The present application relates to novel opioid receptor antagonists and agonists, methods of making these compounds, and methods of use thereof.

1. Field of the Invention
The present invention relates to novel opioid receptor antagonists and agonists, methods of making these compounds, and methods of use.
2. Description of the Background
The opioid receptor system has been extensively studied over the past eight decades, driven primarily by a search for analgesics that do not possess the abuse potential associated with morphine. While these studies were unsuccessful, our understanding of the opioid system has increased tremendously. A significant breakthrough in our understanding of this system came about as a realization that the pharmacology of opioids is receptor based. From this vantage point, the focus of research turned to identifying receptor subtypes with the ultimate goal of assigning specific physiological function to individual receptors. Today, the receptor system is known to be composed of the three distinct subtypes OP1, OP2, and OP3 (delta, kappa and mu), as each of these have been cloned and been shown to derive from three different chromosomes. For a discussion of opioid receptors, see Kirk-Othmer Encyclopedia of Chemical Technology, Volume 17, Fourth Edition, 1996, pp. 858-881. There is however less however as to the number of subtypes within each of the main branches and while much has been learned along these lines, the process of assigning function to subtypes is still an area of active investigation.
The opioid receptor system has been extensively studied over the past eight decades driven primarily by a search for analgesics that do not possess the abuse potential associated with morphine. While this effort has been unsuccessful to date, recent studies have highlighted the delta opioid receptor system as holding the greatest potential for success. Principally, agonists acting through the delta opioid receptor have been shown to modulate pain while minimizing many of the side-effects associated with morphine which acts primarily at the mu opioid receptor. These unwanted side-effects include physical dependence, respiratory depression, and gastrointestinal motility problems. These findings have led to a dramatic increase in the research efforts directed toward the production of potent, highly delta receptor selective agonists. The bulk of this effort has been in discovering small molecules as opposed to peptides due to their enhanced stability in vivo and their ability to penetrate the central nervous system.
The discovery of potent, highly receptor-selective opioid pure antagonists has been a goal of medicinal chemists for many years.1,2 As molecular probes, antagonists have served as useful tools in the study of both the structure as well as the physiological functions of the highly complex opioid receptor system. Much has been accomplished as evidenced by the elegant work of Portoghese and coworkers over the past decade which ultimately has led to the discovery of the naltrexone-based kappa and delta receptor subtype-selective antagonists norbinaltorphimine3 (1, nor-BNI) and naltrindole4 (2, NTI), respectively. Following Portoghese""s lead, workers at SmithKline Beecham recently reported that the octahydroisoquinoline (3, SB 205588) was a second-generation, highly potent and selective delta antagonist formally derived from naltrindole fragmentation.5 One specific research aim has been the discovery of opioid receptor selective reversibly binding ligands from the N-substituted (+)-(3R,4R)-dimethyl-4-(3-hydroxyphenyl)piperidine (4a) class of compounds that display pure antagonist activity.6 These compounds will be useful as molecular probes for the opioid receptor as well as potential drug candidates for the treatment of substance abuse and other CNS disorders.7 While mu antagonists have for years been used in drug abuse therapy, recent findings suggest that kappa antagonists could provide a more effective, long-lasting treatment strategy.8 A great variety of N-substituted derivatives of 4a has been prepared, but until the recent demonstration of mu selectivity for 5a,9 none had shown selectivity between the opioid receptor subtypes. Since the pure antagonist activity of these compounds is not dependent on the N-substituent, multiple changes to this part of the molecule would be expected to affect binding affinity and possibly receptor selectivity but not alter its fundamental antagonist character. This feature distinguishes this class of antagonist from the morphone-based compounds, which display pure antagonist behavior only with N-substituents such as allyl or cyclopropylmethyl but not methyl, ethyl, or phenethyl.10 It is currently believed that the N-substituent in 4a interacts with a lipophilic binding domain which has been described as either very large or quite malleable since a multitude of different types of N-substituent changes provided ligands displaying high binding affinity.11 It has also been determined that maximum potency and selectivity for the mu opioid receptor is achieved when the N-substituent incorporates a lipophilic entity (phenyl or cyclohexyl ring) separated from the piperidine nitrogen by three atoms as illustrated by compounds 5a-d.9,11 The synthesis of xcexa-selective compounds remains an important goal.
Derivatives of N-substituted (xc2x1)-trans-3,4-dimethyl-4-(3-hydroxyphenyl)piperidine, such as 6 and 7, are known to posses nonselective potent opioid pure antagonist activity.12-16 Early investigations of the phenylpiperidine class of opioid antagonists identified the 3-methyl substituent and its trans relative relationship to the 4-substituent as being both necessary and sufficient to impart antagonist activity to the agonist 4-(3-hydroxyphenyl)piperidine.12 This feature distinguished the phenylpiperidines from the oxymorphones which rely on particular N-substituents (i.e. allyl, cyclopropylmethyl) for expression of opioid antagonist activity.17 Further studies demonstrated that the N-substituent in the phenylpiperidine antagonists controls their potency and efficacy.15 Accordingly, there remains a need for compounds which have similar therapeutic effects as the trans-3,4-dimethyl-4-(3-hydroxyphenyl)piperidines, but are based on different structural elements.
