
h
lattice
:
N
c
=
2
3
·
a
2
;
for
the
Φ
r
-
c
lattice
:
N
c
=
2
a
·
b
.
TABLE 4
Molecular weights (M n ), polydispersities (M w /M n ) and
glass transition temperatures (T g ) of DP1, DP2 and AP1 and
charge carrier mobilities (μ) of related polymers DP1 and
AP2 reported in the literature.
μ h and μ s (cm 2 · V −1 · s −1 )
Polymer
M n (M w /M n )
T g (° C.)
at T (° C.)
DP1
6,443 (1.47)
77
1.5 · 10 −7 (25, h)*
DP2
11,426 (1.96)
74
13
DP3
31,000 (4.5)*
146*
9 · 10 −6 (25, h)
AP1
4: 11,041 (2.07)
55
—
AP2
1: 7,939 (1.88)
—
2.8 · 10 −8 (25, e) †
*Uryu, T., Ohkawa, H., Oshima, R. Macromolecules 20, 712-716 (1987). †Turner, S. R. Macromolecules 13, 782-785 (1980).
TABLE 5
Thermal transitions, X-ray results and charge carrier
mobility μ of prepared and related EDA complexes.
d-spacings and
μ h and μ s
Transition temperatures (° C.) and
lattice dimensions
(cm 2 · V −1 · s −1 )
EDA complexes
enthalpy changes (kcal · mru −1 )
(Å) at T (° C.)
Phase and T (° C.)
DP1/A2 (50/50)
—
—
2.0 · 10 −8 (24, h)*
2.0 · 10 −6 (24, e)*
D1/A1 (95/5)
k 23 (1.7) Φ h 81 (0.6) i
Φ h :d 10 (41.3)
1.6 · 10 −3 (Φ h , 70,
g 16 k 23 (1.4) Φ h 81 (0.5)
d 20 (21.0)
h)
i 75 (−0.5) Φ h 16 (−1.5) k 7 g
d 30 (14.1)
<a> (48.1) T (55)
A1/DP1 (50/50)
k 53 (1.2) Φ h 124 (0.39) i
Φ h :d 10 (59.3)
10 −4 (Φ h 50, h)
g 42 Φ h 120 (0.23) i
d 20 (29.6)
i 107 (−0.24) Φ h 35 g
<a> (68.5) T (87)
A1/DP2 (50/50)
k 54 (1.8) Φ h 167 (0.1) i
Φ h :d 10 (59.3)
2.3 · 10 −4 (Φ h , 70,
g 46 Φ h 168 (0.1) i
d 20 (29.6)
h)
i 157 (−0.3) Φ h 35 g
<a> (68.5) T (87)
1.5 · 10 −4 (Φ h , 70,
e)
D1/AP1 (50/50)
g 33 k 43 (1.2) Φ r-c 97 (0.1) N c 132
Φ r-g †:d 10 (62.8)
5.3 · 10 −4 (Φ r-g , 60,
(0.4) i
d 11 (53.7)
h)
g 26 Φ r-c 99 (0.1) N c 132 (0.8) i
d 03 (37.4)
4.8 · 10 −4 (Φ r-g , 60,
i 124 (−0.2) N c 87 (−0.1) Φ r-c 29 g
d 13 (31.9) a (61.8)
e)
b (111.9) T (71)
N c :(63.8, 34.9)
b/a = 1.81 T (110)
Gill, W.D. J. Appl. Phys. 43, 5033-5040 (1972). †The columns with elliptical cross-section organize in a simple rectangular lattice (Φ r-s ) with the columns centered at the corners of the rectangular unit cell.
Example 10
Charge Carrier Mobility of Nanocylinder Compositions
Purification of A and D dendrons and A and D polymers. A and D dendrons and A and D polymers were purified by precipitation from their CH 2 Cl 2 solutions into methanol, followed by filtration and vacuum drying as many times as required to provide samples essentially free of ionic impurities. This level of purity was generally reached after about four precipitations. The absence of ionic impurities was determined by spectroscopy using the time of flight (TOF) method.
Sample Preparation. Liquid crystal cells were assembled from indium tin oxide (ITO) coated glass substrates. The cells were assembled by cementing two substrates separated by mylar spacers. These cells were then filled in the isotropic phase using the capillary effect, and then slowly cooled down to the liquid crystalline phase at a cooling rate of approximately 0.1° C./min. As a result, homeotropic alignment of LC films having the columnar long axis normal to the electrode surfaces was achieved. Polarizing optical microscopy revealed a large domain size, in the range of 200-300 μm. The cell thickness was controlled by the spacers and ranged from 11 to 50 μm. Because the thickness of LC layer was considerably smaller than the domain size, charge carriers can be transported from one electrode to the other without encountering domain boundaries. Because of the low charge generation efficiency in some of the films, double layer films that include a charge generation layer (CGL) were prepared. Metal-free phthalocyanine (H2Pc) was dispersed in polyvinyl butyral (PVB) (poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate, M.W. 50,000-80,000) in a ratio of 40:60% by weight. The CGL was deposited from tetrahydrofuran (anhydrous 99.9%) solution by spin coating onto ITO substrate. Deposited films were dried at 100° C. for 4 hours in order to remove the residual solvent. The CGL thicknesses were measured with a stylus profilometer and were found to be between 0.5 to 0.8 μm. Because of the rough surface of the CGL, alignment for double layer cells was performed by slow cooling from the isotropic phase in the presence of a 1 T magnetic field.
Charge Carrier Mobility—Time of Flight. A conventional time of flight technique was employed to measure the transient photocurrent and to determine the mobility of charge carriers. A 3.6 ns Q-switched Nd:YAG based laser that was frequency doubled and frequency shifted using a H 2 stimulated Raman shifter was used to generate the charge carriers in a constant electric field. Two different charge generation mechanisms (intrinsic and extrinsic) were used. The intrinsic excitation (without the CGL layer) of LC by laser irradiation (λ=320 nm, third anti-Stokes component of a 532 nm pump) into the main absorption band of LC resulted in the creation of electron-hole pairs in a very thin layer, light penetration depth less than 1 μm, near the illuminated electrode. Depending on the polarity of the applied electric field, one charge carrier was eliminated at the illuminated electrode, while the other one moves through the sample towards the counter electrode. The extrinsic excitation (with the CGL layer) was employed with laser irradiation at 680 nm (first Stokes component) into the main absorption band of the dye layer. Charge carriers were formed at the LC/H2Pc interface and injected in to the LC layer. The charge motion creates a displacement current, which was measured with a current to voltage converter and pre-amplifier, and then was digitized with an oscilloscope. The mobility was calculated using the well-known relation μ=l 2 /τ T V, where l is the thickness of the charge transport layer, τ T is the transit time, and V is the applied voltage. Both dispersive and non-dispersive transients were observed depending on the material and degree of alignment. For dispersive transients, we verified that the transients were not due to trap-limited transport by insuring that the transit time scaled linearly with the sample thickness (for several thicknesses). For dispersive transients, the transit time, τ T was defined as the intercept of the asymptotes to pre- and post-transit slopes of the photocurrent plotted in the double logarithmic scale. For non-dispersive transients the transit time was given by the location of a well-defined knee. Typical time of flight transients are shown in FIG. 2 . As indicated in FIG. 3, the mobility was found to be relatively independent of electric field and temperature. The pulse energy was controlled by neutral density filters and kept below 10 μJ/pulse to prevent the space charge build-up. Samples were mounted onto a heating stage with a temperature controller.
Example 11
Electron Diffraction (ED) of Nanocylinder Compositions
Due to the high sensitivity of the D4 ordered structure on electron beam, low-dose EM techniques were employed, including use of a small condenser aperture, small spot size, and reduced beam current and intensity to preserve the specimen integrity. Electron diffraction pattern of ordered domains was recorded at ED mode at a camera length of 120 cm. The images of ED pattern were accurately enlarged and printed, then scanned into the computer and analyzed.
FIG. 4 indicates a homeotropic alignment of hexagonal columnar phase of Pyr-F. The d-spacing of such material was calculated to be <a>=42.9 Å according to the Bragg's equation. In comparison, XRD showed a d-spacing of <a>=44.6 Å. Quantitative analysis of the diffraction spot intensity was carried out. In total, two unique reflections were found. Both reflections were strong. The ratio of intensity of these two reflections was 1:0.32. However, in order to compare with the XRD data, these intensities had to be multiplied by the respective multiplicity factor, which is 1:2. Thus, the ratio relative intensities are approximately 1:0.64. In comparison, XRD showed a ratio of 1:0.57.
The invention being thus described, it will be obvious that the same may be modified or varied in many ways. Such modifications and variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications and variations are intended to be included within the scope of the following claims.
|
This invention relates to novel fluorinated dendrons and to a universal strategy for producing functional fluorinated dendrons programmed to self-assemble into supramolecular nanocylinder compositions containing p-stacks of high electron or hole mobility donors (D), acceptors (A), or D-A complexes in the core. Such nanocylinder compositions are uniquely applicable to devices spanning from single supramolecule to nanoscopic and to macroscopic scales including transistors, photovoltaics, photoconductors, photorefractives, light emissives, and optoelectronics.
| 2
|
BACKGROUND OF THE INVENTION
[0001] This invention relates to luminaire louvers. More particularly, this invention relates to louvers that are sized, shaped, and arranged to improve the performance of luminaires.
[0002] Luminaires (i.e., lighting units) can be used to provide indirect ambient lighting for interior spaces by directing some or all of their lighting to overhead surfaces. These types of luminaires are widely used in commercial installations where diffuse reflected light is desirable. They are especially common in office spaces, where such lighting is preferred for tasks involving video display terminals.
[0003] Luminaires for ambient lighting are commonly suspended from ceilings. They usually have housings that conceal or otherwise shield their lamp(s) from direct view, while directing light upwards through apertures in the top of the luminaire. To minimize glare and maximize visual comfort, these luminaires provide as even a distribution of light (i.e., no bright spots) over as wide an area as possible. Such uniformity of light can be economically attained by using luminaires that (1) are suspended as far as possible from the surface to be illuminated and (2) emit their maximum intensity light at low upward angles. Coincidently, increased setback and wide light distribution also advantageously result in the fewest number of luminaires and the lowest power density (watts per square foot).
[0004] However, suspension lengths are often limited, for example, by low ceiling heights, headroom issues, and the general notion that suspended lighting adds clutter to interior spaces. Even in known luminaires with relatively wide light spread distributions, limited suspension lengths often result in undesirable ceiling brightness and poor ceiling uniformity. In such cases, ceiling uniformity is especially compromised when luminaires are widely spaced to lower energy costs. Undesirable ceiling brightness and poor ceiling uniformity can cause reflected glare on display screens, increasing visual fatigue and reducing worker productivity.
[0005] Luminaires for ambient lighting also are commonly mounted to furniture systems and low office partitions. Mounting heights for such luminaires typically range from about 48″ above the floor to about 65″ above the floor. These luminaires advantageously eliminate overhead lighting and potentially create a visually clean, uncluttered, and spacious-appearing interior environment. Moreover, these luminaires may also have bottom apertures that provide local supplementary direct lighting for office tasks. This eliminates the need for auxiliary task lights and further reduces energy use. Because these luminaires are generally mounted farther from ceilings than suspended luminaires, they potentially create more diffuse ambient light characterized by lower ceiling luminances, greater uniformity of ceiling brightness, and greater visual comfort.
[0006] However, such furniture/partition mounted luminaires (i.e., indirect luminaires mounted below standing eye height) often have a housing with a large height profile to shield their lamps from direct view. Large height profiles can adversely affect the aesthetic appearance of an interior environment and can also adversely impact workstation functionality. For example, a panel-mounted luminaire with a large height profile may prevent a video display terminal from being positioned at the most desirable viewing location.
[0007] While some reduction in height profile is possible with shielding devices (e.g., baffle or louver assemblies, described in detail below), shielding devices can also adversely affect the performance of a luminaire and thus diminish the advantages furniture/partition mounted luminaires have over luminaires suspended from ceilings.
[0008] Luminaire performance for ambient light applications is determined by luminaire efficiency and the maximum intensity angle. Luminaire efficiency is the percentage of light generated by the luminaire's lamp(s) that is emitted from the luminaire; the closer to 100%, the higher the efficiency. The maximum intensity angle is the angle at which the maximum intensity light is emitted from the luminaire; the lower the angle, the wider the light distribution. Higher performance results from either higher efficiency, lower maximum intensity angle, or preferably both.
[0009] Effective shielding devices can contribute to performance by preventing luminaire lamp(s) from being directly viewed while advantageously directing lamp output at low angles that minimize glare (i.e., at angles near but not at or below the viewing angle). However, as mentioned above, shielding devices can also detract from luminaire performance.
[0010] For indirect luminaires employing linear type fluorescent lamps (e.g., 1″ diameter T8 or ⅝″ diameter T5 lamps) or long compact (twin-tube) fluorescent lamps, shielding is often performed by a baffle or louver assembly placed above the lamp(s) in much the same manner as a direct or downlight luminaire is fitted with a baffle or louver assembly below its lamp(s). Typically, such baffles or louvers are made of specular or semi-specular metal or metalized plastic fashioned to advantageously redirect light rays to prevent glare.
[0011] Baffle assemblies typically have vertical blades arranged transversely (crosswise) to the lamp length. These vertical blades extend between two side members arranged parallel to the length of the lamp. Multiple vertical blades are arranged along the lamp length between the side members to form a series of apertures through which lamp light passes. The spacing of the blades combined with their height and the angle of light reflecting off their surfaces determine the longitudinal shielding angle of the luminaire. Similarly, the distance between the baffle side members, the angle of light reflecting off their surfaces, and the vertical distance at which the lamp is positioned below the top of the baffle sides determine the lateral or transverse shielding angle of the luminaire.
[0012] A significant disadvantage of baffle assemblies involves the transverse shielding angle, transverse aperture width, and luminaire height profile. For a given lamp type, indirect luminaires with wide baffle assemblies, which advantageously result in greater overall efficiency with wider light distributions and greater light intensity at lower vertical angles, require the lamp to be located far below the aperture in order to have acceptable lateral shielding. This results in luminaires that are undesirably bulky with noticeably large height profiles, which can compromise the appearance of a space and limit workstation functionality.
[0013] Louver assemblies generally combine a series of transverse (baffle) blades with longitudinal blades positioned between the side members and parallel to the lamp length. (As used herein, “transverse blade” and “cross blade” mean the same thing and are interchangeable.) These transverse and longitudinal blades create an array of multiple, usually rectangular, apertures through which lamp light passes. The result is an assembly wherein the spacing of the transverse and longitudinal blades, their respective heights, and the angle of light reflecting off their surfaces determine the longitudinal and transverse shielding angles of the luminaire.
[0014] Generally, the vertical position of the lamp from the louver assembly has little to no effect on the shielding angle. Thus, luminaire height profile can be advantageously reduced to little more than the lamp diameter and louver height. To the extent that reduced louver blade spacings allow for reduced louver height without compromising the shielding angle, very low profile luminaires can be advantageously constructed.
[0015] Uniform louver assemblies having transverse and longitudinal blades of equal heights, spacings, and surface profiles are very common. They typically are used to construct low-profile, low-brightness luminaires with consistent vertical shielding from all horizontal viewing angles regardless of the position, orientation, and number of lamps (light sources).
[0016] Such uniform louver assemblies, however, have two disadvantages. The first disadvantage adversely affects the efficiency of the luminaire. When louver blades are closely spaced to reduce louver height (and thus advantageously reduce the luminaire height profile) while maintaining the shielding angle, the number and total cross-sectional area of louver blades increases, causing the total open aperture area of the louver to accordingly decrease. This increases the interception and reflection of light rays by louver blades. Typically, luminaire louver blades have a surface reflectance of about 85% to 90%, meaning that about 10% to 15% of the light striking the surface is absorbed (i.e., lost). Consequently, the overall light output of the luminaire decreases and the amount of energy (wattage) required to produce a given lighting level increases. The efficiency and overall performance of the luminaire are therefore lower.
[0017] The second disadvantage of uniform louver assemblies adversely affects the maximum intensity angle. Normally, light rays entering the louver assembly either emanate directly from the lamp or have been redirected to desirable angles by a luminaire reflector. Louvers therefore should only intercept and redirect those light rays emanating directly from the lamp at undesirable angles (i.e., those light rays that have the potential to cause direct brightness and glare). However, some louver blades intercept light rays that are already directed at desirable angles, while not intercepting light rays directed at undesirable angles. This is especially common with respect to longitudinal louver blades in single-lamp linear fluorescent luminaires. Each time a light ray encounters a louver blade surface, it is redirected at a generally higher angle. Thus, redundant louver reflections cause the luminaire output to become more concentrated and to exit the aperture at higher vertical angles. This reduces the luminaire's ability to output high intensities at low vertical angles (i.e., near the shielding angle) and disadvantageously leads to less light diffusion and reduced surface (e.g., ceiling) uniformity. This, in turn, adversely affects visual comfort and the general appearance of a space.
[0018] In view of the forgoing, it would be desirable to be able to provide a louver assembly that improves the performance of luminaires used for indirect ambient lighting.
[0019] It would also be desirable to be able to provide a louver assembly that improves luminaire efficiency.
[0020] It would further be desirable to be able to provide a louver assembly that produces a wide spread light distribution pattern with maximum light intensities at low vertical angles.
SUMMARY OF THE INVENTION
[0021] It is an object of this invention to provide a louver assembly that improves the performance of luminaires used for indirect ambient lighting.
[0022] It is also an object of this invention to provide a louver assembly that improves luminaire efficiency.
[0023] It is further an object of this invention to provide a louver assembly that produces a wide spread light distribution pattern with maximum light intensities at low vertical angles.
[0024] In accordance with the invention, a louver assembly is designed to be positioned in or over the light-emitting opening of a luminaire's housing. The luminaire includes a lampholder for a light source and preferably a reflector that redirects light from the source at desirable angles above a specified shielding angle. The louver assembly includes a plurality of longitudinal and transverse blades dividing the light-emitting opening into a plurality of apertures. The louver blades are sized, shaped, and arranged to (1) shield the light source from view at angles less than the shielding angle, (2) improve luminaire efficiency, and (3) produce a wide spread light distribution pattern with maximum light intensities at low vertical angles. The louver assembly advantageously reduces the unintended interception and redirection of desirable direct and reflected light rays exiting the opening of the luminaire.
[0025] Embodiments of the louver assembly include one or more of the following features in accordance with the invention: differently sized apertures, louver blades having different curvatures on their longitudinal sides, transversely wider apertures directly over (or under) the luminaire's lamp(s) (e.g., no longitudinal louver blades centered over (or under) the lamp(s)), longitudinal louver blades that are nonplanar with transverse louver blades, and louver blades having different heights.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The above and other objects and advantages of the invention will be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which:
[0027] FIGS. 1 and 2 are cross-sectional and partial longitudinal views, respectively, of a typical baffle assembly;
[0028] FIG. 3 is a perspective view of a luminaire employing the baffle assembly of FIGS. 1 and 2 ;
[0029] FIGS. 4 a,b are cross-sectional and partial longitudinal views, respectively, of the luminaire of FIG. 3 positioned for uplighting;
[0030] FIG. 5 is a candlepower distribution curve representing the luminous output in the transverse plane of the luminaire of FIG. 4 a;
[0031] FIGS. 6-8 are cross-sectional, partial longitudinal, and partial perspective views, respectively, of a typical uniform louver assembly;
[0032] FIG. 9 is a cross-sectional view of a luminaire with a typical louver assembly showing disadvantageous redirection of light rays;
[0033] FIG. 10 is a candlepower distribution curve representing the luminous output in the transverse plane of the luminaires of FIGS. 4 a and 9 ;
[0034] FIGS. 11-13 are cross-sectional views of a luminaire with a typical louver assembly showing advantageous interception of undesirable lamp emanations, disadvantageous redirection of lamp emanations, and disadvantageous interception of advantageously reflected light rays, respectively;
[0035] FIGS. 14-16 are cross-sectional views of a luminaire with another embodiment of a typical louver assembly showing advantageous interception of undesirable lamp emanations, disadvantageous redirection of lamp emanations, and disadvantageous interception of advantageously reflected light rays, respectively;
[0036] FIG. 17 is a cross-sectional view of a first embodiment of a louver assembly according to the invention;
[0037] FIG. 17 x is an enlarged cross-sectional view of a longitudinal louver blade of the louver assembly of FIG. 17 according to the invention;
[0038] FIG. 18 is a cross-sectional view of a luminaire employing the louver assembly of FIG. 17 ;
[0039] FIG. 19 is a candlepower distribution curve representing the luminous output in the transverse plane of the luminaires shown in FIGS. 4 a , 9 , and 18 ;
[0040] FIGS. 20 a,b are cross-sectional views of another embodiment of a louver assembly according to the invention;
[0041] FIGS. 21 a,b are cross-sectional and partial perspective views, respectively, of another embodiment of a louver assembly according to the invention;
[0042] FIG. 22 is a cross-sectional view of still another embodiment of a louver assembly according to the invention;
[0043] FIG. 23 is a cross-sectional view of the luminaire of FIG. 18 showing disadvantageous interception of advantageously reflected light rays;
[0044] FIGS. 24 and 25 are perspective and cross-sectional views, respectively, of another embodiment of a louver assembly according to the invention;
[0045] FIG. 26 is a perspective view of a luminaire employing several louvers of FIGS. 24 and 25 ;
[0046] FIG. 27 is a cross-sectional view of another luminaire employing the louver of FIGS. 24 and 25 in which unobstructed and advantageously redirected light rays are shown exiting the luminaire;
[0047] FIG. 28 is a candlepower distribution curve representing the luminous output in the transverse plane of the luminaires shown in FIGS. 9, 18 , and 27 ;
[0048] FIGS. 29 and 30 are perspective and cross-sectional views, respectively, of another embodiment of a louver assembly according to the invention;
[0049] FIG. 30 x is an enlarged cross-sectional view of a portion of the louver assembly of FIGS. 29 and 30 ;
[0050] FIG. 31 is a partial longitudinal view of the louver assembly of FIGS. 29 and 30 ;
[0051] FIG. 32 is a perspective view of a luminaire employing the louver assembly of FIGS. 29-31 ;
[0052] FIG. 33 is a cross-sectional view of the luminaire of FIG. 32 showing unobstructed and advantageously redirected light rays exiting the luminaire;
[0053] FIGS. 34 a,b are cross-sectional and partial perspective views, respectively, of another embodiment of a louver assembly according to the invention;
[0054] FIGS. 35 a,b are cross-sectional and partial perspective views, respectively, of still another embodiment of a louver assembly according to the invention;
[0055] FIGS. 36 a,b are cross-sectional and partial perspective views, respectively, of yet another embodiment of a louver assembly according to the invention;
[0056] FIGS. 37 a,b are cross-sectional and partial perspective views, respectively, of a further embodiment of a louver assembly according to the invention;
[0057] FIGS. 38 a,b are partial top and partial cross-sectional views, respectively, of a circular embodiment of a louver assembly according to the invention; and
[0058] FIGS. 39 a,b are partial top and cross-sectional views, respectively, of a concentric embodiment of a louver assembly according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0059] FIGS. 1 and 2 illustrate how a typical low-brightness baffle assembly controls glare by establishing a shielding angle. Side members and cross (transverse) baffle blades intercept light rays that exit the lamp within the shielding angle. The baffle side members and cross blades are formed with curved profiles and specular finishes to control the redirected rays such that they exit the luminaire in desirable directions that do not violate the shielding angle. Consequently, the viewer is not subjected to direct brightness from the lamp or reflected brightness from the baffle side members and cross blades when viewing the luminaire at sightlines within the shielding angle. The baffle side members advantageously cause the highest angle reflected rays to exit the luminaire parallel to the shielding angle. This contributes to a wide spread distribution. Internal reflectors typically direct all other light rays exiting the luminaire away from the shielding angle. Such luminaires commonly achieve a desirable low-brightness appearance.
[0060] Baffles are commonly used in downlight luminaires, as shown in FIG. 3 , but are also equally effective for uplighting, as shown in FIGS. 4 a,b . However, for a given size lamp and shielding angle, the minimum luminaire height profile is dictated by the aperture width. That is, as the aperture width increases, the luminaire height profile increases (because the lamp needs to be positioned farther away from the aperture in order to maintain the shielding angle) and vice versa.
[0061] The candlepower distribution curve shown in FIG. 5 illustrates the performance of luminaire 400 in which the lamp is a linear fluorescent and, in addition to the baffle assembly, internal reflectors 401 redirect light at (low) angles that do not violate the shielding angle. Commonly, this is referred to as a wide spread or “batwing” distribution. In particular, φ 0 is the maximum light intensity produced by luminaire 400 , angle α 0 is the angle of maximum light intensity, and the shielding angle is 26°.
[0062] FIGS. 6 and 7 illustrate how a typical louver assembly controls glare by establishing a shielding angle. A shielding angle is determined by the louver height and blade spacing. The use of contoured side members and louver blades along with specular finishes is known to achieve low-brightness and high performance. The height of each longitudinal and transverse louver blade is commonly equal to the louver height and, although slight variations in blade surface profiles may require louver blade spacings a and a′ to vary slightly from each other and across the transverse width of the louver, the louver blades and side members are essentially arranged in a uniform array as shown in FIG. 8 . As with baffles, louvers are equally applicable to downlight and uptight applications.
[0063] Notably, however, the luminaire shielding angle and minimum luminaire height are not a function of aperture width. Luminaire shielding angle is solely a function of blade spacing (e.g., a or a′) and louver height as defined in FIGS. 6 and 7 . Consequently, variations in aperture width and lamp position do not affect the shielding angle and, for any given lamp size and position, the minimum luminaire height profile is defined by the louver height.
[0064] FIG. 9 illustrates how uniform louver blade contours (i.e., side profiles/curvatures/shapes) limit performance. In this example, the louver side members and both sides of each of the longitudinal louver blades have identical parabolic shapes. Light rays emanating directly from the lamp that strike the inside surface of the longitudinal blades (i.e., the surface facing the lamp) are advantageously redirected at an angle parallel to the shielding angle. However, light rays striking the outside surface of the longitudinal blades (i.e., the surface facing away from the lamp) have already been redirected at advantageous angles close to the shielding angle by luminaire reflector 901 . The subsequent redirection (to higher angles) by the parabolic louver surfaces of these already reflected lights rays is undesirable and diminishes the wide spread output of the luminaire.
[0065] The result is illustrated in FIG. 10 , where the performance of luminaire 900 is compared with the performance of luminaire 400 (which has the baffle). In particular, louver 600 results in a maximum light intensity of φ 1 and an angle of maximum intensity α 1 . The shielding angle again is 26°. Notably, although a lower profile luminaire can be constructed with the louver, peak candlepower in the transverse plane is significantly reduced and the difference between the peak candlepower angle α 1 and the shielding angle is significantly greater than that obtained with a baffle assembly.
[0066] FIGS. 11-13 further illustrate how a known louver assembly limits the performance of luminaires. Note that in the known louver embodiment shown, the lamp is positioned between and below two longitudinal louver blades. The unshaded portions of those two longitudinal louver blades are superfluous. That is, they add nothing to the establishment of a shielding angle and do not improve luminaire performance. As shown in FIG. 11 , they do not intercept undesired direct lamp emanations, and thus do not contribute to reducing glare. To the contrary, as shown in FIG. 12 , those superfluous louver blade segments disadvantageously intercept desirable lamp emanations (exiting the lamp above the shielding angle). Moreover, other desirable light rays, which had already been desirably reflected by reflector 1301 , as shown in FIG. 13 , are similarly undesirably intercepted by the two superfluous louver blade segments. As described previously, these unnecessary interceptions negatively impact luminaire efficiency. Furthermore, in typical uniform louver assemblies (where all louver blades are identically fashioned to elevate, by reflection, low-angle lamp rays to angles above the shielding angle), the superfluous louver blade sections only disadvantageously redirect desirable light rays to angles farther away from the shielding angle and thus do not contribute to achieving a wide spread distribution (see, e.g., FIG. 12 ).
[0067] FIGS. 14-16 illustrate another known uniform louver assembly that limits luminaire performance. In this embodiment, the lamp is positioned directly beneath a center longitudinal louver blade. The luminaire also includes internal reflectors 1401 that direct light rays at angles at or above the shielding angle. The uniform blade spacings again result in superfluous and/or partially superfluous louver blades. In particular, the center louver blade is entirely unnecessary. Moreover, top portions of the two longitudinal louver blades adjacent the center blade are also superfluous, because they receive only (1) direct lamp rays exiting above the shielding angle and (2) advantageously reflected light rays. Again, the interception and reflection of desirable light rays to higher angles above the shielding angle adversely affects the wide spread output of the luminaire. Furthermore, the center blade unnecessarily reduces the total open aperture area of the luminaire, adversely affecting the luminaire's efficiency (i.e., the percentage of light generated by the luminaire that is emitted from the luminaire).
[0068] FIGS. 17 and 17 x show an embodiment of a louver assembly in accordance with the invention. Louver assembly 1700 has longitudinal baffle blades having longitudinal inner sides b and outer sides c. Inner sides b receive direct light rays from the lamp, while outer sides c do not. As better seen in FIG. 17 x , inner sides b and outer sides c have different curvatures (i.e., shapes, profiles, contours) in accordance with the invention. The curvature of outer sides c are such that reflected light rays incident thereon are advantageously redirected parallel to (or close to) the shielding angle. In this embodiment, outer sides c are preferably flat, planar surfaces that have a minimal effect on the angle of incident light with respect to the shielding angle. The curvature of inner sides b, in contrast, preferably has a radius R 1 as shown in FIG. 17 x . Note that longitudinal sides b and c, as well as the louver cross blades and side members, may have other curvatures than those shown. In as much as the curvature of these blade surfaces defines in part the distance x between the bottom edges of adjacent longitudinal blades (which in turn affects the transverse shielding angle), louver blade spacing a, between two inward curved blade surfaces, may be slightly greater than spacing a″, which is the spacing between one flat and one curved blade side. Alternatively, louver assembly 1700 may have a uniform longitudinal blade spacing of a″.
[0069] FIG. 18 shows a luminaire 1800 that includes louver assembly 1700 . Reflected light rays that would otherwise be redirected away from the shielding angle by known louver assemblies are instead advantageously redirected to angles close to the shielding angle in accordance with the invention.
[0070] The advantageous result is shown in FIG. 19 , where the performance of luminaire 1800 (shown in bold) is compared with known luminaires 400 (which has a baffle assembly) and 900 (which has a known uniform louver assembly). In particular, φ 1 and φ 2 both represent, respectively, the maximum intensity achieved with the louver of invention and known uniform louver 600 of luminaire 900 ( FIG. 9 ). φ 0 represents the maximum intensity achieved with the baffle assembly of luminaire 400 ( FIG. 4 a ). Angle α 2 is the angle of maximum intensity produced by the louver of the invention, and the shielding angle again is 26°. Angles α 0 and α 1 are the angles of maximum intensity for luminaires 400 and 900 , respectively. Advantageously, the louver of invention achieves a distribution where the angle of maximum intensity (angle α 2 , which is 44°) is 30% closer to the shielding angle than angle α 1 achieved by known uniform louver assembly 600 . Accordingly, angle α 2 is equal to that achieved by the baffle assembly (see angle α 0 ). Also significant is that the intensity (φ 2 ) achieved at angle α 2 is about 7% greater than that achieved by known uniform louver 600 at the same angle. More significant is that the louver of the invention achieves a 20% increase in output at an angle just 10° above the shielding angle when compared with that of known uniform louver 600 .
[0071] Although luminaire efficiency and maximum intensity is essentially unchanged by the louver of the invention when compared with known uniform louver assembly 600 of luminaire 900 , the resulting wide spread distribution achieves greater uniformity of surface (e.g., ceiling) brightness and greater visual comfort, particularly in furniture/partition mounted luminaires.
[0072] FIGS. 20 a,b illustrate another embodiment of a louver assembly in accordance with the invention. Louver assembly 2001 is incorporated in a luminaire 2000 employing two parallel elongated lamps 2002 and 2004 . Center longitudinal louver blade 2006 has two identically curved sides, while the other longitudinal louver blades have one planar and one curved side each. Two of these other longitudinal louver blades occur directly over the lamps. While the flat sides of these two blades receive some direct lamp emanations from the respective lamp immediately below them, they receive no direct light rays from the respective other lamp, and their direct exposure is limited to high angle light rays that are redirected above the shielding angle. FIG. 20 b illustrates the advantageous redirection of light rays parallel to the shielding angle, which results in a wide spread distribution.
[0073] FIGS. 21 a,b illustrate another embodiment of a louver assembly in accordance with the invention. Louver assembly 2101 is positioned in the top aperture of a direct/indirect luminaire 2100 . Louver assembly 2101 establishes shielding for sightlines originating above the luminaire. In this embodiment, the shielding angle is again 26° (other angles are, of course, possible) and the angle of maximum uptight intensity provided by louver 2101 advantageously occurs within 15° of the shielding angle. The louver is formed with extended side members that integrate additional reflector segments d into the assemblies. The louver also includes horizontal top extensions f that facilitate mounting. The louver further has cross-blade fillets e that facilitate production when the extended side members are formed by injection molding. Cross-blade extensions e′ allow the transverse blades to be uniquely fashioned below the longitudinal shielding line to divert light rays that otherwise would be disadvantageously redirected by the bottom surfaces of the blades toward the downlight reflectors t.
[0074] FIG. 22 illustrates still another embodiment of a louver assembly in accordance with the invention. Louver assembly 2201 is positioned in the top aperture of a direct/indirect luminaire. Louver 2201 is fashioned and positioned in luminaire 2200 for a lamp position different than that of luminaire 2100 and for providing a shielding angle of 35° instead of 26°. Again, the louver is formed with extended side members that integrate additional reflector segments h into the assemblies. Louver 2201 also includes horizontal top extensions f that facilitate mounting. Cross-blade fillets j facilitate one-piece molding techniques, and cross-blade extensions j′ control the angle of light rays reflected from the bottom surfaces of the cross-blades. Advantageously, the angle of maximum uplight intensity again occurs within 15° of the shielding angle.
[0075] FIG. 23 again shows louver assembly 1700 positioned in luminaire 1800 (from FIG. 18 ). Louver assembly 1700 has substantially uniform longitudinal louver blade spacings and uniform blade heights. And while the wide spread distribution of luminaire 1800 is improved by louver 1700 having longitudinal blades with different longitudinal side curvatures, the performance of luminaire 1800 can be further improved by modifying louver 1700 in accordance with the invention.
[0076] As shown in FIG. 23 , reflector 2301 advantageously redirects light rays at angles above and preferably parallel to the shielding angle. Note that the two center longitudinal louver blades 2303 and 2305 (shown unshaded) unnecessarily intercept those desirable light rays. And although the planar side of louver blade 2303 will redirect in a desirable direction the light rays striking it (see FIG. 18 ), recall that each reflectance of light striking a louver blade loses about 10% to 15% of that light. This adversely affects luminaire efficiency. Moreover, the light shown striking louver blade 2305 will be redirected at an undesirably higher angle. The same is true for light striking louver blades 2303 and 2305 from the right side of luminaire 1800 (not shown).
[0077] Therefore, in accordance with the invention, a further improved louver assembly is shown in FIGS. 24 and 25 . Louver assembly 2400 is similar to louver 1700 except that the superfluous center longitudinal blades are omitted. The apertures of louver 2400 are thus of non-uniform size. Larger apertures are found over the lamps, thus allowing more light to exit the luminaire, improving efficiency, while smaller apertures are transversely adjacent the larger apertures (note transverse widths e and d in FIG. 25 ). In particular, transverse width d is greater than transverse widths e.
[0078] The longitudinal blades of louver 2400 preferably have longitudinal sides with different curvatures b and c as shown. In this embodiment, curvature b is preferably parabolic, while curvature c is preferably planar. Alternatively, other curvatures may be used, and they need not be different from each other (although some benefit may be lost depending on the angles at which those curvatures redirect light).
[0079] FIGS. 26 and 27 show luminaires incorporating louver 2400 . Luminaire 2600 includes several louver assemblies 2400 . FIG. 27 shows large numbers of reflected light rays that are advantageously no longer intercepted and redirected away from the shielding angle, thus improving both efficiency and the wide spread distribution pattern. Moreover, the longitudinal blades advantageously redirect the direct emanations from lamp 2702 and the reflected light from reflector 2701 at low angles parallel to the shielding angle.