Numerous structural types of opioid agonists have been discovered, and several such as methadone, meperidine, fentanyl, and pentazocine as well as others have become important drugs for the treatment of pain.10 However, there are only a few structural types that show potent, opioid pure antagonist activity.10,7 A resurgence in heroin use in recent years coupled with the demonstrated effectiveness of opioid antagonists for the treatment of other substances of abuse has spurred new interest in the development of novel antagonists for opioid receptors.16
The oxymorphone-related compounds such as naloxone (8a) and naltrexone (8b), where the antagonist activity is dependent upon the N-substituent, have received considerable attention over the past few decades.10 For example, pioneering studies by Portoghese and coworkers lead to the development of the prototypical kappa and delta opioid receptor antagonists, norbinaltorphimine (1, nor-BNI) and naltrindole (2, NTI). In contrast, the N-substituted trans-3,4-dimethyl-(3-hydroxyphenyl)piperidine (9a-d) class of pure antagonist has received relatively little attention. Studies with the N-methyl analog 9a as well as many other N-substituted analogs such as 9b, 9c (LY255582), and 9d showed that the pure antagonist activity was dependent on the 3-methyl substituent and its trans relative relationship to the 4-methyl substituent on the piperidine ring and, unlike the oxymorphone class, was independent of the nature of the N-substituent.7,16,17,6,13,14 Interestingly, the 3,4-dimethyl cis isomer 9e was found to be a mixed agonist-antagonist. May and coworkers18 reported that 2,9xcex1-dimethyl-5-(3-hydroxyphenyl)morphan (10a), which has the 9-methyl group in a configuration comparable to the cis-3,4-dimethyl-4-(3-hydroxyphenyl)piperidine (9e) with the 5-(3-hydroxyphenyl) group locked in an equatorial conformation relative to the piperidine ring in the morphan structure, was a weak but pure antagonist.
Neither 2,9xcex2-dimethyl-5-(3-hydroxyphenyl)morphan (10b) nor 2,4xcex2-dimethyl-5-(3-hydroxyphenyl)morphan (10g) have not been reported, due to a lack of synthetic accessibility to these structural isomers. Accordingly, the successful synthetic preparation of 2,9xcex2-morphans and 2,4xcex2-morphans remains an important goal of in the field opioid receptor-binding compounds.
In search of analgesics possessing a reduced side-effect profile relative to morphine, much effort has been expended towards finding opioids which operate via xcex4 or xcexa opioid receptors as opposed to the xcexc opioid receptor which meditates the actions of morphine and its congeners.10 BW373U86 (11)19 and SNC-80 (12)20 represent one class of opioid agonists discovered to be selective for the xcex4 opioid receptor. Due to the lack of a clear opioid message substructure (i.e., a tyramine component similar to the enkephalins), compounds 11 and 12 have been referred to as non-classical opioid ligands.5 The piperazine subunit of 11 and 12 is not commonly found in compounds showing activity at the opioid receptors. In contrast, piperidine ring compounds are found in many different classes of opioids.27 If the internal nitrogen atom in compounds 11 or 12 is transposed with the benzylic carbon, piperidine ring analogs such as 13 would be obtained. Even though there are common structural elements between structures 11 or 12 and 13, the expected difference between in basicity between the piperidinyl amino group of 11 or 12 and the di-phenyl substituted amine of 13 is sufficient such that it cannot be predicted whether similarity to suggest that 13 would interact with opioid receptors similar to 11 or 12. It is also interesting to note that compound 13 has some structural elements in common with cis-3-methylfentanyl (14),21,22 a non-classical opioid ligand selective for the mu opioid receptor. Accordingly, the preparation of compound 13 and related structures remains an important goal.
(1) Dhawan, B. N.; Cesselin, F.; Raghubir, R.; Reisine, T.; Bradley, P. B.; Portoghese, P. S.; Hamon, M. International Union of Pharmacology. XII. Classification of opioid receptors. Pharmacol. Rev. 1996, 48, 567-592.
(2) Martin, W. R. The evolution of concepts of opioid receptors. In The Opiate Receptors, Pasternak, G. W. Eds.; Humana Press Inc.: New Jersey, 1988, pp. 3-22.
(3) Portoghese, P. S.; Nagase, H.; Lipkowski, A. W.; Larson, D. L.; Takemori, A. E. Binaltorphimine-related bivalent ligands and their kappa opioid receptor antagonist selectivity [published erratum appears in J. Med. Chem. 1988 October;31(10):2056]. J. Med. Chem. 1988, 31, 836-841.
(4) Portoghese, P. S. An approach to the design of receptor-type-selective non-peptide antagonists of peptidergic receptors: xcex4 opioid antagonists. J. Med. Chem. 1991, 34(6), 1757-1762.
(5) Dondio, G.; Ronzoni, S.; Eggleston, D. S.; Artico, M.; Petrillo, P.; Petrone, G.; Visentin, L.; Farina, C.; Vecchietti, V.; Clarke, G. D. Discovery of a novel class of substituted pyrrolooctahydroisoquinolines as potent and selective xcex4 opioid agonists, based on an extension of the message-address concept. J. Med. Chem. 1997, 40, 3192-3198.
(6) Zimmerman, D. M.; Nickander, R.; Horng, J. S.; Wong, D. T. New structural concepts for narcotic antagonists defined in a 4-phenylpiperidine series. Nature 1978, 275, 332-334.
(7) Zimmerman, D. M.; Leander, J. D. Invited perspective, selective opioid receptor agonists and antagonists: Research tools and potential therapeutic agents. J. Med. Chem. 1990, 33, 895-902.