[0080] These advantageous results are shown in FIG. 28 , where the performance (shown in bold) of louver 2400 in luminaire 2700 is compared with that of the louvers in luminaires 900 and 1800 of FIGS. 9 and 18 , respectively. In particular, louver 2400 results in a maximum intensity of φ 3 and an angle of maximum intensity α 3 . The shielding angle again is 26°. Louver 2400 achieves a distribution where the angle of maximum intensity closely approximates that achieved by louver assembly 1700 (i.e., the louver with strategically shaped longitudinal blades). However, the maximum intensity φ 3 achieved at angle α 3 is 5% greater than that achieved by louver 1700 and is about 12% greater than that achieved by known uniform louver assembly 600 at the same angle. Maximum intensity φ 3 is accordingly also about 5% greater than the maximum intensity achieved by louver assembly 600 at any angle (recall that φ 1 approximates φ 2 ). More significantly, louver 2400 achieves a 28% increase in output at an angle just 10° above the shielding angle when compared to known uniform louver assembly 600 . The resulting wide spread distribution achieves greater uniformity of surface (e.g., ceiling) brightness and greater visual comfort than that possible with known louvers, particularly in furniture/partition mounted luminaires.
[0081] FIGS. 29-33 show another embodiment of a louver assembly in accordance with the invention. Louver 2900 has two interior longitudinal louver blades 2902 and 2904 that each have a height less than that of the louver side members and cross (transverse) blades. In other words, the tops of the longitudinal blades are nonplanar with the tops of the side members and cross blades, where “top” is defined as the side farthest from the luminaire lamp(s). Louver blades 2902 and 2904 preferably have longitudinal sides of different curvatures (e.g., curvatures k and h′ as shown in FIG. 30 x , which may be planar and parabolic, respectively), and cross blades 3006 are preferably uniformly spaced by a distance m ( FIG. 31 ). In one embodiment of the invention, the inner (lamp facing) side of louver side members 3008 ( FIGS. 30 and 30 x ) preferably have a surface curvature formed by two parabolic shapes h and j that have a common edge coincident with line j′. Line j′ passes through point f 2 and is tangent to the top of lamp 3007 . Specifically, shapes h and j have focal points f 1 and f 2 , respectively, that are coincident with the lowest angle direct lamp rays incident to the respective shapes. Shapes h and j advantageously redirect these lamp rays (and all other light rays passing through the respective focal points) parallel to the shielding angle. Note that the longitudinal blades, as well as the side members, are not limited to having one shape per longitudinal side, but alternatively can have multiple shapes per longitudinal side.
[0082] FIGS. 32 and 33 show luminaire 3200 fitted with louver assembly 2900 . Louver 2900 reduces the obstruction and disadvantageous redirection of light rays exiting the luminaire near the shielding angle. Moreover, louver 2900 advantageously redirects obstructed rays to angles close to the shielding angle, thus achieving high luminaire efficiency and a wide spread distribution. Note that the overall aperture width of the louver relative to the shielding angle, louver height, and location of the lamp determines the height x (see FIG. 30 x ) of louver blades 2902 and 2904 .
[0083] FIGS. 34 a,b show another embodiment of a louver assembly in accordance with the invention. Louver assembly 3401 is positioned in the top aperture of a direct/indirect luminaire 3400 . Louver 3401 establishes shielding for sightlines originating above luminaire 3400 . The tops of the longitudinal blades are nonplanar with the tops of the side members and cross blades. The longitudinal blades preferably have longitudinal sides with different curvatures as described above. In this embodiment, the shielding angle is 35°, and the louver is formed with extended side members that advantageously integrate additional reflector segments n into the assemblies. Horizontal top extensions s advantageously facilitate mounting of the louver in a luminaire. Cross-blade fillets p facilitate production when louver 3401 is formed by injection molding, and cross-blade extensions p′ allow transverse blades 3406 to be uniquely fashioned below the longitudinal shielding line to divert light rays that otherwise would be disadvantageously redirected by the bottom surfaces of the blades toward downlight reflectors t. Louver 3401 advantageously produces an angle of maximum uptight intensity that occurs within 15° of the shielding angle.
[0084] FIGS. 35 a,b show still another embodiment of a louver assembly in accordance with the invention. Louver assembly 3501 is positioned in the top aperture of a direct/indirect luminaire 3500 . Louver 3501 is fashioned uniquely for a lamp position differing from that of luminaire 3400 and for producing a shielding angle of 26°. Again, the louver is formed with extended side members that integrate additional reflector segments q into the assemblies. Louver 3501 also has horizontal top extensions s that facilitate mounting of the louver in a luminaire. Cross-blade fillets r facilitate one-piece molding techniques, and cross-blade extensions r′ control the angle of light rays reflected from the bottom surfaces of the cross-blades. Notably, as in the previous two embodiments, the tops of the two interior longitudinal louver blades are nonplanar with and lie below (although slightly in this embodiment) the tops of the cross blades and side members. The longitudinal blades preferably have longitudinal sides with different curvatures as described above. The angle of maximum uptight intensity produced by louver 3501 again advantageously occurs within 15° of the shielding angle.
[0085] FIGS. 36 a,b show yet another embodiment of a louver assembly in accordance with the invention. Louver assembly 3601 is positioned in the top aperture of a direct/indirect luminaire 3600 . Louver 3601 is fashioned uniquely for a pair of lamps or twin-tube lamp to produce a shielding angle of 35°. Again, the louver is formed with extended side members that integrate additional reflector segments v into the assemblies. Louver 3601 is also formed with horizontal top extensions s that facilitate mounting of the louver in a luminaire. Louver 3601 is further formed with cross-blade fillets w to facilitate one-piece molding techniques. Cross-blade extensions w′ control the angle of light rays reflected from the bottom surfaces of the cross blades. Notably, although the overall height of the two interior longitudinal louver blades is substantially similar to the effective height of the transverse louver blades (i.e., the height of the cross blades above the longitudinal shielding line), the tops of the longitudinal blades are set below the tops of the cross blades and side members (i.e., the tops are nonplanar) and, accordingly, the longitudinal louver blades extend beyond and below the longitudinal shielding line.
[0086] FIGS. 37 a,b show a further embodiment of a louver assembly in accordance with the invention. Louver assembly 3701 is positioned in the top aperture of a direct/indirect luminaire 3700 . In this embodiment, the tops of longitudinal blades 3702 and 3704 are planar with the tops of side members 3708 and 3710 and the cross blades. The cross blades are made up of either both outboard and center blade sections 3705 and 3706 , or only center blade section 3706 .
[0087] Because the longitudinal louver blades advantageously extend inward (i.e., downward as shown in FIG. 37 a ) and beyond the longitudinal shielding line of the center cells, the minimum effective aperture cell depth (designated y′) of the outboard aperture cells is greater than the aperture cell depth (designated y) of the center aperture cells. Therefore, the spacing of the outboard cross blades can be increased relative to that of the center cross blades. Accordingly, the curved, low-brightness profile of the outboard cross blades is extended to a longitudinal shielding line occurring at a depth coinciding with the increased effective depth of the outboard cells. Specifically, in this embodiment, the shielding angle is 26° and the effective depth of the outboard louver cells y′ is approximately twice the effective depth y of the center cells such that the spacing of the outboard cross blades is twice that of the center cross blades.
[0088] Other relative depth and spacing relationships are possible, including the omission of outboard cross blades 3705 entirely as suggested above, because any low angle direct lamp emanations they receive will otherwise be redirected to desirable angles by the adjacent (intersecting) side members. (In some constructions, however, these outboard cross blades may serve to position and/or support the longitudinal and center cross blades or prevent direct view of non-optical features within the luminaire.)
[0089] Notably, the performance of louver 3701 is substantially equivalent to the performance of louver 3501 . While potentially more difficult to fabricate than louver assembly 3501 , louvers such as 3701 employ cross blades of reduced height profile directly over the lamp (albeit there being more center cross blades at a reduced blade-to-blade spacing than louver 3501 ). This reduced height profile provides greater clearance between the lamp and the louver assembly, which may allow higher wattage (hotter) lamps to be used. Alternatively, the reduced louver height profile, combined with an increase in the size of the outboard aperture cells, may allow the luminaire height profile to be further reduced without adversely affecting efficiency.
[0090] Louvers of the invention may also be used in direct luminaires, where the louver assembly is mounted in a light emitting opening in the bottom of the luminaire. Accordingly, louvers of the invention may further be used in direct/indirect luminaires having openings in their tops and bottoms, where the louver assembly may be mounted in the top opening (as shown in the embodiments above), the bottom opening, or both. Louvers of the invention may still further be used in luminaires employing multiple lamps, compact fluorescent lamps, circular type lamps, point sources such as tungsten-halogen and high-intensity discharge lamps, as well as other types of light sources. Furthermore, louvers of the invention may have non-orthogonal, concentric, and radial blade arrangements for use in luminaires with non-elongated light sources. FIGS. 38 a,b and FIGS. 39 a,b show such alternative embodiments of louver assemblies in accordance with the invention.
[0091] Thus it is seen that high performance louvers and luminaires are provided. One skilled in the art will appreciate that the invention can be practiced by other than the described embodiments, which are presented for purposes of illustration and not of limitation, and the present invention is limited only by the claims which follow.
|
Lighting louvers formed by transverse and longitudinal blades improve the performance of indirect ambient light luminaires by increasing light output, widening the output of the luminaire's maximum intensity light, or both. These lighting louvers include at least one of the following features: non-symmetrically shaped apertures, wider apertures over (or under) the luminaire's lamp(s), longitudinal blades of shorter height nearest the lamps, and longitudinal blades having differently curved longitudinal sides. Each of these features contributes to improved luminaire performance.
| 5
|
GRANT REFERENCE
This invention was made with government support under grants R01-DA-06301-02 and P50-DA06634 awarded by the National Institute on Drug Abuse. The government has certain rights in the invention. Additional support was received from Resolution Pharmaceuticals.
FIELD OF THE INVENTION
The tropane skeleton is a basic structural unit that can lead to compounds with diverse central nervous system (CNS) activity. Due to the rigid nature of the structure, the possibility exists for the preparation of highly selective compounds. This application describes the synthesis of tropane derivatives that selectively bind to the serotonin (5-HT) transporter and thus have the potential for the treatment of major depression, attention-deficit hyperactivity disorder, obesity and cocaine addiction. Furthermore, it describes the synthesis of trialkyltin and iodinated derivatives, that are useful for the preparation of radiolabeled compounds that can be used to map the 5-HT transporters and are therefore useful as diagnostic agents for depression.
BACKGROUND OF THE INVENTION
Major depression represents one of the most common mental illnesses, affecting between 5-10% of the population. The disease is characterized by extreme changes in mood which may also be associated with psychoses. It has generally been found that most antidepressant agents exert significant effects on the regulation of monoamine neurotransmitters. The tricyclic antidepressants, such as imipramine, are the most commonly used drugs for the treatment of depression. Their ability to inhibit the neuronal uptake of norepinephrine is believed to be a major factor behind their efficacy.
A number of new types of antidepressants have been developed in recent years. Two compounds that are currently marketed in the United States are trazodone and fluoxetine. Both of these compounds interact with the regulation of 5-HT. Trazodone controls the actions of 5-HT while fluoxetine is a potent and selective inhibitor of 5-HT reuptake. 3-Chloroimipramine which inhibits both 5-HT and norepinephrine reuptake has been extensively used as an antidepressant in Europe and Canada. Other compounds which are of current interest or have been examined as antidepressants include fluvoxamine, citalopram, zimeldine, sertraline, bupropion and nomifensine. All of these drugs inhibit monamine uptake mechanisms, but differ in selectivity between the dopamine, 5-HT and norepinephrine transporters.
Considerable attention has recently been directed to the condition known as attention-deficit hyperactivity disorder. Children with this condition tend to be very active physically but have great difficulty with situations requiring long periods of attention. Consequently, they tend to underachieve academically and can be very disruptive. Furthermore, these behavioral problems often persist in modified forms into adulthood. The condition appears to be associated with the effect of monoamines in the cerebral cortex, which are involved with control of attention. A number of stimulant drugs such as dextroamphetamine, methylphenidate as well as the tricyclic antidepressants, antipsychotic agents and clonidine have been used as medications to control the disorder. Many of these drugs interact with the monoamine uptake transporters.
Cocaine addiction represents a major societal problem. The development of compounds that can modify the biological actions of cocaine would be very beneficial for the treatment of cocaine addiction. Cocaine is an inhibitor of both the dopamine and serotonin transporter, and so potent and selective compounds for this transporter can modify the biological consequences of cocaine.
Development of radiopharmaceuticals for the functional brain imaging has progressed rapidly in recent years. Both position emission tomography (PET) and single photon emission computed tomography (SPECT) ligands are now successfully employed for the study of receptors of the central nerve system (CNS) including ligands for the dopamine, muscarenic, opiate and benzodiazepine receptors. In particular, a large number of dopamine transporter imaging agents based on cocaine or tropane derivatives, have been reported. Although a large number of tropane derivatives have been developed into the radiolabeled ligands for the dopamine transporters, there are very few radiolabeled ligands available for the serotonin transporters. (Kung, H. F., et al. J. Nucl. Med. 1994, 35, 93p.; Mathis, C. A., et al., J. Labelled compd. Radiopharm. 1994, 34, 905), and no radioligand is available for the serotonin transporters based on tropane derivatives.
It has previously been shown that cocaine and related compounds are potent inhibitors of dopamine reuptake and this leads to compounds with reinforcing properties. In recent years a number of new extremely potent cocaine analogs have been prepared based on the tropane structure (Abraham et al., Journal of Medicinal Chemistry 1992, 35, 141; Boja et al., European Journal of Pharmacology, 1990, 183, 329; Boja et al., European Journal of Pharmacology, 1991, 194, 133; Carroll et al., Journal of Medicinal Chemistry, 1992, 35, 969; Carroll et al., Journal of Medicinal Chemistry, 1992, 35, 1813; Carroll et al., Journal of Medicinal Chemistry, 1992, 35, 2497, Cline et al., Journal of Pharmacology and Experimental Therapeutics, 1992, 260, 1174; Cline et al., Synapse, 1992, 12, 37; Kozikowski et al., Medicinal Chemistry Research, 1991, 1, 312; Kosikowski et al., Journal of Medicinal Chemistry, 1992, 35, 4764; Lewin et al., Journal of Medicinal Chemistry, 1992, 35, 135; Madras et al., Molecular Pharmacology, 1989, 36, 518, Carroll, F. I., et al., J. Chem. Soc., Chem. Commun. 1993, 44-46; Carroll, F. I. et al., J. Med. Chem. 1995, 38, 379; Carroll, F. I. et al., J. Med. Chem. 1993, 36, 2886; Carroll et al. J. Med. Chem. 1994, 37, 2865; Meltzer, P. C., et al. J. Med. Chem. 1993, 36, 855-862; Carroll, F. I., et al. J. Med. Chem. 1995, 38, 379-388; Boja, J. W., et al. J. Med. Chem. 1994, 37, 1220-1223; Carroll, F. I., et al. J. Med. Chem. 1994, 37, 2865; Kozikowski, A. P., et al. Biorg. Med. Chem. Lett. 1993, 3, 1327-1332; Simoni, D. et al., J. Med. Chem. 1993, 36, 3975-3977; Kozikowski, A. P., et al. J. Med. Chem. 1995, 38, 3086-3093; Kozikowski, A. P., et al. J. Med. Chem. 1994, 37, 3440-3442; Meltzer, P. C. et al., J. Med. Chem. 1994, 37, 2001-2010; Madras, B. K., et al. Synapse 1996, 24, 340-348; Chen, Z., et al., Tetrahedron Lett. 1997, 38, 1121-1124; Kelkar, S. V. et al., J. Med. Chem. 1994, 37, 3875-3877; Chen, Z., et al. J. Med. Chem. 1996, 39, 4744-4749; Xu, L. et al. J. Med. Chem. 1997, 40, 858-863; Moldt et al., U.S. Pat. No. 5,369,113, issued Nov. 29, 1994; Moldt et al., U.S. Pat. No. 5,374,636, issued Dec. 20, 1994; Kozikowski, U.S. Pat. No. 5,391,744, issued Feb. 21, 1995; Kuhar, et al., U.S. Pat. No. 5,380,848, issued Jan. 10, 1995; Carroll, et al., U.S. Pat. No. 5,128,118, issued Jul. 7, 1992; Kozikowski, U.S. Pat. No. 5,268,480, issued Dec. 7, 1993). All of these compounds are based on the tropane skeleton. These compounds tend to selectively bind to the dopamine transporter and certain structural variations can lead to compounds that bind with very high selectivity to the dopamine reuptake site (Carroll et al., J. Med. Chem., 1992, 35, 2497). Only a few tropane derivatives have been prepared that exhibit a preference for binding to the 5-HT transporter over the dopamine transporter (Boja, J. W., et al., J. Med. Chem. 1994, 37, 1220; Blough, B. E., et al., J. Med. Chem. 1996, 39, 4027-4035; Davies, H. M. L., et al., J. Med. Chem. 1996, 39, 2554; Blough, B. E. et al., J. Med. Chem., 1997, 40, 3861-3864). All of these tropane derivatives are very similar to each other because they are all derived from cocaine as starting material.
In principle, the tropane skeleton is ideally suited to prepare highly selective compounds because it is a rigid structure and so derivatives will have rather limited conformational flexibility. It would therefore be very valuable if the binding selectivity of the tropane skeleton could be altered by appropriate structural changes so that analogs favoring binding to the 5-HT reuptake site could be prepared. In a previous Davies, et al. patent application filed Jan. 22, 1996, Ser. No. 08/589,820 now U.S. Pat. No. 5,760,055, and entitled Biologically Active Tropane Derivatives, which application is incorporated herein by reference, it is taught how the novel chemistry that was there developed has enabled preparation of a much wider range of tropane analogs than was previously accessible, leading to novel structures with moderate potency and improved selectivity for the 5-HT transporter (Davies, H. M. L., et al. Eur. J. Pharmacol. 1993, 244, 93; Davies, H. M. L. et al., J. Med. Chem. 1994, 37, 1262; Bennett, B. A. et al., J. Pharmacol. Exp. Ther. 1995, 272, 1176). The work that formed the basis of the previous incorporated by reference U.S. patent application has appeared as a published article (Davies, H. M. L. et al. J. Med. Chem. 1996, 39, 2554).