(8) Rothman, R. B.; Gorelick, D. A.; Eichmiller, P. R.; Hill, B. H.; Norbeck, J.; Liberto, J. G. An open-label study of a functional opioid kappa antagonist in the treatment of opioid dependence. In Problems of Drug Dependence, 1997. Proceedings of the 59th Annual Scientific Meeting, The College on Problems of Drug Dependence, Inc., Harris, L. S. Eds.; U. S. Department of Health and Human Services: Rockville, Md., 1997; Vol. 178, pp. 309.
(9) Thomas, J. B.; Mascarella, S. W.; Rothman, R. B.; Partilla, J. S.; Xu, H.; McCullough, K. B.; Dersch, C. M.; Cantrell, B. E.; Zimmerman, D. M.; Carroll, F. I. Investigation of the N-substituent conformation governing potency and xcexc receptor subtype-selectivity in (+)-(3R,4R)-dimethyl-4-(3-hydroxyphenyl)piperidine opioid antagonists. J. Med. Chem. 1998, 41(11), 1980-1990.
(10) Aldrich, J. V. Analgesics. In Burger""s Medicinal Chemistry and Drug Discovery, Wolff, M. E. Eds.; John Wiley and Sons, Inc.: 1996; Vol. 3: Therapeutic Agents.
(11) Mitch, C. H.; Leander, J. D.; Mendelsohn, L. G.; Shaw, W. N.; Wong, D. T.; Cantrell, B. E.; Johnson, B. G.; Reel, J. K.; Snoddy, J. D.; Takemori, A. E.; Zimmerman, D. M. 3,4-Dimethyl-4-(3-hydroxyphenyl)piperidines: Opioid antagonists with potent anorectant activity. J. Med. Chem. 1993, 36(20), 2842-2850.
(12) Zimmerman, D. M.; Smits, S.; Nickander, R. Further investigation of novel 3-methyl-4-phenylpiperidine narcotic antagonists. In Proceedings of the 40th Annual Scientific Meeting of the Committee on Problems of Drug Dependence, 1978, pp. 237-247.
(13) Zimmerman, D. M.; Smits, S. E.; Hynes, M. D.; Cantrell, B. E.; Leander, J. D.; Mendelsohn, L. G.; Nickander, R. Drug Alcohol Depend. 1985, 14, 381-402.
(14) Mitch, C. H.; Leander, J. D.; Mendelsohn, L. G.; Shaw, W. N.; Wong, D. T.; Zimmerman, D. M.; Gidda, S. J.; Cantrell, B. E.; Scoepp, D. D.; Johnson, B. G.; Leander, J. D. J. Med. Chem. 1994, 37, 2262-2265.
(15) Evans, D. A.; Mitch, C. H.; Thomas, R. C.; Zimmerman, D. M.; Robey, R. L. Application of metalated enamines to alkaloid synthesis. An expedient approach to the synthesis of morphine-based analgesics. J. Am. Chem. Soc. 1980, 102, 5955-5956.
(16) Kreek, M. J. Opiates, opioids and addiction. Mol. Psychiatry 1996, 1(3), 232-254.
(17) Zimmerman, D. M.; Gidda, J. S.; Cantrell, B. E.; Schoepp, D. D.; Johnson, B. G.; Leander, J. D. Discovery of a potent, peripherally selective trans-3,4-dimethyl-4-(3-hydroxyphenyl)piperidine opioid antagonist for the treatment of gastrointestinal motility disorders. J. Med. Chem. 1994, 37(15), 2262-2265.
(18) Awaya, H.; May, E. L.; Aceto, M. D.; Merz, H.; Rogers, M. E.; Harris, L. S. Racemic and optically active 2,9-dimethyl-5-(m-hydroxyphenyl)morphans and pharmacological comparison with the 9-demethyl homologues. J. Med. Chem. 1984, 27, 536-539.
(19) Chang, K. J.; Rigdon, G. C.; Howard, J. L.; McNutt, R. W. A novel potent and selective nonpeptidic delta opioid receptor agonist, BW373U86. J. Pharm. Exp. Ther. 1993, 267, 852-857.
(20) Calderon, S. N.; Rothman, R. B.; Porreca, F.; Flippen-Anderson, J. L.; McNutt, R. W.; Xu, H.; Smith, L. E.; Bilsky, E. J.; Davis, P.; Rice, K. C. Probes for narcotic receptor mediated phenomena. 19. Synthesis of (+)-4-[(xcex1R)-xcex1-(2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-methoxybenzyl]-N,N-diethylbenzamide (SNC-80): A highly selective, nonpeptide xcex4 opioid receptor agonist. J. Med. Chem. 1994, 37, 2125-2128.
(21) Van Bever, W. F.; Niemegeers, C. J. E.; Janssen, P. A. J. Synthetic analgesics. Synthesis and pharmacology of the diastereoisomers of N-(3-methyl-1-(2-phenylethyl)-4-piperidyl)-N-phenylpropanamide and N-(3-methyl-1-(1-methyl-2-phenylethyl)-4-piperidyl)-N-phenylpropanamide. J. Med. Chem. 1974, 17(10), 1047-1051.
(22) Xu, H.; Kim, C.-H.; Zhu, Y. C.; Weber, R. J.; Rice, K. C.; Rothman, R. B. (+)-cis-Methylfentanyl and its analogs bind pseudoirreversibly to the mu opioid binding site: Evidence for pseudoallosteric modulation. Neuropharmacology 1991, 30, 455-462.
It is an object of the present invention to provide novel compounds which bind to opioid receptors.