It has now been discovered that if the tropane system is modified, particularly at the aryl moiety as hereinafter described, compounds can be produced that are over 800 times more potent at the 5-HT transporter compared to the dopamine transporter and have much lower binding affinities to the norepinephrine than those that were described in the prior referred to U.S. Patent application (see examples 1 and 2 below). Since these tropanes (as described below) bind preferentially to the 5-HT transporter, they may preferentially block 5-UT transport, thus increasing synaptic levels of 5-HT. This should be helpful in treating diseases related to 5-HT function. Furthermore, many of the tropanes are iodinated compounds or the alkyltin precursors to the iodinated compounds. The high binding affinities and 5-HT selectivities of these iodinated compounds mean that the [I-125]-derivatives and others may be useful as diagnostic agents for the treatment of depression.
Accordingly, it is a primary objective of the present invention to provide a process for development of new tropane analogs which bind selectively to the 5-HT transporter.
Another primary objective of the present invention is to prepare a series of tropane analogs which are candidates for treatment of chronic depression.
A still further primary objective of the present invention is to prepare a series of tropane analogs which are candidates for the treatment of cocaine addiction.
Another objective of the present invention is to prepare a series of tropane analogs that are iodinated compounds or the alkyltin precursors to the iodinated compounds, whose [I123} derivatives should be 5-HT selective SPECT (single photon emission computed tomography) diagnostic agents for depression.
An even further objective of the present invention is to provide a wide range of tropane derivatives which can be systematically used and tested to determine structure-activity relationships for binding at dopamine, 5-HT and norepinephrine transporters.
The method and manner of accomplishing each of the above objectives as well as others will become apparent from the description of the invention that follows. It is understood that modifications may be made to the steps of the synthesis and to the compounds prepared without departing from the spirit and scope of the invention, as long as the compounds which are prepared selectively bind to the serotonin reuptake transporters.
SUMMARY OF THE INVENTION
Biologically active derivatives of the tropane ring system are provided which selectively bind either to the 5-HT or DA reuptake site, leading to compounds which have use for the treatment of clinical depression, attention deficit disorder, obesity and cocaine addiction.
According to one aspect of the present invention, there are provided compounds of Formula (1): ##STR1## wherein R 1 is selected from the group consisting of hydrogen and C 1 to C 8 alkyl; R 2 is selected from the group consisting of hydrogen, iodo, radio isotopic halo, C 1 to C 8 alkyl, and tri lower alkyl (C 1 to C 8 ) tin; and R 1 and R 2 may be fused by a --N(Me)CH═CH-- to form a pyrrole ring; R 3 is selected from the group consisting of hydrogen, iodo, or C 1 to C 8 alkyl; R 4 is selected from the group consisting of hydrogen and C 1 to C 8 alkyl; and R 5 is selected from the group consisting of hydrogen or C 1 to C 8 alkyl, and salts, solvates and hydrates thereof.
According to another aspect of the invention, there is provided a pharmaceutical composition comprising a compound of Formula (1) wherein R 1 through R 5 are as previously defined, the amount being an effective amount to bind to the 5-HT transporter, and being in conjunction with a pharmaceutically acceptable carrier.
In another of its aspects, the invention provides the use of compounds of Formula (1) as 5-HT transporter antagonists for the treatment of medical conditions mediated by 5-HT transporter stimulation.
According to another aspect of the invention, there is provided a radiopharmaceutical composition comprising a compound of Formula (1) wherein one of R 2 or R 3 is a radio halo and the other is hydrogen, C 1 to C 8 alkyl, and R 1 and R 4 and R 5 are as previously defined, and a pharmaceutically acceptable carrier such as a physiologically buffered saline.
In a further aspect of the invention, there is provided a method for imaging 5-HT transporters in vivo, comprising the step of administering systemically to a patient an effective amount of a radiopharmaceutical composition comprising a compound of Formula (1) wherein one of R2 or R3 is a radio halo and the other is hydrogen, C 1 to C 8 alkyl, and R 1 and R 4 and R 5 are as previously defined, and a pharmaceutically acceptable carrier, allowing the radiopharmaceutical to localize within the brain, and then taking an image of the brain of the patient so treated.
Compounds of the present invention are those of Formula (1) in which R 1 is selected from the group consisting of hydrogen and C 1 to C 8 alkyl; R 2 is selected from the group consisting of hydrogen, iodo, radioisotopic halo, C 1 to C 8 alkyl and tri lower alkyl (C 1 to C 8 ) tin; and R 1 and R 2 may be fused by a --N(Me)CH═CH-- to form a pyrrole ring; R 3 is selected from the group consisting of hydrogen, iodo, or C 1 to C 8 alkyl; R 4 is selected from the group consisting of hydrogen and C 1 to C 8 alkyl; and R 5 is selected from the group consisting of hydrogen or C 1 to C 8 alkyl, and salts, solvates and hydrates thereof.
A preferred group of compounds of this invention are represented by Formula (1) wherein R 1 is selected from the group consisting of hydrogen and C 1 to C 8 alkyl, and R 2 or R 3 , either one or both, are selected from hydrogen, I 123 , I 125 , I 131 and 18F, R 4 is hydrogen, and R 5 is alkyl. In a broader sense, R 2 or R 3 can be radioisotopic halo, tributyltin, trimethyltin, hydrogen, and/or C 1 to C 8 alkyl.
DETAILED DESCRIPTION OF THE INVENTION
In the process used to prepare 3-aryltropane derivatives are prepared by reacting 8-azabicyclo[3.2.1]oct-2-ene with an aryl Grignard reagent in the presence of catalytically effective amounts of copper (I) and/or copper (II) salts (see U.S. Pat. Nos. 5,262,428 and 5,342,949). The 3-aryl-tropane derivative starting material can be conveniently prepared by decomposing functionalized vinyldiazomethanes in the presence of certain pyrroles preferably in substantial excess of the stoichiometric amount, using a decomposition catalyst, preferably a rhodium catalyst. The catalyst may also be a copper, palladium or silver salt catalyst. This provides a bicyclic intermediate containing the basic tropane ring system which is thereafter converted to an 8-azabicyclo[3.2.1] oct-2-ene, which itself may be used as a starting material to react with an aryl Grignard reagent in providing the synthesis route to the unique tropane analogs of the present invention. The earlier referred to process U.S. Pat. Nos. 5,262,428 and 5,342,949 are incorporated herein by reference.
The focus of this application is on the composition of matter of tropane derivatives of the general formula: ##STR2## wherein R 1 is hydrogen or C 1 to C 8 alkyl, R 2 is hydrogen, iodo or C 1 to C 8 alkyl, and R 1 and R 2 may be fused by a--N(Me)CH═CH-- to form a pyrrole ring, R 3 is hydrogen, iodo or C 1 to C 8 alkyl, R 4 is hydrogen or C 1 to C 8 alkyl, and R 5 is hydrogen, or C 1 to C 8 alkyl. The very most preferred compounds are: ##STR3## wherein either R 1 or R 2 is iodo and the other position is hydrogen or C 1 to C 8 alkyl.
The synthesis of the tropane derivatives can be achieved by the general scheme shown below. The general experimental procedure for the final synthesis step has been described in detail in U.S. Pat. No. 5,262,428. The details of the earlier process steps have been reported (Davies, et al., Journal of Organic Chemistry, 1991, 56, 5696).
The synthesis route to the basic tropane derivatives is illustrated in this series of equations shown below. The process is similar to that described in our earlier-referenced co-pending incorporated by reference application Ser. No. 08/589,520. Basically, it is the reaction of a vinyldiazomethane with a nitrogen-protected pyronyl, as illustrated in the schematic tertiary butyl pyronyl, in the presence of a rodium II catalyst. As illustrated, the rodium II catalyst is rodium octanoate. The reaction provides as its product the basic tropane skeleton. This is then selectively reduced at the 6, 7 position using a Wilkinson's catalyst. Nitrogen protecting groups are removed by acid hydrolysis using for example trifluoryl acetic acid. Conversion of the amine to N-methyl is achieved by reductive methylation using for example formaldehyde and sodium cyano borohydride. The conversion of the amine or the N-methyl to an aryl derivative (last of the three equations shown below) is achieved by copper catalyzed 1-4 addition of the appropriate Grignard reagent. ##STR4##
For further details on the synthesis technique, see the previously incorporated by reference pending application. However, since the present application involves as its invention the compounds as distinct from the process of synthesis, further details of the process need not be provided herein.
The synthesis route to prepare the organotin precursors to the iodinated compounds is illustrated below and is described in conjunction with example 11 with particularity. ##STR5##
As illustrated in the above-shown equations, an aryl bromide derivative is initially converted to its Grignard reagent, using cupric-induced 1-4 addition which introduces the aryl group into the 3 position of the tropane. Radical induced addition of tributyltin hydride is initiated by azobisisobutyronitrile and results in the formation of a readily separable mixture of organotin products. The organotin products are the precursors for producing the non-radioactive iodine compounds as well as the I 123 and I 125 derivatives.
The novel tropane analogs synthesized by the vinylcarbenoid scheme listed above were tested for their ability to interact with 5-HT and dopamine transporters by displacement of radioligand binding to transporter sites. Low concentrations (10-20 pM) of [I 125 ]RTI-55, the potent tropane analog recently synthesized by Carroll's group (Boja et al., European Journal of Pharmacology, 1991, 184, 329), was used to label dopamine transporters in rat striatal membranes, while [ 3 H]paroxetine (Habert et al., European Journal of Pharmacology, 1985, 118, 107) was used to label 5-HT transporter sites in rat frontal cortex and [3H]nisoxetine was used to label the NE transporter sites.
In Davies, et al., U.S. Ser. No. 08/589,820, filed Jan. 22, 1996 now U.S. Pat. No. 5,760,055, which is incorporated herein by reference, the synthesis and utility of a series of novel tropanes was described. The synthesis of these compounds was based on a new synthetic method to the tropane. The p-tolyl derivative (for references on recent in vivo biological studies on this compound, see Porrino, L. J. et al., Life Sciences, 1994, 54, 511.47. (b) Hemby, S. E. et al. J. Pharmacol. Exp. Ther. 1995, 272, 1176-1186. (c) Porrino, L. J. et al. J. Pharmacol. Exp. Ther. 1995, 272, 901.), the 1-naphthyl derivative (WF30) and the 4-isopropyl phenyl derivative represent prototypical members of the class of tropanes that can be derived from this chemistry. Many compounds with binding affinity in the 1-20 nM were prepared and in general these compounds were moderately selective for the dopamine transporter. In contrast, the 2-naphthyl derivative was much more potent leading to the most potent tropane analog that has been prepared although it was unselective. However, introduction of bulky aryl substituents resulted in a compound that was quite selective for the 5-HT transporter.
The 5-HT selectivity seen of the current compounds is in sharp contrast to that of most of the previously prepared tropane analogs as these tended to be selective for the dopamine transporter. A further improvement was seen with the 4-(1-methylethenyl)phenyl derivative which was the most selective compound described in the previous case. In this current patent application, the structure is disclosed of novel tropanes that have structural elements such that further increase serotonin selectivity, and additionally, a group of iodinated derivatives that retain the serotonin selectivity, and as the radiolabeled forms, would be selective radioligands for the 5-HT transporter.
Acid addition salts of the compound of Formula 1 are most suitably formed from pharmaceutically acceptable acids, and include, for example, those formed with inorganic acids, e.g. hydrochloric, sulphuric or phosphoric acids and organic acids, e.g. succinic, maleic, acetic or fumaric acid. Other non-pharmaceutically acceptable salts, e.g. oxalates, may be used for example in the isolation of compounds of Formula 1 for laboratory use, or for subsequent conversion to a pharmaceutically acceptable acid addition salt. Also included within the scope of the invention are solvates and hydrates of the invention.
The conversion of a given compound salt to a desired compound salt is achieved by applying standard techniques in which an aqueous solution of the given salt is treated with a solution of base, e.g. sodium carbonate or potassium hydroxide, to liberate the free base which is then extracted into n appropriate solvent, such as ether. The free base is then separated from the aqueous portion, dried, and treated with the requisite acid to give the desired salt.
Compounds of Formula (1), wherein R 2 or R 3 are a radioisotopically labeled iodide, can be prepared by reacting compounds of Formula (1), wherein R 2 or R 3 is tri(loweralkyl)tin, with radioisotopic iodide source, for example, a solution of radioisotopically labeled sodium iodide (e.g. as a solution in 1N NaOH), in the presence of an acid and an oxidizing agent in an alcoholic solvent. Preferred conditions are Chloramine T and hydrochloric acid in ethanol.
The compounds of the invention wherein R 2 or R 3 are radioisotopic iodide are formulated as radiopharmaceutical compositions together with any physiologically and radiologically tolerable vehicle appropriate for administering the compound systemically. Included among such vehicles are phosphate buffered saline solutions, buffered for example to pH 7.4.
For use in medicine, the compounds of the present invention can be administered in a standard pharmaceutical composition. The present invention therefore provides, in a further aspect, pharmaceutical compositions comprising a pharmaceutically acceptable carrier and a Formula (1) compound or a pharmaceutically acceptable salt, solvate or hydrate thereof, in an amount effective to bind to the 5-HT transporter.
The compounds of the present invention may be administered by any convenient route, for example by oral, parenteral, buccal, sublingual, nasal, rectal or transdermal administration and the pharmaceutical compositions formulated accordingly.
Compounds of Formula (1) and their pharmaceutically acceptable salts which are active when given orally can be formulated as liquids, for example syrups, suspensions or emulsions, or as solid forms such as tablets, capsules and lozenges. A liquid formulation will generally consist of a suspension or solution of the compound or pharmaceutically acceptable salt in a suitable pharmaceutical liquid carrier, for example, ethanol, glycerine, non-aqueous solvent, for example, polyethylene glycol, oils, or water with a suspending agent, preservative, flavouring or colouring agent. A composition in the form of a tablet can be prepared using any suitable pharmaceutical carrier routinely used for preparing solid formulations. Examples of such carriers include magnesium stearate, starch, lactose, sucrose and cellulose. A composition in the form of a capsule can be prepared using routine encapsulation procedures. For example, pellets containing the active ingredient can be prepared using standard carriers and then filled into hard gelatin capsule; alternatively, a dispersion or suspension can be prepared using any suitable pharmaceutical carrier, for example, aqueous gums, celluloses, silicates or oils and the dispersion or suspension filled into a soft gelatin capsule.
Typical parenteral compositions consist of a solution or suspension of the compound or pharmaceutically acceptable salt in a sterile aqueous carrier or parenterally acceptable oil, for example, polyethylene glycol, polyvinyl pyrrolidone, lecithin, arachis oil or sesame oil. Alternatively, the solution can be lyophilized and then reconstituted with a suitable solvent just prior to administration.
Compositions for nasal administration may conveniently be formulated as aerosols, drops, gels and powders. Aerosol formulations typically comprise a solution or fine suspension of the active substance in a physiologically acceptable aqueous or non-aqueous solvent and are usually presented in single or multidose quantities in sterile form in a sealed container, which can take the form of a cartridge or refill for use with an atomizing device. Alternatively, the sealed container may be a unitary dispensing device such as a single dose nasal inhaler or an aerosol dispenser fitted with a metering valve which is intended for disposal after use. Where the dosage form comprises an aerosol dispenser, it will contain a propellant which can be a compressed gas such as compressed air or an organic propellant such as flurochlorohydrocarbon. The aerosol dosage forms can also take the form of a pump-atomizer.
Compositions suitable for buccal or sublingual administration include tablets, lozenges, and pastilles, wherein the active ingredient is formulated with a carrier such as sugar, acacia, tragacanth, or gelatin and glycerine. Compositions for rectal administration are conveniently in the form of suppositories containing a conventional suppository base such as cocoa butter.
Preferably, the composition is in unit dose form such as a tablet, capsule or ampoule. Suitable unit doses, i.e. therapeutically effective amounts, can be determined during clinical trials designed appropriately for each of the conditions for which administration of a chosen compound is indicated and will of course vary, depending on the desired clinical endpoint. It is anticipated that dosage sizes appropriate for administering the compounds of the examples will be roughly equivalent to, or slightly less than those used currently for fluoxetine. Accordingly, each dosage unit for oral administration may contain from 1 to about 500 mgs and will be administered in a frequency appropriate for initial and maintenance treatments.
For imaging and diagnostic purposes, it is contemplated that the present compounds will be administered to patients by intravenous injection or infusion at doses suitable (e.g. between 1 and 10 mCi) to generate an image of the compound as localized within the brain, using for example a gamma camera. Preferably, the compounds will be administered and allowed to localize within the brain for 30 minutes to 48 hours prior to generating an image of the brain of the patient so treated. It is further contemplated that the method of the present invention can usefully be applied diagnose to patients suspected of suffering from depression. For these patients, diagnosis can be aided or confirmed by determining the intensity of radiolabeled compound relative to the brain of a healthy patient; lower image intensity is indicative of an underabundance of 5-HT transporter, and this is expected to be indicative of a depressed state.
The following examples are offered to further illustrate but not limit the invention.
Table 1 demonstrates the binding affinities of a series of tropanes to the dopamine (DA), serotonin (5-HT) and norepinephrine (NE) transporters (Examples 1-13). The first two compounds are the isopropenyl derivatives 1 and 2, that represent the compounds of best selectivity and potency disclosed in the previous incorporated by reference U.S. patent application. The best 5-HT/DA potency ratio was 150 and the best 5-HT/NE potency ratio was 970. Considerable improvement in selectivity was seen in many of the new compounds (3-13). The arylpyrrole derivative of example 4 is most notable with a 5-HT/DA potency ratio of 590 and a 5-HT/NE potency ratio of >25,000. The enhanced selectivity would enable these exhibit their activities cleanly at the 5-HT transporter and avoid side effects due to interactions at the other transporters. In terms of development of diagnostic agents, the iodinated compounds 11-13 are particularly relevant. The high binding affinities of these compounds makes their I-123 and I-125 analogs very interesting radioligands. In particular, the I-123 analogs are promising as SPECT agents for mapping the 5-HT transporters.
TABLE 1__________________________________________________________________________IC.sub.50 and K.sub.i values of tropane analogs in displacing bindingof [.sup.125 I]RTI-55, [.sup.3 H]paroxetine and [.sup.3 H]nisoxetinebinding inrat brain membranes.sup.17d,23 ##STR6## 5-HT/DA 5-HT/NE (5-HT) (DA) (NE) potency potencyEx. R.sub.1 R.sub.2 R.sub.3 R.sub.4 K.sub.i (nM) IC.sub.50 (nM) K.sub.i (nM) ratio ratio__________________________________________________________________________1 Me H H Me 0.82 ± 0.38 7.2 ± 2.1 794 ± 110 8.8 9702 Me H H H 0.11 ± 0.02 16 ± 4.9 94 ± 18 150 8503 --N(Me)CH═CH-- H Me 25.6 ± 4.1 703 ± 222 >10,000 24 >15,0004 --N(Me)CH═CH-- H H 1.05 ± 0.2 614 ± 98 >10,000 590 >25,0005 H Me Me Me 9.22 ± 2.4 51.3 ± 15.5 4134 ± 785 6 4486 H Me Me H 0.404 ± 0.1 96.3 ± 17.1 1251 ± 124 240 30977 Et H H Me 1.13 ± 0.3 22.1 ± 7.76 1135 ± 606 20 10008 Et H H H 0.194 ± 0.1 37.9 ± 12.9 347 ± 54.8 200 17909 H Me H Me 1.17 ± 0.46 1.59 ± 0.66 292 ± 71.7 1.5 25010 H Me H H 0.236 1.94 ± 0.96 25.6 ± 9.6 8 10811 H I H H 0.619 ± 0.078 51.3 ± 5.6 49.7 ± 10.6 83 8012 H I Me H 0.566 ± 0.027 401 ± 73 365 ± 118 708 64513 H Me I H 0.131 ± 0.030 66.5 ± 11.1 66.7 ± 17.1 507 509__________________________________________________________________________
Table 1 summarizes each of the examples 1-13 presented. As earlier mentioned, examples 1 and 2 are representative of compounds in our previously incorporated and now patent application Ser. No. 08/589,820, filed Jan. 22, 1996, now U.S. Pat. No. 5,760,005. As can be seen in the examples illustrating the invention of the present application (examples 3-13), there is a significant improvement in 5-HT/DA potency ratio indicating that the compounds are much more receptive to the 5-HT transporter site and are therefore much better candidates for antidepressants. Most importantly as illustrated in examples 11, 12 and 13, the radiolabeled compounds, because of their high potency ratio and their radio sensitivity, can be successfully used as imaging agents. As a result, these imaging agents can be used to map out the serotonin receptor sites in the brain. Thus, for example, one can see a map of the serotonin receptor sites in a normal brain, and the serotonin receptor sites in a brain of a person suffering from depression, and by comparing the patterns one can predict a person needing treatment simply by looking at the image produced by the radiolabeled imaging agents of compounds 11, 12 and 13.
This invention represents the first tropane ring system compounds that are highly potent as serotonin selective uptake agents. Thus it can be seen that the invention accomplishes each of its stated objectives by the evidence summarized in Table 1.
The procedures for each of examples 3-13 are set forth below.
EXAMPLE 3 ##STR7## 8-Methyl-2β-propanoyl-3β-[4-(N-methyl-2-pyrrolyl)phenyl]-8-azabicyclo[3,2,1]octane(3)
(2:1:0.1 pet ether/ether/Et 3 N, 55%). 1 H NMR (400 MHz, CDCl 3 ) δ 7.28 (d, 2 H, J=8.8 Hz), 7.24 (d, 2 H, J=8.8 Hz), 6.68 (s, 1 H), 6.17 (m, 2 H), 3.63 (s, 3 H), 3.51 (br d, 1 H, J=6.2 Hz), 3.39 (m, 1 H), 3.09 (bs, 1 H), 2.98 (m, 1 H), 2.62 (dt, 1 H, J=2.0, 16.6 Hz), 2.40 (dq, 1 H, J=15.0, 7.5 Hz), 2.31-2.10 (m, 2 H), 2.41 (s, 3 H), 1.81-1.65 (m, 4 H), 0.75 (t, 3 H, J=7.5 Hz). ##STR8## 8-Methyl-2β-propanoyl-3β-[4-(N-methyl-2-pyrrolyl)phenyl]-8-azabicyclo[3,2,1]octane fumarate salt (3a).
(69%). IR (neat) 3436, 1696, 1384, 1111 cm -1 ; 1 H NMR (300 MHz, D 2 O) δ 7.19 (d, 2 H, J=8.0 Hz), 7.04 (d, 2 H, J=8.0 Hz), 6.62 (s, 1 H), 6.43 (s, 1 H), 6.00 (m, 2 H), 3.84 (m, 2 H), 3.37 (s, 3 H), 3.45-3.34 (m, 1 H), 3.23 (d, 1 H, J=5.7 Hz), 2.60 (s, 3 H), 2.54 (t, 1 H, J=14 Hz), 2.36-1.90 (m, 5 H), 1.74 (br d, 1 H, J=15 Hz), 1.20 (dq, 1 H, J=14, 7.5 Hz), 0.36 (t, 3 H, J=7.5 Hz). 13 C NMR (75.45 MHz, D 2 O/CD 3 OD) δ 221.6, 172.5, 138.1, 135.9, 133.4, 129.9, 129.0, 126.1, 109.2, 65.6, 64.8, 54.1, 40.2, 40.0, 35.5, 34.5, 32.2, 25.0, 23.5, 6.8. Anal. Calcd for C 26 H 32 O 5 N 2 : C, 69.01; H, 7.13; N, 6.19. Found: C, 68.75; H, 7.14; N, 6.09.
EXAMPLE 4 ##STR9## 2.beta.-Propanoyl-3β-[4-(N-methyl-2-pyrrolyl)phenyl]-8-azabicyclo[3.2.1]octane (4).
(8% Et 3 N/ether, 42%) 1 H NMR (CDCl 3 ) δ 7.29 (d, 2 H, J=9.3 Hz), 7.17 (d, 2 H,=9.3 Hz), 6.64 (m, 1 H), 6.18 (m, 2 H), 3.72 (m, 1 H), 3.60 (s, 3 H), 3.64 (d, 1 H, J=6.8 Hz), 3.30 (dt, 1 H, J=6.9, 13.7 Hz), 2.93 (d, 1 H, J=6.9 Hz), 2.42 (dt, 1 H, J=13.7, 2.5 Hz), 2.22-1.80 (m, 3 H), 1.80-1.49 (m, 4 H), 0.66 (t, 3 H, J=6.5 Hz). ##STR10## 2β-Propanoyl-3β-[4-(N-methyl-2-pyrrolyl)phenyl]-8-azabicyclo[3.2.1]octane fumarate salt.
(71% yield). IR (neat) 3422, 1692, 1609 cm -1 ; 1 H NMR (300 MHz, D 2 O) δ 7.18 (d, 2 H, J=6.4 Hz), 7.04 (d, 2 H, J=6.4 Hz), 6.64 (m, 1 H), 6.47 (s, 2 H), 5.98-6.04 (m, 2 H), 4.06 (m, 1 H), 3.98 (br d, 1 H, J=5.5 Hz), 3.37 (s, 3 H), 3.34 (m, 1 H), 2.38 (dt, 1 H, J=2.0, 13.8 Hz), 2.20-1.96 (m, 6 H), 1.68 (m, 1 H), 1.23 (dq, 1 H, J=15, 7.5Hz), 0.4 (t, 3 H, J=7.5 Hz). 13 C NMR (75.45 MHz, D 2 O/CD 3 OD) δ 221.4, 172.9, 138.8, 136.0, 133.2, 129.8, 128.9, 108.4, 57.0, 55.9, 52.9, 40.3, 35.6, 35.2, 30.7, 26.7, 25.6, 24.7, 6.9. Anal. Calcd for C 25 H 30 O 5 N 2 : C, 68.47; H, 6.9; N, 6.39. Found: C, 68.75; H, 7.14; N, 6.09.
EXAMPLE 5 ##STR11## 8-Methyl-2β-Propanoyl-3β-[4-(2-methylpropenyl)phenyl]-8-azabicyclo[3.2.1]octane (5)
(3:1:0.2 pet ether/ether/Et 3 N, 56%). 1 H NMR (400 MHz, CDCl 3 ) δ 7.15 (d, 2 H, J=8.1 Hz), 7.10 (d, 2 H, J=8.1 Hz), 6.18 (s, 1 H), 3.45 (m, 1 H), 3.34 (m, 1 H), 2.93 (s, 1 H), 2.88 (m, 1 H), 2.62 (ddd, 1 H, J=12.3, 12.3, 2.3 Hz), 2.25 (q, 2 H, J=8.5 Hz), 2.19 (s, 3 H), 2.08 (m, 1 H), 1.87 (s, 3 H), 1.82 (s, 3 H), 1.72 (m, 4 H), 0.82 (t, 3 H, J=8.5 Hz). ##STR12## Typical procedure of the preparation of tropane salts. 8-Methyl-2β-Propanoyl-3β-[4-(2-methylpropenyl)phenyl]-8-azabicyclo[3.2.1]octane fumarate salt.
The tropane (180 mg, 0.578 mmol) was dissolved in 2-propanol (10 mL) at room temperature (warm up carefully if necessary). Fumaric acid (63.7 mg, 0.55 mmol) was added and the mixture was warmed to 50° C. until all the solids dissolved. The mixture was cooled to room temperature and the solvents were evaporated. Ether (20 mL) was added and the mixture was stirred for 2 h. The solid was collected by filtration and washed with ether (175 mg, 71%). IR (neat) 3086, 2965, 2942 1690, 1339 cm -1 ; 1 H NMR (400 MHz, D 2 O) δ 7.12 (d, 2 H, J=7.1 Hz), 7.04 (d, 2 H, J=7.1 Hz), 6.51 (s, 1 H), 6.14 (s, 1 H), 3.90 (m, 2 H), 3.44 (dt, 1 H, J=5.2, 13.7 Hz), 3.28 (d, 1 H, J=5.2 Hz), 2.64 (s, 3 H), 2.50 (t, 1 H, J=14.5 Hz), 2.36-2.16 (m, 2 H), 2.12-1.98 (m, 3 H), 1.90 (br d, 1 H, J=15.3 Hz), 1.73 (s, 3 H), 1.67 (s, 3 H), 1.25 (dq, 1 H, J=19.5, 7.5 Hz), 0.41 (t, 3 H, J=7.5 Hz). 13 C NMR (75.5 MHz, D 2 O) δ 221.1, 172.4, 138.8, 138.0, 137.1, 135.9, 130.2, 128.5, 125.2, 65.5, 64.7, 54.1, 40.1, 40.0, 34.4, 32.1, 27.3, 25.0, 23.6, 19.7, 6.9. Anal. Calcd for C 25 H 33 O 5 N: C, 70.23; H, 7.78; N, 3.28. Found: C, 70.20; H, 7.76; N, 3.27.
EXAMPLE 6 ##STR13## 2.beta.-Propanoyl-3β-[4-(2-methylpropenyl)phenyl]-8-azabicyclo[3.2.1]octanem (6).
(8%-15% Et 3 N/Et 2 O, 67%): IR (neat) 2937, 2912, 1698, 1409 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 7.12 (d, 2 H, J=8.0 Hz), 7.08 (d, 2 H, J=8.0 Hz), 6.20 (s, 1 H), 3.71 (m, 1 H), 3.57 (br d, 1 H, J=6.5 Hz), 3.21 (ddd, 1 H, J=12.0, 5.2, 5.2 Hz), 2.98 (br d, 1 H, J=5.2 Hz), 2.42 (dt, 1 H, J=2.0, 12.0 Hz), 2.20-1.94 (m, 3 H), 1.87 (s, 3 H), 1.82 (s, 3 H), 1.78-1.53 (m, 3 H), 0.68 (t, 3 H, J=6.5 Hz). 13 C NMR (75.462 MHz, CDCl 3 ) δ 140.5, 137.6, 135.9, 129.3, 127.8, 125.3, 112.0, 56.8, 56.2, 53.9, 39.0, 36.6, 34.1, 29.4, 27.9, 27.0, 19.5, MS m/z (rel intensity) 297.3 (46), 240.2 (59), 129.1 (18), 83.1 (100), 82.1 (54), 69.2 (83), 68.2 (60), 57.2 (26), 55.1 (17). Anal. Calcd for C 20 H 27 ON C, 80.76; H, 9.15; N, 4.71. Found: C, 80.64; H, 9.08; N, 4.66.
EXAMPLE 7 ##STR14## (R)-8-Methyl-2β-propanoyl-3β-[4-(1-ethylethenyl)phenyl]-8-azabicyclo[3.2.1]octanem (7)
3:1:0.2 pet ether/ether/Et 3 N, 41%). IR (neat) 2960, 2935, 1714, 1353 cm -1 ; 1 H NMR (400 Hz, CDCl 3 ) δ 7.31 (d, 2 H, J=7.6 Hz), 7.17 (d, 2 H, J=7.6 Hz), 5.25 (s, 1 H), 4.94 (s, 1 H), 3.50 (m, 1 H), 3.48 (br d, 1H), 2.99 (s, 1 H), 2.97 (m, 1 H), 2.60 (dt, 1 H, J=1.5, 13.3 Hz), 2.46 (q, 2 H, J=7.6 Hz), 2.42 (s, 3 H), 2.36 (dq, 1 H, J=17, 6.8 Hz), 2.30-2.05 (m, 3 H), 1.79-1.50 (m, 3H), 1.13 (t, 3 H, J=7.6 Hz), 0.68 (t, 3 H, J=6.8 Hz). 13 C NMR (75.5 MHz, CDCl 3 ) δ 210.5, 149.7, 142.4, 138.8, 127.1, 125.7, 110.2, 64.7, 62.3, 59.1, 41.9, 35.1, 34.0, 33.6, 27.7, 26.3, 25.1, 12.8, 7.6. MS m/z (rel intensity) 311.3 (13), 254.3 (36), 97.3 (36), 96.2 (25), 86.0 (62), 84.0 (100), 83.0 (38), 82.0 (40), 57.1 (11). Anal. Calcd for C 21 H 29 ON: C, 80.98, H, 9.39; N, 4.49. Found: C, 80.96; H, 9.35; N, 4.47. [α] 25 D=+41.5° (c 0.91, CHCl 3 ).
EXAMPLE 8 ##STR15## (R)-2.beta.-Propanoyl-3β-[4-(1-ethylethenyl)phenyl]-8-azabicyclo[3.2.1]octane (8)
(1:6 Et 3 N/ether, 36%). 1 H NMR (400 Hz, CDCl 3 ) δ 7.31 (d, 2 H, J=8.8 Hz), 7.10 (d, 2 H, J=8.8 Hz), 5.22 (s, 1 H), 5.05 (s, 1 H), 3.74-3.69 (m, 1 H), 3.58 (br d, 1 H, J=5.2 Hz), 3.42 (dt, 1 H, J=6.0, 11.7 Hz), 2.91 (d, 1 H, J=6.0 Hz), 2.51-2.39 (m, 3 H), 2.23-1.95 (m, 4 H), 1.79-1.50 (m, 4 H), 1.08 (t, 3 H, J=6.0 Hz), 0.66 (t, 3H, J=6.6 Hz). ##STR16## (R)-2β-Propanoyl-3β-[4-(1-ethylethenyl)phenyl]-8-azabicyclo[3.2.1]octane fumarate.
(66%). IR (neat) 3435, 3192, 1697, 1609, 1376 cm -1 ; 1 H NMR (400 Hz, D 2 O) δ7.34 (d, 2 H, J=6.8 Hz), 7.07 (d, 2 H, J=6.8 Hz), 6.51 (s, 2 H), 5.19 (s, 1 H), 4.96 (s, 1 H), 4.10 (m, 1 H), 4.04 (m, 1 H), 3.42 (ddd, 1 H, J=12.9, 12.9, 6.2 Hz), 3.27 (d, 1 H, J=6.2 Hz), 2.44 (t, 1 H, J=12.9 Hz), 2.34 (q, 2 H, J=6.7 Hz), 2.15-1.96 (m, 6 H), 1.77 (m, 1 H), 1.28 (dq, 1 H, J=17.6, 6.8 Hz), 0.86 (t, 3 H, J=6.7 Hz), 0.40 (t, 3 H, J=6.8 Hz). 13 C NMR (75.5 MHz, D 2 O) δ 221.3, 172.6, 151.0, 141.3, 139.3, 135.9, 128.7, 127.6, 112.1, 56.9, 55.9, 52.8, 40.3, 35.1, 30.7, 28.3, 26.7, 25.5, 13.3, 6.8. Anal. Calcd for C 24 H 31 O 5 N: C, 69.71; H, 7.56; N, 3.39. Found: C, 69.60; H, 7.54; N, 3.35.
EXAMPLE 9 ##STR17## (R)-(E)-8-Methyl-2β-propanoyl-3β-[4-(1-propenyl)phenyl]-8-azabicyclo[3.2.1]octane (9).
4:1:0.2 pet ether/ether/Et 3 N, 57%. IR (neat) 2958, 2935, 1716, 1689 CM -1 ; 1 H NMR (400 Hz, CDCl 3 ) δ 7.20 (d, 2 H, J=8.5 Hz), 7.14 (d, 2 H, J=8.5 Hz), 6.32 (d, 1 H, J=16.4 Hz), 6.15 (dq, 1 H, J=16.4, 6.9 Hz), 3.46 (m, 2 H), 3.35 (m, 1 H), 2.97 (s, 1 H), 2.92 (m, 1 H), 2.58 (dt, 1 H, J=1.7, 14.3 Hz), 2.39 (s, 3 H), 2.34 (dq, 1 H, J=17, 8.0 Hz), 2.18 (m, 1 H), 1.84 (d, 3 H, J=6.9 Hz), 1.79-1.55 (m, 4 H), 0.68 (t, 3 H, J=7.4 Hz). 13 C NMR (75.5 MHz, CDCl 3 ) δ 210.6, 142.0, 135.5, 130.9, 127.4, 125.6, 124.9, 64.5, 62.4, 59.3, 42.0, 35.2, 34.1, 33.7, 26.4, 25.2, 18.4, 7.7; Anal. Calcd for C 20 H 27 ON: C, 80.76; H, 9.15; N, 4.71. Found: C, 80.77; H, 9.22; N, 4.67. [α] 25 D=+43.0° (c 1.06, CHCl 3 ).