It is another object of the present invention to provide novel compounds which are opioid receptors antagonists that bind with high affinity.
It is another object of the present invention to provide novel opiates that are selective for the kappa receptor as compared to the delta and mu receptors.
It is another object of the present invention to provide novel opiates that are selective for the mu and kappa receptors as compared to the delta receptor.
It is another object of the present invention to provide novel opiates that are selective for the delta receptor as compared to the mu and kappa receptors.
It is another object of the present invention to provide novel opiates that are pure antagonists at the mu, delta and kappa receptors.
It is another object of the present invention to provide methods of making the novel compounds.
It is another object of the present invention to provide methods of treating a variety of disease states with the novel opiate compounds of the present invention.
The objects of the present invention may be accomplished with compounds represented by formula (I), or pharmaceutically acceptable salts thereof:
where
R1 is hydrogen, an alkyl group, an aryl group, or an aralkyl group;
R2 is hydrogen, an alkyl group, an aryl group, or an alkaryl group; and
R3 is
each X is, independently, halogen, xe2x80x94OH, xe2x80x94OR, an alkyl group, an aryl group, xe2x80x94NH2, xe2x80x94NHR, xe2x80x94N(R)2, xe2x80x94CF3, xe2x80x94CN or xe2x80x94C(O)NH2, xe2x80x94C(O)NHR, or xe2x80x94C(O)N(R)2;
each R is, independently, an alkyl group, an aryl group or an alkaryl group;
n is 0 or an integer from 1 to 5; and
Ra is hydrogen or an alkyl group.
The objects above may also be accomplished with compounds represented by formula
(II): or pharmaceutically acceptable salts thereof,
where
R1 is an alkyl group or aralkyl group; and
R3, R4, R5, R6 are each, independently, hydrogen, an alkyl group, xe2x80x94OH, xe2x80x94NH2, xe2x80x94NHR, xe2x80x94N(R)2, halogen, xe2x80x94OR, xe2x80x94CF3, xe2x80x94CN, xe2x80x94NO2, or xe2x80x94NHC(O)R;
each R is, independently, an alkyl group, an aryl group, or an alkaryl group; and
R7 is hydrogen or an alkyl group.
The objects of the present invention may be also accomplished with compounds represented by formula (III), or pharmaceutically acceptable salts thereof:
where
R1 is an alkyl group or an aralkyl group;
R2 is hydrogen, an alkyl group, an aralkyl group, xe2x95x90O, xe2x80x94NH2, xe2x80x94NHR, xe2x80x94N(R)2, xe2x80x94NHC(O)R, xe2x80x94NRC(O)R, xe2x80x94NHC(O)R5, or xe2x80x94NRC(O)R5;
R3 and R4 may be hydrogen or methyl, with the proviso that when R3 is methyl then R4 is hydrogen and when R3 is hydrogen then R4 is methyl;
each R is, independently, an alkyl group, an aryl group, or an alkaryl group; and
R5 is
each X is, independently, halogen, xe2x80x94OH, xe2x80x94OR, an alkyl group, an aryl group, xe2x80x94NH2, xe2x80x94NHR, xe2x80x94N(R)2, xe2x80x94CF3, xe2x80x94CN, xe2x80x94C(O)NH2, xe2x80x94C(O)NHR, or xe2x80x94C(O)N(R)2;
each R is, independently, an alkyl group, an aryl group, or an alkaryl group;
n is 0 or an integer from 1 to 5; and
Ra is hydrogen or an alkyl group.
The objects above may be accomplished with compounds represented by formula (IV), or pharmaceutically acceptable salts thereof:
where
Ra and Rb are each, independently, hydrogen or an alkyl group, or Ra and Rb, together, form a cycloalkyl group;
each X is, independently, an alkyl group;
O is a five- or six-membered aryl or heteroaryl group;
each Z is, independently, an alkyl group, xe2x80x94OH, xe2x80x94OR, halogen, xe2x80x94CF3, xe2x80x94CN, xe2x80x94NH2, xe2x80x94NHR, or xe2x80x94N(R)2;
each R is, independently, an alkyl group, an aryl group, or an alkaryl group;
each W is an alkyl group;
n is 0 or an integer from 1 to 4;
y is 0 or an integer from 1 to 5;
z is 0 an integer from 1 to 8; and
R5 is an alkyl group, alkenyl group, or aralkyl group.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings.

Opiate compounds, methods of making and methods of use


The invention is related to ionic compounds, derivatives of malononitrile, in which the anionic load has been displaced. An ionic compound disclosed by the invention includes an anionic portion combined with at least one cationic portion M+m in sufficient number to ensure overall electronic neutrality; the compound is further comprised of M as a hydroxonium, a nitrosonium NO+, an ammonium xe2x80x94NH4+, a metallic cation with the valence m, an organic cation with the valence m, or an organometallic cation with the valence m. The anionic portion corresponds to one of the formulas RDxe2x80x94Yxe2x80x94C(Cxe2x89xa1N)2xe2x88x92 or Zxe2x80x94C(Cxe2x89xa1N)2xe2x88x92 in which Z is an electroattractive group, RD is an organic radical, and Y is a carbonyl, a thiocarbonyl, a sulfonyl, a sulfinyl, or a phosphonyl. The compounds can be used notably for ionic conducting materials, electronic conducting materials, colorants, and the catalysis of various chemical reactions.

The present invention is concerned with ionic compounds derived from malononitrile in which the anionic charge is delocalized, and their uses.