EXAMPLE 10 ##STR18## (R)-(E)-2β-Propanoyl-3β-[4-(1-propenyl)phenyl]-8-azabicyclo[3.2.1]octane (10).
(1:5 ether/Et 3 N, 48%). 1 H NMR (400 Hz, CDCl 3 ) δ 7.22 (d, 2 H, J=7.8 Hz), 7.06 (d, 2 H, J=7.8 Hz), 6.34 (d, 1 H, J=15.6 Hz), 6.19 (dq, 1 H, J=15.6, 6.8 Hz), 3.70 (m, 1 H), 3.56 (d, 1 H, J=7.6 Hz), 3.20 (dt, 1 H, J=13, 5.9 Hz), 2.88 (d, 1 H, J=5.9 Hz), 2.76 (br s, 1 H), 2.42 (dt, 1 H, J=1.4, 13 Hz), 2.21-1.94 (m, 2 H), 1.86(d, 3 H, J=6.8 Hz), 1.75-1.51 (m, 4 H), 0.39 (t, 3 H, J=7.6 Hz). ##STR19## (R)-(E)-2β-Propanoyl-3β-[4-(1-propenyl)phenyl]-8-azabicyclo[3.2.1]octane fumarate salt (10a).
(73%). IR (neat) 3416, 3170, 1693, 1598, 1385 cm -1 ; 1 H NMR (400 Hz, D 2 O) δ 7.22 (d, 2 H, J=7.5 Hz), 7.01 (d, 2 H, J=7.5 Hz), 6.28 (d, 1 H, J=16 Hz), 6.24 (d, 1 H, J=15 Hz), 6.21 (m, 1 H), 4.10 (br s, 1 H), 4.01 (br s, 1H), 3.41 (m, 1 H), 3.25 (m, 1 H), 2.42 (t, 1 H, J=14 Hz), 2.18-1.94 (m, 6 H), 1.75 (d, 1 H, J=17 Hz), 1.66 (d, 3 H, J=6.4 Hz), 1.30 (m, 1 H), 0.40 (t, 3 H, J=6.7 Hz). 13 C NMR (75.5 MHz, D 2 O/CD 3 OD) δ 220.9, 200.8, 172.3, 138.5, 138.3, 135.9, 131.0, 128.9, 128.1, 127.3, 56.9, 55.9, 52.8, 49.9, 40.3, 35.2, 30.8, 26.7, 25.6, 24.7, 18.7, 6.8. Anal. Calcd for C 23 H 29 O 5 N.0.2H 2 O: C, 68.53; H, 7.35; N, 3.47. Found: C, 68.45; H, 7.42; N, 3.36.
EXAMPLES 11-13 ##STR20## Typical procedure for the conjugate addition: 2β-Propanoyl-3β-[4-(2-(trimethylsilylacetylenyl)phenyl]-8-azabicyclo[3.2.1]octane.
4-(2-(Trimethylsilylacetylenyl)phenylmagnesium bromide was generated as follows: a portion (10%) of the bromide (2.50 g, 9.64 mmol) in THF (20 mL) was added to magnesium turnings (0.262 g, 10.8 mmol). Two drops of dibromoethane was added. The reaction was initiated by heating. Once the reaction was started, the remaining bromide was added dropwise. The mixture was refluxed for 2 h after the addition and cooled to room temperature. The resulting Grignard reagent (dark brown) was added dropwise to thoroughly dried copper bromidedimethyl sulfide complex (0.300 g, 1.48 mmol). The mixture was stirred at room temperature for 15 min. and cooled to 0° C. A solution of 2-propanoyl-8-aza-bicyclic[3.2.1]oct-2-ene (0.325 g, 1.96 mmol) in THF (40 mL) was added dropwise. The ice bath was left in place and stirring was continued overnight. The solution was cooled to -78° C. and a solution of HCl (g) in dry ether (50 mL) (prepared by bubbling HCl gas into ether for 30 min.) was added in such a way that the temperature was kept below -70° C. at all times. The reaction mixture was poured into ice water (50 g) and warmed to room temperature. The organic layer was separated out (keep the aqueous layer) and washed with aqueous HCl solution (10%, 3×30 mL). The combined aqueous solution was basified with aqueous NH 3 , saturated with sodium chloride and extracted with methylene chloride (4×60 mL). The combined extracts were dried (MgSO 4 ) and evaporated. Flash chromatography of the residue over silica gel using 10% triethylamine: 90% ether gave the tropane as a light yellow liquid (436 mg, 65%): [α] 25 D=-95.8° (c 0.95, CHCl 3 ); FTIR (neat) 2955, 2154, 1697, 1408 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.36 (d, 2 H, J=8.4 Hz), 7.09 (d, 2 H, J=8.4 Hz), 3.71 (m, 1 H), 3.55 (br d, 1 H, J=5.5 Hz), 3.20 (ddd, 1 H, J=13, 5.0, 5.0 Hz), 2.89 (br d, 1 H, J=5.0 Hz), 2.42 (ddd, 1 H, J=13, 13, 2.7 Hz), 2.26-1.90 (m, 3 H), 1.78-1.62 (m, 4 H), 0.69 (t, 3 H, J=7.2 Hz), 0.23 (s, 9 H); 13 C NMR (75.45 MHz, CDCl 3 ) δ 214.7, 143.1, 132.0, 127.5, 121.1, 104.9, 93.9, 56.1, 55.6, 53.3, 38.5, 36.4, 33.4, 29.0, 27.4, 6.8, -0.2; Anal. Calcd for C 21 H 29 NOSi: C, 74.28; H, 8.61; N, 4.13. Found: C, 74.24; H, 8.67; N, 4.06. ##STR21## 2β-Propanoyl-3β-(4-acetylenylphenyl)-8-azabicyclo[3.2.1]octane.
Tropane was dissolved in THF (20 mL) and TBAF (1.21 mL, 1.21 mmol, 1M in THF) was added dropwise at room temperature. The mixture was stirred for 2 h. Saturated aqueous NH 4 Cl (10 mL) was added, followed by NH 4 OH (10 mL). The mixture was saturated with solid NaCl and extracted with CH 2 Cl 2 (5×20 mL). The combined organic extracts were washed with brine, dried (MgSO 4 ) and evaporated. Chromatography of the residue over silica using 10% Et 3 N/ether gave tropane (237 mg, 81%): [α] 25 D=-112.2° (c 1.05, CHCl 3 ); FTIR (neat) 2977, 2936, 1685, 1406 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.38 (d, 2 H, J=8.2 Hz), 7.11 (d, 2 H, J=8.2 Hz), 3.71 (m, 1 H), 3.57 (br d, 1 H, J=6.0 Hz), 3.20 (ddd, 1 H, J=13, 5.4, 5.4 Hz), 3.04, (s, 1 H), 2.90 (br d, 1 H, J=5.4 Hz), 2.43 (ddd, 1 H, J=13, 13, 2.9 Hz), 2.31-1.93 (m, 3 H), 1.78-1.52 (m, 4 H), 0.70 (t, 3 H, J=7.3 Hz); 13 C NMR (75.45 mHz, CDCl 3 ) δ 214.7, 143.6, 132.2, 127.7, 120.1, 110.9, 83.5, 56.2, 55.7, 53.4, 38.5, 36.4, 33.4, 29.1, 27.5, 6.9; Anal. Calcd for C 18 H 21 NO: C, 80.86; H, 7.92; N, 5.24. Found: C, 80.82; H, 7.95; N, 5.31. ##STR22## (E)-2β-Propanoyl-3β-[4-(2-tributylstannylethenyl)phenyl]-8-azabicyclo[3.2.1]octane.
Tropane (145 mg, 0.54 mmol) was dissolved in benzene (7 mL) and AIBN (10 mg, 0.06 mmol) was added. The mixture was lowered into an oil bath set at 80° C. Bu 3 SnH (0.29 mL, 1.08 mmol) was added in one portion. Refluxing was continued for 3 h. The solvents were removed and chromatography of the residue over silica chromatography using 5%-15% Et 3 N/ether gave tropane (233 mg, 77%): [α] 25 D=-69.6° (c 1.19, CHCl 3 ); FTIR (neat) 2955, 2922, 1704, 1460 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.31 (d, 2 H, J=8.4 Hz), 7.10 (d, 2 H, J=8.4 Hz), 6.86 (d, 1 H, J=31 Hz), 6.65 (d, 1 H, J=31 Hz), 3.75-3.68 (m, 1 H), 3.58 (br d, 1 H, J=5.9 Hz), 3.20 (ddd, 1 H, J=13, 5.1, 5.1 Hz), 2.91 (br d, 1 H, J=5.1 Hz), 2.43 (ddd, 1 H, J=13, 13, 2.2 Hz), 2.26-1.95 (m, 3 H), 1.78-1.22 (m, 18 H), 0.98-0.80 (m, 14 H), 0.70 (t, 3 H, J=7.0 Hz); 13 C NMR (75.45 MHz, CDCl 3 ) δ 215.0, 145.6, 141.8, 137.01, 129.0, 127.7, 126.0, 56.3, 55.8, 53.5, 38.7, 36.3, 33.8, 29.0, 27.6, 27.2, 13.7, 9.5, 7.0; Anal. Calcd for C 30 H 49 NOSn: C, 64.53; H, 8.84; N, 2.51. Found: C, 64.45; H, 8.92; N, 2.56. ##STR23## (E)-2β-Propanoyl-3β-[4-(2-iodoethenyl)phenyl]-8-azabicyclo[3.2.1]octane.
The vinyltin tropane (73 mg, 0.13 mmol) was dissolved in CH 2 Cl 2 (9 mL) and argon was padded through for 10 min. Iodine (200 mg, 0.78 mmol) was added and the mixture was stirred at room temperature overnight. Aqueous Na 2 S 2 O 3 solution was then added followed by NH 4 OH. The mixture was saturated with solid NaCl and extracted with CH 2 Cl 2 (5×20). The combined organic extracts were dried (MgSO 4 ) and evaporated. Chromratography of the residue over silica using 5-15% Et 3 N/ether gave lodonated tropane (26 mg, 51%): [α] 25 D=-71.0° (c 51, CHCl 3 ); FTIR (neat) 3328, 2970, 2937, 2914, 1693 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.35 (d, 1 H, J=15.0 Hz), 7.18 (d, 2 H, J=8.0 Hz), 7.09 (d, 2 H, J=8.0 Hz), 6.76 (d, 1 H, J=15.0 Hz), 3.69 (br s, 1 H), 3.57 (br d, 1 H, J=6.2 Hz), 3.17 (ddd, 1 H, J=11.3, 5.1, 5.1 Hz), 2.89 (br d, 1 H, J=5.5 Hz), 2.80 (b s, 1 H), 2.41 (ddd, 1 H, J=11.3, 11.3, 2.7 Hz), 2.28-1.93 (m, 3 H), 1.79-1.48 (m, 4 H), 0.68 (t, 3 H, J=6.9 Hz); 13 C NMR (75.45 MHz, CDCl 3 ) δ 214.7, 144.5, 142.8, 135.9, 127.9, 126.0, 76.2, 56.2, 55.7, 53.5, 38.6, 36.3, 33.6, 29.1, 27.5, 7.0; Anal. Calcd for C 18 H 22 NOI: C, 54.69; H, 5.61; N, 3.54. Found: C, 54.68; H, 5.66; N, 3.48. ##STR24## (E)-2β-Propanoyl-3β-[4-1-propynyl)phenyl]-8-azabicyclo[3.2.1]octane.
4-(Propynyl)phenylmagnesium bromide was generated as follows: A portion (10%) of the bromide (1.33 g, 6.82 mmol) in THF (15 mL) was added to magnesium turnings (0.182 g, 7.5 mmol). Two drops of dibromoethane was added. The reaction was initiated by heating. Once the reaction was started, the remaining bromide was added dropwise. The mixture was refluxed for 2 h after the addition and cooled to room temperature. The resulting Grignard reagent (dark brown) was added dropwise to thoroughly dried copper bromide-dimethyl sulfide complex (0.207 g, 1.02 mmol). The mixture was stirred at room temperature for 15 min. and cooled to 0° C. A solution of 2-propanoyl-8-aza-bicyclic[3.2.1]oct-2-ene (0.225 g, 1.36 mmol) in THF (30 Iti) was added dropwise. The ice bath was left in place and stirring was continued overnight. The solution was cooled to -78° C. and a solution of HCl (g) in dry ether (50 mL) (prepared by bubbling HCl gas into ether for 30 min.) was added in such a way that the temperature was kept below -70° C. at all times. The reaction mixture was poured into ice water (50 g) and warmed to room temperature. The organic layer was separated out (keep the aqueous layer) and washed with aqueous HCl solution (10%, 3×30 mL). The combined aqueous solution was basified with aqueous NH 3 , saturated with sodium chloride and extracted with methylene chloride (4×60 mL). The combined extracts were dried (MgSO 4 ) and evaporated. Flash chromatography of the residue over silica gel using 5% triethylamine: 95% ether gave the tropane as a light yellow liquid (176 mg, 46%): [α] 25 D=-89.0° (c 1.02, CHCl 3 ); FTIR (neat) 3321, 2940, 2915, 1696, 1509 cm -1 ; 1 H NMR (CDCl 3 ) d 7.23 (d, 2 H, J=8.4 Hz), 7.09 (d, 2 H, J=8.4 Hz), 3.71 (m, 1 H), 3.55 (br d, 1 H, J=5.5 Hz), 3.20 (ddd, 1 H, J=13, 5.9, 5.9 Hz), 2.89 (br d, 1 H, J=5.9 Hz), 2.42 (ddd, 1 H, J=13, 13, 2.7 Hz), 2.26-1.90 (m, 3 H), 1.78-1.62 (m, 4 H), 0.69 (t, 3 H, J=7.2 Hz); 13 C NMR (75.45 MHz, CDCl 3 ) δ 214.6, 141.8, 131.3, 127.3, 121.9, 85.5, 79.3, 56.0, 55.6, 53.3, 38.5, 36.3, 33.4, 29.0, 27.4, 6.8, 4.1; Anal. Calcd for C 19 H 23 NO.1/8 H 2 O: C, 80.46; H, 8.26; N, 4.94. Found: C, 80.55, H, 8.14; N, 4.73. ##STR25## (Z) and (E)-2β-Propanoyl-3β-[4-(2-tributylstannylpropenyl) phenyl]-8-azabicyclo[3.2.1]octane.
Tropane (126 mg, 0.45 mmol) was dissolved in benzene (5 mL) and AIBN (20 mg, 0.12 mmol) was added. The mixture was lowered into an oil bath set at 90° C. Bu 3 SnH (0.24 mL, 0.90 mmol) was added in one portion. Refluxing was continued for 4 h. More AIBN (10 mg, 0.06 mmol) and Bu 3 SnH (0.12 mL, 0.45 mmol) were added. Refluxing was continued overnight. The solvents were removed and chromatography of the residue over silica chromatography using 5% Et 3 N/ether gave A (16.5 mg, 23%): [α] 25 D=-69.2° (c0.8); FTIR (neat) 2954, 2923, 1700, 1463, 1406 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.17 (d, 1 H, J=1.5 Hz), 7.05 (b s, 4 H), 3.69 (m, 1 H), 3.57 (br d, 1 H, J=6.2 Hz), 3.18 (ddd, 1 H, J=14.5, 5.4, 5.4 Hz), 2.89 (br d, 1 H, J=5.4 Hz), 2.42 (ddd, 1 H, J=14.5, 14.5, 2.5 Hz), 2.54-1.95 (m, 3 H), 2.07 (d, 3 H, J=1.5 Hz), 1.78-1.15 (m, 16 H), 0.91-0.60 (m, 18 H); 13 C NMR (75.45 MHz, CDCl 3 ) δ 215.0, 144.1, 140.7, 140.5, 139.5, 127.6, 127.3, 56.2, 55.7, 53.5, 38.8, 36.4, 33.9, 29.0, 28.1, 27.5, 27.3, 13.6, 10.5, 7.0; Anal. Calcd for C 31 H 51 NOSn: C, 65.04; H, 8.98; N, 2.45. Found: C, 65.06, H, 9.03; N, 2.43. B (106 mg, 42%): [α] 25 D=-66.5° (c0.8, CHCl 3 ); FTIR (neat) 2953, 2923, 2870, 1700, 1458, 1408 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.17 (d, 2 H, J=8.4 Hz), 7.10 (d, 2 H, J=8.4 Hz), 6.52 (d, 1 H, J=1.5 Hz), 3.71 (m, 1 H), 3.57 (br d, 1 H, J=6.2 Hz), 3.22 (ddd, 1 H, J=13.2, 5.1, 5.1 Hz), 2.90 (br d, 1 H, J=5.9 Hz), 2.43 (ddd, 1 H, J=13.2, 3.2, 2.6 Hz), 2.24-1.95 (m, 3 H), 2.07 (d, 3 H, J=1.5 Hz), 1.78-1.21 (m, 16 H), 0.95-0.80 (m, 15 H), 0.69 t, 3 H, J=7.9 Hz); 13 C NMR (75.45 MHz, CDCl 3 ) δ 215.2, 143.8, 140.2, 138.5, 136.4, 128.9, 127.2, 56.3, 55.8, 53.5, 38.8, 36.3, 33.8, 29.2, 29.1, 27.6, 27.3, 21.1, 13.7, 9.2, 6.9; Anal. Calcd for C 31 H 51 NOSn: C, 55.04; H, 8.98, N, 2.45. Found: C, 64.99, H, 8.96; N, 2.53. ##STR26## (Z)-2β-Propanoyl-3β-[4-(2-iodopropenyl)phenyl]-8-azabicyclo[3.2.1]octane.
The vinyltin tropane (40 mg, 0.070 mmol) was dissolved in CH 2 Cl 2 (5 mL) and argon was passed through for 10 min. Iodine (107 mg, 0.42 mmol) was added and the mixture was stirred at room temperature overnight. Aqueous Na 2 S 2 O 3 solution was then added, followed by NH 4 OH. The mixture was saturated with solid NaCl and extracted with CH 2 Cl 2 (5×20). The combined organic extracts were dried (MgSO 4 ) and evaporated. Chromatography of the residue over silica using 5-15% Et 3 N/ether gave iodonated tropane (16.2 mg, 57%): [α] 25 D=-97.3° (c 0.3, CHCl 3 ); FTIR (neat) 2937, 2911, 1694, 1406 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.34 (d, 2 H, J=8.1 Hz), 7.12 (d, 2H, J=8.1 Hz), 6.60 (s, 1 H), 3.73 (m, 1 H), 3.59 (br d, 1 H, J=5.1 Hz), 3.25 (ddd, 1 H, J=15, 5.5, 5.5 Hz), 2.90 (br d, 1 H, J=5.5 Hz), 2.69 (s, 3 H), 2.45 (ddd, 1 H, J=15, 15, 2.2 Hz), 2.22-1.95 (m, 3 H), 1.78-1.55 (m, 4 H), 0.68 (t, 3 H, J=7.3 Hz); 13 C NMR (75.45 MHz, CDCl 3 ) δ 215.2, 141.6, 136.8, 134.3, 128.6, 127.2, 100.0, 56.1, 55.7, 53.4, 38.9, 36.4, 35.3, 33.5, 29.0, 27.5, 7.0; Anal. Calcd for C 19 H 24 NOI: C, 55.75; H, 5.91; N, 3.42. Found: C, 55.97; H, 6.00; N, 3.25. ##STR27## (E)-2β-Propanoyl-3.beta.-[4-(2-iodopropenyl)phenyl]-8-azabicyclo[3.2.1]octane.
The vinyltin tropane (53.6 mg, 0.094 mmol) was dissolved in CH 2 Cl 2 (7 mL) and argon was passed through for 10 min. Iodine (143 mg, 0.56 mmol) was added and the mixture was stirred at room temperature overnight. Aqueous Na 2 S 2 O 3 solution was then added followed by NH 4 OH. The mixture was saturated with solid NaCl and extracted with CH 2 Cl 2 (5×20). The combined organic extracts were dried (MgSO 4 ) and evaporated. Chromatography of the residue over silica using 5-15% Et 3 N/ether gave iodinated tropane (28.9 mg, 75%): [α] 25 D=-77.1° (c 0.28, CHCl 3 ); FTIR (neat) 2938, 2913, 1700, 1406 cm -1 ; 1 H NMR (CDCl 3 ) δ 7.20 (d, 1 H, J=1.1 Hz), 7.11 (s, 4 H), 3.73 (m, 1 H), 3.59 (br d, 1 H, J=5.5 Hz), 3.20 (ddd, 1 H, J=14.2, 5.1, 5.1 Hz), 2.90 (br d, 1 H, J=5.1 Hz), 2.58 (d, 3 H, J=1.1 Hz), 2.41 (ddd, 1 H, J=14.2, 2.6, 2.6 Hz), 2.2-1.96 (m, 3 H), 1.76-1.50 (m, 4 H), 0.67 (t, 3 H, J=7.3 Hz); 13 C NMR (75.45 MHz, CDCl 3 ) δ 214.8, 141.5, 140.4, 135.6, 128.2, 7.5, 98.1, 56.2, 55.7, 53.4, 38.6, 36.3, 33.6, 29.3, 29.1, 27.6, 6.9; Anal. Calcd for C 19 H 24 NOI: C, 55.75; H, 5.91; N, 3.42. Found: C, 55.95; H, 6.00; N, 3.35.
|
Biologically active derivatives of the tropane ring system are provided which selectively bind either to the 5-HT or DA reuptake site, leading to compounds which have use for the treatment of clinical depression, attention deficit disorder, obesity and cocaine addiction.
| 0
|
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application Ser. No. 14/936,408, filed Nov. 9, 2015, which in turn is a continuation of U.S. patent application Ser. No. 13/703,875, filed Dec. 12, 2012 (now U.S. Pat. No. 9,224,403, issued Dec. 29, 2015), which in turn is the 371 National Stage of International Application No. PCT/EP2011/060555 having an international filing date of Jun. 23, 2011. PCT/EP2011/060555 claims priority to U.S. Provisional Patent Application No. 61/361,237, filed Jul. 2, 2010. The entire contents of U.S. Ser. No. 14/936,408, U.S. Ser. No. 13/703,875 (now U.S. Pat. No. 9,224,403), PCT/EP2011/060555 and U.S. 61/361,237 are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
[0002] The present invention generally relates to digital audio coding and more precisely to coding techniques for audio signals containing components of different characters.
BACKGROUND
[0003] A widespread class of coding method for audio signals containing speech or singing includes code excited linear prediction (CELP) applied in time alternation with different coding methods, including frequency-domain coding methods especially adapted for music or methods of a general nature, to account for variations in character between successive time periods of the audio signal. For example, a simplified Moving Pictures Experts Group (MPEG) Unified Speech and Audio Coding (USAC; see standard ISO/IEC 23003-3) decoder is operable in at least three decoding modes, Advanced Audio Coding (AAC; see standard ISO/IEC 13818-7), algebraic CELP (ACELP) and transform-coded excitation (TCX), as shown in the upper portion of accompanying FIG. 2 .
[0004] The various embodiments of CELP are adapted to the properties of the human organs of speech and, possibly, to the human auditory sense. As used in this application, CELP will refer to all possible embodiments and variants, including but not limited to ACELP, wide- and narrow-band CELP, SB-CELP (sub-band CELP), low- and high-rate CELP, RCELP (relaxed CELP), LD-CELP (low-delay CELP), CS-CELP (conjugate-structure CELP), CS-ACELP (conjugate-structure ACELP), PSI-CELP (pitch-synchronous innovation CELP) and VSELP (vector sum excited linear prediction). The principles of CELP are discussed by R. Schroeder and S. Atal in Proceedings of the IEEE International Conference on Acoustics, Speech, and Signal Processing ( ICASSP ), vol. 10, pp. 937-940, 1985, and some of its applications are described in references 25-29 cited in Chen and Gersho, IEEE Transactions on Speech and Audio Processing , vol. 3, no. 1, 1995. As further detailed in the former paper, a CELP decoder (or, analogously, a CELP speech synthesizer) may include a pitch predictor, which restores the periodic component of an encoded speech signal, and a pulse codebook, from which an innovation sequence is added. The pitch predictor may in turn include a long-delay predictor for restoring the pitch and a short-delay predictor for restoring formants by spectral envelope shaping. In this context, the pitch is generally understood as the fundamental frequency of the tonal sound component produced by the vocal chords and further coloured by resonating portions of the vocal tract. This frequency together with its harmonics will dominate speech or singing. Generally speaking, CELP methods are best suited for processing solo or one-part singing, for which the pitch frequency is well-defined and relatively easy to determine.
[0005] To improve the perceived quality of CELP-coded speech, it is common practice to combine it with post filtering (or pitch enhancement by another term). U.S. Pat. No. 4,969,192 and section II of the paper by Chen and Gersho disclose desirable properties of such post filters, namely their ability to suppress noise components located between the harmonics of the detected voice pitch (long-term portion; see section IV). It is believed that an important portion of this noise stems from the spectral envelope shaping. The long-term portion of a simple post filter may be designed to have the following transfer function:
[0000]
H
E
(
z
)
=
1
+
α
(
z
T
+
z
-
T
2
-
1
)
,
[0000] where T is an estimated pitch period in terms of number of samples and a is a gain of the post filter, as shown in FIGS. 1 and 2 . In a manner similar to a comb filter, such a filter attenuates frequencies 1/(2T), 3/(2T), 5/(2T), . . . , which are located midway between harmonics of the pitch frequency, and adjacent frequencies. The attenuation depends on the value of the gain α. Slightly more sophisticated post filters apply this attenuation only to low frequencies—hence the commonly used term bass post filter—where the noise is most perceptible. This can be expressed by cascading the transfer function H E described above and a low-pass filter H LP . Thus, the post-processed decoded S E provided by the post filter will be given, in the transform domain, by
[0000]
S
E
(
z
)
=
S
(
z
)
-
α
S
(
z
)
P
LT
(
z
)
H
LP
(
z
)
,
where
P
LT
(
z
)
=
1
-
z
T
+
z
-
T
2
[0000] and S is the decoded signal which is supplied as input to the post filter. FIG. 3 shows an embodiment of a post filter with these characteristics, which is further discussed in section 6.1.3 of the Technical Specification ETSI TS 126 290, version 6.3.0, release 6. As this figure suggests, the pitch information is encoded as a parameter in the bit stream signal and is retrieved by a pitch tracking module communicatively connected to the long-term prediction filter carrying out the operations expressed by P LT .
[0006] The long-term portion described in the previous paragraph may be used alone. Alternatively, it is arranged in series with a noise-shaping filter that preserves components in frequency intervals corresponding to the formants and attenuates noise in other spectral regions (short-term portion; see section III), that is, in the ‘spectral valleys’ of the formant envelope. As another possible variation, this filter aggregate is further supplemented by a gradual high-pass-type filter to reduce a perceived deterioration due to spectral tilt of the short-term portion.
[0007] Audio signals containing a mixture of components of different origins—e.g., tonal, non-tonal, vocal, instrumental, non-musical—are not always reproduced by available digital coding technologies in a satisfactory manner. It has more precisely been noted that available technologies are deficient in handling such non-homogeneous audio material, generally favouring one of the components to the detriment of the other. In particular, music containing singing accompanied by one or more instruments or choir parts which has been encoded by methods of the nature described above, will often be decoded with perceptible artefacts spoiling part of the listening experience.
SUMMARY OF THE INVENTION
[0008] In order to mitigate at least some of the drawbacks outlined in the previous section, it is an object of the present invention to provide methods and devices adapted for audio encoding and decoding of signals containing a mixture of components of different origins. As particular objects, the invention seeks to provide such methods and devices that are suitable from the point of view of coding efficiency or (perceived) reproduction fidelity or both.
[0009] The invention achieves at least one of these objects by providing an encoder system, a decoder system, an encoding method, a decoding method and computer program products for carrying out each of the methods, as defined in the independent claims. The dependent claims define embodiments of the invention.
[0010] The inventors have realized that some artefacts perceived in decoded audio signals of non-homogeneous origin derive from an inappropriate switching between several coding modes of which at least one includes post filtering at the decoder and at least one does not. More precisely, available post filters remove not only interharmonic noise (and, where applicable, noise in spectral valleys) but also signal components representing instrumental or vocal accompaniment and other material of a ‘desirable’ nature. The fact that the just noticeable difference in spectral valleys may be as large as 10 dB (as noted by Ghitza and Goldstein, IEEE Trans. Acoust., Speech, Signal Processing , vol. ASSP-4, pp. 697-708, 1986) may have been taken as a justification by many designers to filter these frequency bands severely. The quality degradation by the interharmonic (and spectral-valley) attenuation itself may however be less important than that of the switching occasions. When the post filter is switched on, the background of a singing voice sounds suddenly muffled, and when the filter is deactivated, the background instantly becomes more sonorous. If the switching takes place frequently, due to the nature of the audio signal or to the configuration of the coding device, there will be a switching artefact. As one example, a USAC decoder may be operable either in an ACELP mode combined with post filtering or in a TCX mode without post filtering. The ACELP mode is used in episodes where a dominant vocal component is present. Thus, the switching into the ACELP mode may be triggered by the onset of singing, such as at the beginning of a new musical phrase, at the beginning of a new verse, or simply after an episode where the accompaniment is deemed to drown the singing voice in the sense that the vocal component is no longer prominent. Experiments have confirmed that an alternative solution, or rather circumvention of the problem, by which TCX coding is used throughout (and the ACELP mode is disabled) does not remedy the problem, as reverb-like artefacts appear.
[0011] Accordingly, in a first and a second aspect, the invention provides an audio encoding method (and an audio encoding system with the corresponding features) characterized by a decision being made as to whether the device which will decode the bit stream, which is output by the encoding method, should apply post filtering including attenuation of interharmonic noise. The outcome of the decision is encoded in the bit stream and is accessible to the decoding device.
[0012] By the invention, the decision whether to use the post filter is taken separately from the decision as to the most suitable coding mode. This makes it possible to maintain one post filtering status throughout a period of such length that the switching will not annoy the listener. Thus, the encoding method may prescribe that the post filter will be kept inactive even though it switches into a coding mode where the filter is conventionally active.
[0013] It is noted that the decision whether to apply post filtering is normally taken frame-wise. Thus, firstly, post filtering is not applied for less than one frame at a time. Secondly, the decision whether to disable post filtering is only valid for the duration of a current frame and may be either maintained or reassessed for the subsequent frame. In a coding format enabling a main frame format and a reduced format, which is a fraction of the normal format, e.g., ⅛ of its length, it may not be necessary to take post-filtering decisions for individual reduced frames. Instead, a number of reduced frames summing up to a normal frame may be considered, and the parameters relevant for the filtering decision may be obtained by computing the mean or median of the reduced frames comprised therein.
[0014] In a third and a fourth aspect of the invention, there is provided an audio decoding method (and an audio decoding system with corresponding features) with a decoding step followed by a post-filtering step, which includes interharmonic noise attenuation, and being characterized in a step of disabling the post filter in accordance with post filtering information encoded in the bit stream signal.
[0015] A decoding method with these characteristics is well suited for coding of mixed-origin audio signals by virtue of its capability to deactivate the post filter in dependence of the post filtering information only, hence independently of factors such as the current coding mode. When applied to coding techniques wherein post filter activity is conventionally associated with particular coding modes, the post-filtering disabling capability enables a new operative mode, namely the unfiltered application of a conventionally filtered decoding mode.
[0016] In a further aspect, the invention also provides a computer program product for performing one of the above methods. Further still, the invention provides a post filter for attenuating interharmonic noise which is operable in either an active mode or a pass-through mode, as indicated by a post-filtering signal supplied to the post filter. The post filter may include a decision section for autonomously controlling the post filtering activity.
[0017] As the skilled person will appreciate, an encoder adapted to cooperate with a decoder is equipped with functionally equivalent modules, so as to enable faithful reproduction of the encoded signal. Such equivalent modules may be identical or similar modules or modules having identical or similar transfer characteristics. In particular, the modules in the encoder and decoder, respectively, may be similar or dissimilar processing units executing respective computer programs that perform equivalent sets of mathematical operations.
[0018] In one embodiment, encoding the present method includes decision making as to whether a post filter which further includes attenuation of spectral valleys (with respect to the formant envelope, see above). This corresponds to the short-term portion of the post filter. It is then advantageous to adapt the criterion on which the decision is based to the nature of the post filter.
[0019] One embodiment is directed to an encoder particularly adapted for speech coding. As some of the problems motivating the invention have been observed when a mixture of vocal and other components is coded, the combination of speech coding and the independent decision-making regarding post filtering afforded by the invention is particularly advantageous. In particular, such a decoder may include a code-excited linear prediction encoding module.
[0020] In one embodiment, the encoder bases its decision on a detected simultaneous presence of a signal component with dominant fundamental frequency (pitch) and another signal component located below the fundamental frequency. The detection may also be aimed at finding the co-occurrence of a component with dominant fundamental frequency and another component with energy between the harmonics of this fundamental frequency. This is a situation wherein artefacts of the type under consideration are frequently encountered. Thus, if such simultaneous presence is established, the encoder will decide that post filtering is not suitable, which will be indicated accordingly by post filtering information contained in the bit stream.
[0021] One embodiment uses as its detection criterion the total signal power content in the audio time signal below a pitch frequency, possibly a pitch frequency estimated by a long-term prediction in the encoder. If this is greater than a predetermined threshold, it is considered that there are other relevant components than the pitch component (including harmonics), which will cause the post filter to be disabled.
[0022] In an encoder comprising a CELP module, use can be made of the fact that such a module estimates the pitch frequency of the audio time signal. Then, a further detection criterion is to check for energy content between or below the harmonics of this frequency, as described in more detail above.
[0023] As a further development of the preceding embodiment including a CELP module, the decision may include a comparison between an estimated power of the audio signal when CELP-coded (i.e., encoded and decoded) and an estimated power of the audio signal when CELP-coded and post-filtered. If the power difference is larger than a threshold, which may indicate that a relevant, non-noise component of the signal will be lost, and the encoder will decide to disable the post filter.
[0024] In an advantageous embodiment, the encoder comprises a CELP module and a TCX module. As is known in the art, TCX coding is advantageous in respect of certain kinds of signals, notably non-vocal signals. It is not common practice to apply post-filtering to a TCX-coded signal. Thus, the encoder may select either TCX coding, CELP coding with post filtering or CELP coding without post filtering, thereby covering a considerable range of signal types.
[0025] As one further development of the preceding embodiment, the decision between the three coding modes is taken on the basis of a rate-distortion criterion, that is, applying an optimization procedure known per se in the art.
[0026] In another further development of the preceding embodiment, the encoder further comprises an Advanced Audio Coding (AAC) coder, which is also known to be particularly suitable for certain types of signals. Preferably, the decision whether to apply AAC (frequency-domain) coding is made separately from the decision as to which of the other (linear-prediction) modes to use. Thus, the encoder can be apprehended as being operable in two super-modes, AAC or TCX/CELP, in the latter of which the encoder will select between TCX, post-filtered CELP or non-filtered CELP. This embodiment enables processing of an even wider range of audio signal types.
[0027] In one embodiment, the encoder can decide that a post filtering at decoding is to be applied gradually, that is, with gradually increasing gain. Likewise, it may decide that post filtering is to be removed gradually. Such gradual application and removal makes switching between regimes with and without post filtering less perceptible. As one example, a singing episode, for which post-filtered CELP coding is found to be suitable, may be preceded by an instrumental episode, wherein TCX coding is optimal; a decoder according to the invention may then apply post filtering gradually at or near the beginning of the singing episode, so that the benefits of post filtering are preserved even though annoying switching artefacts are avoided.