It is known and particularly interesting to introduce ionic groups in organic molecules or polymers having various functions. Coulombic forces correspond, indeed, to the stronger interactions which are available at the molecular level, and the ionic groups modify in a very noted manner the molecules to which they are attached. Coloring materials which are made soluble in water by means of sulfonate or carboxylate functions may be mentioned.
However, the xe2x80x94CO2xe2x88x921/mMm+ or xe2x80x94SO3xe2x88x921/mMm+ groups of this type are not dissociated, and they cause no solubility in solvents except water or certain highly polar protic solvents such as light alcohols, which considerably restrict the scope of their use.
On the other hand, salts of the compounds [RFSO2xe2x80x94Nxe2x80x94SO2RF]xe2x88x921/mMm+ in which RF is a perfluorinated group and Mm+ is a cation of valence m+ which are soluble and are dissociated in ordinary aprotic media or solvating polymers, are known. It is however considered that the existence of two perfluoroalkylsulfonyl groups (in particular the existence of fluorine atoms on the a atom of carbon of each sulfonyl group) which exert an important attracting power on the electrons of the anionic charge, is a necessary condition to obtain properties of solubility and dissociation. For example, the pKa of the acid H[CF3SO2xe2x80x94Nxe2x80x94SO2CF3] is only 1.95, as compared to that of the non-fluorinated acid CH3SO3H (pKa=0.3) and is clearly inferior to that of the perfluorinated acid CF3SO3H (pKa less than xe2x88x929) because of the basic character of the central nitrogen atom.
Surprisingly, the inventors have found that the compounds containing ionic groups xe2x80x94C(CN)2xe2x88x92 have excellent properties of solubility and dissociation, even when they contain no highly electroattractive perfluorinated groups.
The present invention consequently aims at supplying a family of ionic compounds having a good solubility and a good dissociation, without requiring complex modifications of the starting molecule. The precursors of the molecules of the invention are for the most part industrial products and/or easily accessible. In addition, it should be noted that the absence, or at least the decrease of the perfluorinated fraction in the compounds of the invention, enables to reduce production costs of the compounds and consequently the cost of the resulting applications.
An object of the present invention is an ionic compound which is a derivative of malononitrile comprising an anionic part which is associated to at least one cationic part M+m in a sufficient number to provide for the electronic neutrality of the whole, characterized in that M is a hydroxonium, a nitrosonium NO+, an ammonium xe2x80x94NH4+, a metallic cation having a valency m, an organic cation having a valency m or an organometallic cation having a valency m, and in that the ionic part corresponds to one of the formulae RDxe2x80x94Yxe2x80x94C(Cxe2x89xa1N)2xe2x88x92 or Zxe2x80x94C(Cxe2x89xa1N)2xe2x88x92 in which:
Z represents an electroattractor radical having a Hammett parameter at least equal to that of a phenyl radical, selected from:
j) xe2x80x94CN, xe2x80x94NO2, xe2x80x94SCN, xe2x80x94N3, FSO2xe2x80x94, xe2x80x94CF3, Rxe2x80x2FCH2xe2x80x94 (Rxe2x80x2F being a perfluorinated radical, preferably CF3xe2x80x94), fluoroalkyloxy, fluoroalkylthioxy, fluoroalkenyloxy, fluoroalkenylthioxy radicals;
jj) radicals comprising one or more aromatic nuclei possibly containing at least one nitrogen, oxygen, sulfur or phosphorus atom, said nuclei possibly being condensed nuclei and/or said nuclei possibly carrying at least one substituent selected from halogens, xe2x80x94CN, xe2x80x94NO2, xe2x80x94SCN, xe2x80x94N3, CF2xe2x95x90CFxe2x80x94Oxe2x80x94, radicals RFxe2x80x94 and RFCH2xe2x80x94 in which RF is a perfluoroalkyl alkyl having 1 to 12 carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having at least one cationic ionophorous group and/or at least one anionic ionophorous group;
xe2x80x83with the proviso that one substituent Z may be a monovalent radical, a multivalent radical, or part of a multivalent radical (including a dendrimer) carrying at least one group xe2x80x94C(Cxe2x89xa1N)2, or a segment of a polymer;
Y represents a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfinyl group or a phosphonyl group and:
RD is a radical selected from:
a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic or heterocyclic radicals, including polycyclic radicals;
b) alkyl or alkenyl radicals comprising at least one functional ether, thioether, amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy;
c) aryl, arylalkyl, arylalkenyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or at least one substituent of the nucleus comprises heteroatoms such as nitrogen, oxygen, sulfur;
d) radicals comprising condensed aromatic cycles which possibly comprise at least one heteroatom selected from nitrogen, oxygen, sulfur;
e) halogenated or perhalogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl radicals, said radicals possibly comprising functional ether, thioether, imine, amine, carboxyl, carbonyl or hydroxy groups;
f) radicals RCC(Rxe2x80x2)(Rxe2x80x3)xe2x80x94Oxe2x80x94 in which RC is an alkyl perfluorinated radical and Rxe2x80x2 et Rxe2x80x3 are independently from one another a hydrogen atom or a radical such as defined in a), b), c) or d) above [for example CF3CH2Oxe2x80x94, (CF3)3COxe2x80x94, (CF3)2CHOxe2x80x94, CF3CH(C6H5)Oxe2x80x94, xe2x80x94CH2(CF2)2CH2xe2x80x94];
g) radicals (RB)2Nxe2x80x94, in which the radicals RB which are identical or different are such as defined in a), b), c), d) and e) above, one of the RB may be a halogen atom, or the two radicals RB together form a divalent radical which constitutes a cycle with N;
h) polymer radicals;
i) radicals having one or more cationic ionophorous groups and/or one or more anionic ionophorous groups;
xe2x80x83with the proviso that one substituent RD may be a monovalent radical, part of a multivalent radical carrying a plurality of xe2x80x94Yxe2x80x94Cxe2x88x92(Cxe2x89xa1N)2 groups or a segment of a polymer;
xe2x80x83with the proviso that when Y is a carbonyl and RD is a perfluoroalkyl radical having 1 to 3 carbon atoms, or when Z is xe2x80x94CN, M is different from an alkali metal.