[0028] In one embodiment, the decision as to whether post filtering is to be applied is based on an approximate difference signal, which approximates that signal component which is to be removed from a future decoded signal by the post filter. As one option, the approximate difference signal is computed as the difference between the audio time signal and the audio time signal when subjected to (simulated) post filtering. As another option, an encoding section extracts an intermediate decoded signal, whereby the approximate difference signal can be computed as the difference between the audio time signal and the intermediate decoded signal when subjected to post filtering. The intermediate decoded signal may be stored in a long-term prediction buffer of the encoder. It may further represent the excitation of the signal, implying that further synthesis filtering (vocal tract, resonances) would need to be applied to obtain the final decoded signal. The point in using an intermediate decoded signal is that it captures some of the particularities, notably weaknesses, of the coding method, thereby allowing a more realistic estimation of the effect of the post filter. As a third option, a decoding section extracts an intermediate decoded signal, whereby the approximate difference signal can be computed as the difference between the intermediate decoded signal and the intermediate decoded signal when subjected to post filtering. This procedure probably gives a less reliable estimation than the two first options, but can on the other hand be carried out by the decoder in a standalone fashion.
[0029] The approximate difference signal thus obtained is then assessed with respect to one of the following criteria, which when settled in the affirmative will lead to a decision to disable the post filter:
[0030] a) whether the power of the approximate difference signal exceeds a predetermined threshold, indicating that a significant part of the signal would be removed by the post filter;
[0031] b) whether the character of the approximate difference signal is rather tonal than noise-like;
[0032] c) whether a difference between magnitude frequency spectra of the approximate difference signal and of the audio time signal is unevenly distributed with respect to frequency, suggesting that it is not noise but rather a signal that would make sense to a human listener;
[0033] d) whether a magnitude frequency spectrum of the approximate difference signal is localized to frequency intervals within a predetermined relevance envelope, based on what can usually be expected from a signal of the type to be processed; and
[0034] e) whether a magnitude frequency spectrum of the approximate difference signal is localized to frequency intervals within a relevance envelope obtained by thresholding a magnitude frequency spectrum of the audio time signal by a magnitude of the largest signal component therein downscaled by a predetermined scale factor.
[0000] When evaluating criterion e), it is advantageous to apply peak tracking in the magnitude spectrum, that is, to distinguish portions having peak-like shapes normally associated with tonal components rather than noise. Components identified by peak tracking, which may take place by some algorithm known per se in the art, may be further sorted by applying a threshold to the peak height, whereby the remaining components are tonal material of a certain magnitude. Such components usually represent relevant signal content rather than noise, which motivates a decision to disable the post filter.
[0035] In one embodiment of the invention as a decoder, the decision to disable the post filter is executed by a switch controllable by the control section and capable of bypassing the post filter in the circuit. In another embodiment, the post filter has variable gain controllable by the control section, or a gain controller therein, wherein the decision to disable is carried out by setting the post filter gain (see previous section) to zero or by setting its absolute value below a predetermined threshold.
[0036] In one embodiment, decoding according to the present invention includes extracting post filtering information from the bit stream signal which is being decoded. More precisely, the post filtering information may be encoded in a data field comprising at least one bit in a format suitable for transmission. Advantageously, the data field is an existing field defined by an applicable standard but not in use, so that the post filtering information does not increase the payload to be transmitted.
[0037] In other embodiments, an audio decoder for decoding an encoded audio bitstream is disclosed. The audio decoder is capable of being operated in at least three different decoding modes. The audio decoder includes a demultiplexer for obtaining audio data and control information from the encoded audio bitstream. The audio decoder also includes a first audio decoder configured to operate in a first decoding mode using a first decoding technique and a second audio decoder configured to operate in a second decoding mode using a second decoding technique. The second decoding technique is different from the first decoding technique. The audio decoder also includes a pitch predictor integrated into the second audio decoder. The pitch predictor includes a long-term prediction filter and a short-term prediction filter. The audio decoder further includes a selector for selecting one of the at least three different decoding modes based on at least some of the control information. Lastly, the audio decoder includes an output interface for outputting a decoded audio signal. The decoded audio signal is processed at least in part by the first audio decoder or the second audio decoder.
[0038] It is noted that the methods and apparatus disclosed in this section may be applied, after appropriate modifications within the skilled person's abilities including routine experimentation, to coding of signals having several components, possibly corresponding to different channels, such as stereo channels. Throughout the present application, pitch enhancement and post filtering are used as synonyms. It is further noted that AAC is discussed as a representative example of frequency-domain coding methods. Indeed, applying the invention to a decoder or encoder operable in a frequency-domain coding mode other than AAC will only require small modifications, if any, within the skilled person's abilities. Similarly, TCX is mentioned as an example of weighted linear prediction transform coding and of transform coding in general.
[0039] Features from two or more embodiments described hereinabove can be combined, unless they are clearly complementary, in further embodiments. The fact that two features are recited in different claims does not preclude that they can be combined to advantage. Likewise, further embodiments can also be provided by the omission of certain features that are not necessary or not essential for the desired purpose.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] Embodiments of the present invention will now be described with reference to the accompanying drawings, on which:
[0041] FIG. 1 is a block diagram showing a conventional decoder with post filter;
[0042] FIG. 2 is a schematic block diagram of a conventional decoder operable in AAC, ACELP and TCX mode and including a post filter permanently connected downstream of the ACELP module;
[0043] FIG. 3 is a block diagram illustrating the structure of a post filter;
[0044] FIGS. 4 and 5 are block diagrams of two decoders according to the invention;
[0045] FIGS. 6 and 7 are block diagrams illustrating differences between a conventional decoder ( FIG. 6 ) and a decoder ( FIG. 7 ) according to the invention;
[0046] FIG. 8 is a block diagram of an encoder according to the invention;
[0047] FIGS. 9 and 10 are a block diagrams illustrating differences between a conventional decoder ( FIG. 9 ) and a decoder ( FIG. 10 ) according to the invention; and
[0048] FIG. 11 is a block diagram of an autonomous post filter which can be selectively activated and deactivated.
DETAILED DESCRIPTION OF EMBODIMENTS
[0049] FIG. 4 is a schematic drawing of a decoder system 400 according to an embodiment of the invention, having as its input a bit stream signal and as its output an audio signal. As in the conventional decoders shown in FIG. 1 , a post filter 440 is arranged downstream of a decoding module 410 but can be switched into or out of the decoding path by operating a switch 442 . The post filter is enabled in the switch position shown in the figure. It would be disabled if the switch was set in the opposite position, whereby the signal from the decoding module 410 would instead be conducted over the bypass line 444 . As an inventive contribution, the switch 442 is controllable by post filtering information contained in the bit stream signal, so that post filtering may be applied and removed irrespectively of the current status of the decoding module 410 . Because a post filter 440 operates at some delay—for example, the post filter shown in FIG. 3 will introduce a delay amounting to at least the pitch period T—a compensation delay module 443 is arranged on the bypass line 444 to maintain the modules in a synchronized condition at switching. The delay module 443 delays the signal by the same period as the post filter 440 would, but does not otherwise process the signal. To minimize the change-over time, the compensation delay module 443 receives the same signal as the post filter 440 at all times. In an alternative embodiment where the post filter 440 is replaced by a zero-delay post filter (e.g., a causal filter, such as a filter with two taps, independent of future signal values), the compensation delay module 443 can be omitted.
[0050] FIG. 5 illustrates a further development according to the teachings of the invention of the triple-mode decoder system 500 of FIG. 2 . An ACELP decoding module 511 is arranged in parallel with a TCX decoding module 512 and an AAC decoding module 513 . In series with the ACELP decoding module 511 is arranged a post filter 540 for attenuating noise, particularly noise located between harmonics of a pitch frequency directly or indirectly derivable from the bit stream signal for which the decoder system 500 is adapted. The bit stream signal also encodes post filtering information governing the positions of an upper switch 541 operable to switch the post filter 540 out of the processing path and replace it with a compensation delay 543 like in FIG. 4 . A lower switch 542 is used for switching between different decoding modes. With this structure, the position of the upper switch 541 is immaterial when one of the TCX or AAC modules 512 , 513 is used; hence, the post filtering information does not necessary indicate this position except in the ACELP mode. Whatever decoding mode is currently used, the signal is supplied from the downstream connection point of the lower switch 542 to a spectral band replication (SBR) module 550 , which outputs an audio signal. The skilled person will realize that the drawing is of a conceptual nature, as is clear notably from the switches which are shown schematically as separate physical entities with movable contacting means. In a possible realistic implementation of the decoder system, the switches as well as the other modules will be embodied by computer-readable instructions.
[0051] FIGS. 6 and 7 are also block diagrams of two triple-mode decoder systems operable in an ACELP, TCX or frequency-domain decoding mode. With reference to the latter figure, which shows an embodiment of the invention, a bit stream signal is supplied to an input point 701 , which is in turn permanently connected via respective branches to the three decoding modules 711 , 712 , 713 . The input point 701 also has a connecting branch 702 (not present in the conventional decoding system of FIG. 6 ) to a pitch enhancement module 740 , which acts as a post filter of the general type described above. As is common practice in the art, a first transition windowing module 703 is arranged downstream of the ACELP and TCX modules 711 , 712 , to carry out transitions between the decoding modules. A second transition module 704 is arranged downstream of the frequency-domain decoding module 713 and the first transition windowing module 703 , to carry out transition between the two super-modes. Further a SBR module 750 is provided immediately upstream of the output point 705 . Clearly, the bit stream signal is supplied directly (or after demultiplexing, as appropriate) to all three decoding modules 711 , 712 , 713 and to the pitch enhancement module 740 . Information contained in the bit stream controls what decoding module is to be active. By the invention however, the pitch enhancement module 740 performs an analogous self actuation, which responsive to post filtering information in the bit stream may act as a post filter or simply as a pass-through. This may for instance be realized through the provision of a control section (not shown) in the pitch enhancement module 740 , by means of which the post filtering action can be turned on or off. The pitch enhancement module 740 is always in its pass-through mode when the decoder system operates in the frequency-domain or TCX decoding mode, wherein strictly speaking no post filtering information is necessary. It is understood that modules not forming part of the inventive contribution and whose presence is obvious to the skilled person, e.g., a demultiplexer, have been omitted from FIG. 7 and other similar drawings to increase clarity.
[0052] As a variation, the decoder system of FIG. 7 may be equipped with a control module (not shown) for deciding whether post filtering is to be applied using an analysis-by-synthesis approach. Such control module is communicatively connected to the pitch enhancement module 740 and to the ACELP module 711 , from which it extracts an intermediate decoded signal s i _ DEC (n) representing an intermediate stage in the decoding process, preferably one corresponding to the excitation of the signal. The detection module has the necessary information to simulate the action of the pitch enhancement module 740 , as defined by the transfer functions P LT (z) and H LP (z) (cf. Background section and FIG. 3 ), or equivalently their filter impulse responses p LT (z) and h LP (n). As follows by the discussion in the Background section, the component to be subtracted at post filtering can be estimated by an approximate difference signal s AD (n) which is proportional to [(s i _ DEC *p LT )*h LP ](n), where * denotes discrete convolution. This is an approximation of the true difference between the original audio signal and the post-filtered decoded signal, namely
[0000] s ORIG ( n )− s E ( n )= s ORIG ( n )−( s DEC ( n )−α[ s DEC *P LT *h LP ]( n )),
[0000] where α is the post filter gain. By studying the total energy, low-band energy, tonality, actual magnitude spectrum or past magnitude spectra of this signal, as disclosed in the Summary section and the claims, the control section may find a basis for the decision whether to activate or deactivate the pitch enhancement module 740 .
[0053] FIG. 8 shows an encoder system 800 according to an embodiment of the invention. The encoder system 800 is adapted to process digital audio signals, which are generally obtained by capturing a sound wave by a microphone and transducing the wave into an analog electric signal. The electric signal is then sampled into a digital signal susceptible to be provided, in a suitable format, to the encoder system 800 . The system generally consists of an encoding module 810 , a decision module 820 and a multiplexer 830 . By virtue of switches 814 , 815 (symbolically represented), the encoding module 810 is operable in either a CELP, a TCX or an AAC mode, by selectively activating modules 811 , 812 , 813 . The decision module 820 applies one or more predefined criteria to decide whether to disable post filtering during decoding of a bit stream signal produced by the encoder system 800 to encode an audio signal. For this purpose, the decision module 820 may examine the audio signal directly or may receive data from the encoding module 810 via a connection line 816 . A signal indicative of the decision taken by the decision module 820 is provided, together with the encoded audio signal from the encoding module 810 , to a multiplexer 830 , which concatenates the signals into a bit stream constituting the output of the encoder system 800 .
[0054] Preferably, the decision module 820 bases its decision on an approximate difference signal computed from an intermediate decoded signal s i _ DEC , which can be subtracted from the encoding module 810 . The intermediate decoded signal represents an intermediate stage in the decoding process, as discussed in preceding paragraphs, but may be extracted from a corresponding stage of the encoding process. However, in the encoder system 800 the original audio signal s ORIG is available so that, advantageously, the approximate difference signal is formed as:
[0000] s ORIG ( n )−( s i _ DEC ( n )−α[( s i _ DEC *p LT )* h LP ]( n )).
[0000] The approximation resides in the fact that the intermediate decoded signal is used in lieu of the final decoded signal. This enables an appraisal of the nature of the component that a post filter would remove at decoding, and by applying one of the criteria discussed in the Summary section, the decision module 820 will be able to take a decision whether to disable post filtering.
[0055] As a variation to this, the decision module 820 may use the original signal in place of an intermediate decoded signal, so that the approximate difference signal will be [(s i _ DEC *p LT )*h LP ](n). This is likely to be a less faithful approximation but on the other hand makes the presence of a connection line 816 between the decision module 820 and the encoding module 810 optional.
[0056] In such other variations of this embodiment where the decision module 820 studies the audio signal directly, one or more of the following criteria may be applied:
Does the audio signal contain both a component with dominant fundamental frequency and a component located below the fundamental frequency? (The fundamental frequency may be supplied as a by-product of the encoding module 810 .) Does the audio signal contain both a component with dominant fundamental frequency and a component located between the harmonics of the fundamental frequency? Does the audio signal contain significant signal energy below the fundamental frequency? Is post-filtered decoding (likely to be) preferable to unfiltered decoding with respect to rate-distortion optimality?
[0061] In all the described variations of the encoder structure shown in FIG. 8 —that is, irrespectively of the basis of the detection criterion—the decision section 820 may be enabled to decide on a gradual onset or gradual removal of post filtering, so as to achieve smooth transitions. The gradual onset and removal may be controlled by adjusting the post filter gain.
[0062] FIG. 9 shows a conventional decoder operable in a frequency-decoding mode and a CELP decoding mode depending on the bit stream signal supplied to the decoder. Post filtering is applied whenever the CELP decoding mode is selected. An improvement of this decoder is illustrated in FIG. 10 , which shows a decoder 1000 according to an embodiment of the invention. This decoder is operable not only in a frequency-domain-based decoding mode, wherein the frequency-domain decoding module 1013 is active, and a filtered CELP decoding mode, wherein the CELP decoding module 1011 and the post filter 1040 are active, but also in an unfiltered CELP mode, in which the CELP module 1011 supplies its signal to a compensation delay module 1043 via a bypass line 1044 . A switch 1042 controls what decoding mode is currently used responsive to post filtering information contained in the bit stream signal provided to the decoder 1000 . In this decoder and that of FIG. 9 , the last processing step is effected by an SBR module 1050 , from which the final audio signal is output.
[0063] FIG. 11 shows a post filter 1100 suitable to be arranged downstream of a decoder 1199 . The filter 1100 includes a post filtering module 1140 , which is enabled or disabled by a control module (not shown), notably a binary or non-binary gain controller, in response to a post filtering signal received from a decision module 1120 within the post filter 1100 . The decision module performs one or more tests on the signal obtained from the decoder to arrive at a decision whether the post filtering module 1140 is to be active or inactive. The decision may be taken along the lines of the functionality of the decision module 820 in FIG. 8 , which uses the original signal and/or an intermediate decoded signal to predict the action of the post filter. The decision of the decision module 1120 may also be based on similar information as the decision modules uses in those embodiments where an intermediate decoded signal is formed. As one example, the decision module 1120 may estimate a pitch frequency (unless this is readily extractable from the bit stream signal) and compute the energy content in the signal below the pitch frequency and between its harmonics. If this energy content is significant, it probably represents a relevant signal component rather than noise, which motivates a decision to disable the post filtering module 1140 .
[0064] A 6-person listening test has been carried out, during which music samples encoded and decoded according to the invention were compared with reference samples containing the same music coded while applying post filtering in the conventional fashion but maintaining all other parameters unchanged. The results confirm a perceived quality improvement.
[0065] Further embodiments of the present invention will become apparent to a person skilled in the art after reading the description above. Even though the present description and drawings disclose embodiments and examples, the invention is not restricted to these specific examples. Numerous modifications and variations can be made without departing from the scope of the present invention, which is defined by the accompanying claims.
[0066] The systems and methods disclosed hereinabove may be implemented as software, firmware, hardware or a combination thereof. Certain components or all components may be implemented as software executed by a digital signal processor or microprocessor, or be implemented as hardware or as an application-specific integrated circuit. Such software may be distributed on computer readable media, which may comprise computer storage media (or non-transitory media) and communication media (or transitory media). As is well known to a person skilled in the art, computer storage media includes both volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer readable instructions, data structures, program modules or other data. Computer storage media includes, but is not limited to, RAM, ROM, EEPROM, flash memory or other memory technology, CD-ROM, digital versatile disks (DVD) or other optical disk storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to store the desired information and which can be accessed by a computer. Further, it is well known to the skilled person that communication media typically embodies computer readable instructions, data structures, program modules or other data in a modulated data signal such as a carrier wave or other transport mechanism and includes any information delivery media.
|
In one embodiment, an audio decoder for decoding an encoded audio bitstream is disclosed. The audio decoder is capable of being operated in at least three different decoding modes. The audio decoder includes a demultiplexer for obtaining audio data and control information from the encoded audio bitstream. The audio decoder also includes a first audio decoder configured to operate in a first decoding mode using a first decoding technique and a second audio decoder configured to operate in a second decoding mode using a second decoding technique. The audio decoder also includes a pitch predictor integrated into the second audio decoder. The pitch predictor includes a long-term prediction filter and a short-term prediction filter. The audio decoder further includes a selector for selecting one of the at least three different decoding modes based on at least some of the control information.
| 6
|
Subsets and Splits
No community queries yet
The top public SQL queries from the community will appear here once available.