According to an embodiment of the invention, the cation is a metallic cation selected from cations of alkali metals, cations of alkali-earth metals, cations of transition metals, cations of trivalent metals, cations of rare earths. By way of example, Na+, Li+, K+, Sm3+, La3+, Ho3+, Sc3+, Al3+, Y3+, Yb3+, Lu3+, Eu3+, may be mentioned.
The cation may also be an organometallic cation, such as a metallocenium. By way of example, the cations derived from ferrocene, titanocene, zirconocene, from an indenocenium or a metallocenium arene, cations of transition metals complexed with ligands of phosphine type possibly having a chirality, organometallic cations having one or more alkyl or aryl groups covalently fixed to an atom or a group of atoms, may be mentioned. Specific examples include methylzinc, phenylmercury, trialkyltin or trialkyllead, chloro[ethylene-bis(indenyl)] zirconium (IV) or tetrakis-(acetonitrile)palladium(II). The organo-metallic cation may be part of a polymer chain.
In a specific embodiment of the invention, the organic cation is an onium cation selected from the group consisting of R3O+(oxonium), NR4+(ammonium), RC(NHR2)2+(amidinium), C(NHR2)3+(guanidinium), C5R6N+(pyridinium), C3R5N2+(imidazolium), C3R7N2+(imidazolinium), C2R4N3+(triazolium), SR3+(sulfonium), PR4+(phosphonium), IR2+(iodonium), (C6R5)3C+(carbonium) cations. In a given onium cation, the radicals R may all be similar. However, an onium cation may also include radicals R which are different from one another. A radical R may be a H or it may be selected from the following radicals:
alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl radicals, dialkylamino radicals and dialkylazo radicals;
cyclic or heterocyclic radicals possibly comprising at least one lateral chain comprising heteroatoms such as nitrogen, oxygen, sulfur;
cyclic or heterocyclic radicals possibly comprising heteroatoms in the aromatic nucleus;
groups comprising a plurality of aromatic or heterocyclic nuclei, condensed or non-condensed, possibly containing at least one nitrogen, oxygen, sulfur or phosphorus atom.
When an onium cation carries at least two radicals R which are different from H, these radicals may together form a cycle which is aromatic or non-aromatic, possibly enclosing the center carrying the cationic charge.
When the cationic part of a compound of the invention is an onium cation, it may be either in the form of an independent cationic group which is bound to the cationic part only by the ionic bond between the positive charge of the cation and the negative charge of the anionic part. In this case, the cationic part may be part of a recurring unit of a polymer.
An onium cation may also be part of the radical Z or the radical RD carried by the anionic center. In this case, a compound of the invention constitutes a zwitterion. When the cation of a compound of the invention is an onium cation, it may be selected so as to introduce in the compound substituents enabling to give specific properties to said compound. For example, the cation M+ may be a cationic heterocycle with aromatic character, including at least one alkylated nitrogen atom in the cycle. By way of example, an imidazolium, a triazolium, a pyridinium, a 4-dimethyl-amino-pyridinium may be mentioned, said cations possibly carrying a substituent on the carbon atoms of the cycle. Among these cations, those in which the salts have a melting point lower than 150xc2x0 C., more particularly lower than 25xc2x0 C.
A compound of the invention in which the cation M is a group carrying a diazoic group having xe2x80x94Nxe2x95x90Nxe2x80x94, xe2x80x94Nxe2x95x90N+, a sulfonium group, an iodonium group, a phosphonium group or a substituted or non-substituted arene-ferrocenium cation, possibly incorporated in the polymeric network, is interesting inasmuch as it is activatable by a source of actinic energy of suitable wavelength. Specific examples of such compounds include those in which the cation is a diaryliodonium cation, a dialkylaryliodonium cation, a triarylsulfonium cation, a trialkylaryl sulfonium cation, or a substituted or non-substituted phenacyl-dialkyl sulfonium cation. The above cations may be part of a polymer chain.
The cation M of a compound of the invention may be an organic cation incorporating a group 2,2xe2x80x2[azobis(2-2xe2x80x2-imidazolinio-2-yl)propane]2+ or 2,2xe2x80x2-azobis(2-amidiniopropane)2+. The compound the invention is then particularly interesting as a free radical initiator, which is thermally activatable and non-volatile, soluble in polar organic solvents and in aprotic solvating monomers and polymers.
A specific family of compounds of the invention is the one which comprises a group RDYxe2x80x94. The compounds in which Y is xe2x80x94SO2xe2x80x94 or xe2x80x94COxe2x80x94 are especially preferred.
The choice of substituent RD enables to adjust the properties of a compound of the invention. In an embodiment, RD is selected from alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl having 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl or alkenylaryl radicals having 5 to 24 carbon atoms.
According to another embodiment, RD is selected from alkyl or alkenyl radicals having 1 to 12 carbon atoms and possibly comprising at least one heteroatom O, N or S in the main chain or in a lateral chain, and/or possibly carrying a hydroxy group, a carbonyl group, an amine group or a carboxyl group.
According to another embodiment, RD is selected from aryl, arylalkyl, alkylaryl or alkenylaryl radicals, in which the aromatic nuclei and/or their substituents comprise heteroatoms such as nitrogen, oxygen, sulfur.
Substituent RD may be a polymer radical, for example a poly(oxyalkylene) radical. A compound of the invention is then in the form of a polymer carrying an ionic group xe2x80x94Yxe2x80x94C(CN)2xe2x88x92, M+.
RD may be a recurring unit of a polymer, for example an oxyalkylene unit or a styrene unit. The compound of the invention is then in the form of a polymer in which at least part of the recurring units carry a lateral group on which an ionic group xe2x80x94Yxe2x80x94C(CN)2xe2x88x92, M+ is fixed. By way of example, there may be mentioned a poly(oxyalkylene) in which at least certain oxyalkylene units carry a substituent xe2x80x94Yxe2x80x94C(CN)2xe2x88x92, M+ or a polystyrene in which at least certain styrene units carry a substituent xe2x80x94Yxe2x80x94C(CN)2xe2x88x92, M+.
A particular category of compounds according to the invention comprises the compounds in which substituent RD has at least one anionic ionophorous group and/or at least one cationic ionophorous group. The anionic group may for example be a carboxylate function (xe2x80x94CO2xe2x88x92), a sulfonate function (xe2x80x94SO3xe2x88x92), a sulfonimide function (xe2x80x94SO2NSO2xe2x80x94) or a sulfonamide function (xe2x80x94SO2Nxe2x80x94). The ionophorous group may for example be an iodonium, sulfonium, oxonium, ammonium, amidinium, guanidinium, pyridinium, imidazolium, imidazolinium, triazolium, phosphonium or carbonium group. The cationic ionophorous group may act totally or partially as a cation M.
When RD includes at least one ethylenic unsaturation and/or a condensable group and/or a dissociable group by thermal means, by photochemical means or by ionic dissociation, the compounds of the invention are reactive compounds which may be subject to polymerizations, cross-linkings or condensations, possibly with other monomers. They may also be used to fix ionophorous groups on the polymers carrying a suitable reactive function.
A substituent RD may be a mesomorphous group or a chromophore group or a self-doped electronically conductive polymer or a hydrolyzable alkoxysilane.
A substituent RD may include a group capable of trapping free radicals, for example a hindered phenol or a quinone.
A substituent RD may also include a dissociating dipole, for example an amide function, a sulfonamide function or a nitrile function.
A substituent RD may also include a redox couple, a disulfide group, a thioamide group, a ferrocene group, a phenothiazine group, a bis(dialkylaminoaryl) group, a nitroxide group or an aromatic imine group.
A substituent RD may also include a complexing ligand, or an optically active group.
Another category of compounds of the invention comprises compounds in which Y is a carbonyl group, RDxe2x80x94COxe2x80x94 representing an amino acid, or an optically or biologically active polypeptide.
According to another variant, a compound according to the invention comprises a substituent RD which represents a radical having a valency v higher than 2, itself including at least one group xe2x80x94Yxe2x80x94C(CN)2xe2x88x92, M+. In this case, the negative charges which are present on the anionic part of the compound of the invention should be compensated by the appropriate number of cations or cationic ionophorous groups M.
When a compound of the present invention corresponds to the formula Zxe2x80x94C(CN)2xe2x88x92, M+ in which Z is an electroattractor group which is not bonded to the nitrogen atom carrying the negative charge by means of a group xe2x80x94SOxxe2x80x94, Z is advantageously selected from the group consisting of xe2x80x94OCnF2n+1, xe2x80x94OC2F4H, xe2x80x94SCnF2n+1 and xe2x80x94SC2F4H, xe2x80x94OCFxe2x95x90CF2, xe2x80x94SCFxe2x95x90CF2, n being a whole number from 1 to 8. Z may also be a radical CnF2n+1CH2xe2x80x94, n being a whole number from 1 to 8.
The compounds of the invention may be obtained by a process in which a compound RDxe2x80x94Yxe2x80x94L or Zxe2x80x94L is reacted with a compound [Axe2x80x94C(CN)2]nxe2x88x92mnMxe2x80x2m+,
Z and RD being such as defined previously,
Mxe2x80x2 being H or a cation such as defined previously for M,
L represents an electronegative starting group such as a halogen, a N-imidazoyl radical, a N-triazoyl radical, a compound giving an activated ester (for example a succinimidyloxy, a benzotriazoloxy or a O-acylurea), an alkoxide group, a RDxe2x80x94Yxe2x80x94Oxe2x80x94 group or a RDxe2x80x94Yxe2x80x94Sxe2x80x94 group, and
A represents a cation Mm+, a trialkylsilyl group, a trialkyl germanyl group, a trialkylstannyl group or a tertioalkyl group, in which the alkyl substituents have 1 to 6 carbon atoms.
By way of example, there should be mentioned the reaction of a flurosulfonyl fluoride with a di-salt of malononitrile according to the following reaction scheme:
FSO2xe2x80x94F+[NaC(CN)2]xe2x88x92Na+xe2x86x92NaF+[FSO2xe2x80x94C(CN)2]xe2x88x92Na+.
The use of a compound [Axe2x80x94C(CN)2]nxe2x88x92mnMxe2x80x2m+ in which A is a tertioalkyl group is advantageous, since such a group is a proton precursor by formation of the corresponding alkene. The use of the trialkylsilyl group is especially interesting when the starting group is a fluorine, due to the very high stability of the bond Fxe2x80x94Si.
When a compound [Axe2x80x94C(CN)2]nxe2x88x92mnMxe2x80x2m+ in which A is the proton is used, it is advantageous to carry out the reaction in the presence of a tertiary base or a congested base T capable of forming the salt Lxe2x88x92(HT+) by combination with the proton, in order to promote the formation of the compound of the invention. The base may be selected among alkylamides (for example triethylamine, di-isopropylamine, quinuclidine), 1,4-diazobicyclo[2,2,2]octane (DABCO); pyridines (for example pyridine, alkylpyridines, dialkylaminopyridines); imidazoles (for example N-alkylimidazoles, imidazo[1,1-a]pyridine); amidines (for example 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU)); guanidines (for example tetramethyl guanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (HPP). An alkali metal salt of malononitrile can also be used as a base.
By way of example of such a process, the process in which a carbonyl chloride RDCOCl is reacted with malononitrile in the presence of DABCO may be mentioned.
A compound of the invention may also be obtained by direct coupling between a malononitrile salt and a carboxylic acid by means of a coupling agent. When Z=CO, it is advantageous to use a compound RZX of the type pseudo-halide directly prepared in-situ (X=RCO2, SCO, PTO, BzO . . . ) from RCOOH by action of the condensation agents used in the synthesis of peptides (molecular dehydrating agents). Such agents are described for example in Synthesis p. 453 (1972) and in Ann. Rev. Biochem 39, 841 (1970). The compounds of the invention are then prepared from RCOOH to which the molecular dehydration agent is added, and also the compound (1/nM)[(NC)2CH] in stoichiometric proportions in a polar solvent. Preferably, the condensation agent is selected from carbodiimides, for example cyclohexyl carbodiimide or diisopropyl carbodiimide; carbonates and oxalates of succinimidyl, phthalimidyl, benzotriazolyl, of nitro-, dinitro- or perhalo-phenols, of trifluoroethyl, of trichloroethyl; the mixture Pxcfx863-diethylazodicarboxylate (DEAD) or Pxcfx863-dithiodipyridine; carbonyldiimidazole (Im)2CO or phenylphosphorodiimidazole xcfx86PO(Im)2; amide acetals, for example dimethylformamide di-neopentyl acetal (CH3)2NCH[OCH2C(CH2)2]2; 2-alcoxy-1-alkoxycarbonyl-1,2-dihydroquinoline; salts of O-benzo triazol-1-yl-N,N,Nxe2x80x2,Nxe2x80x2-tetramethyluronium or O-benzo triazol-1-yloxytrisdimethylaminophosphonium; aromatic sultones, for example 2,2-(6-nitronaphth[1,8-cd]-1,2-oxathiazoyl) oxide, iosbutyl chloroformate, diphenylphosphochloroiridate, ethylene chlorophosphite, diethylethylene pyrophosphite, bis(2-oxo-3-oxazolidinyl)phosphinyl chloride; 2-ter-butyl-5-methyl isooxazolium salts (Woodward""s reagent L).
The cation of the compound obtained according to either of the processes described above may be replaced by the known processes of cationic exchange, either by precipitation or selective extractions, or by the use of ion exchange resins.
In addition, the substituent RD of a compound of the invention may be modified by known reactions. For example, a substituent RD which comprises an allyl group maybe converted by reaction with a peroxide to give an expoxidized substituent RD. A group xe2x80x94NHR may be converted into a vinylester group by reaction with potassium tert-butoxide and vinylchloroformate. Processes to carry out these modifications and others are available to one skilled in the art.
The ionic compounds of the present invention comprise at least one ionophorous group on which substituents of highly various natures are fixed. Bearing in mind the large possible choice for the substituents, the compounds of the invention enable to provide properties of ionic conduction in most organic, liquid or polymer medias having even a low polarity. The applications are important in the field of electrochemistry, in particular for storing energy in primary or secondary generators, in supercapacitances, in combustible batteries and in electroluminescent diodes. The compatibility of the ionic compounds of the invention with polymers or organic liquids enables to provide noted antistatic properties, even when the amount of ionic compound is extremely low. The compounds of the invention which are polymers, as well as polymeric compounds obtained from the compounds of the invention having the property of polymerizing or copolymerizing, have the properties listed above with the advantage of having an unmovable anionic charge. This is why another object of the present invention consists of an ionically conductive material made of an ionic compound of the present invention in solution in a solvent.
According to an embodiment, the ionic compound used for preparing an ionically conductive material is selected from compounds in which the cation is ammonium, or a cation derived from a metal, in particular lithium or potassium, zinc, calcium, rare earth metals, or an organic cation, such as a substituted ammonium, an imidazolium, a triazolium, a pyridinium, a 4-dimethylamino-pyridinium, said cations possibly carrying a substituent on the carbon atoms of the cycle. The ionically conductive material thus obtained has a high conductivity and solubility in solvents, due to the low interactions between the positive charge and the negative charge. Its range of electrochemical stability is wide, and it is stable in reducing as well as oxidizing media. Moreover, the compounds which have an organic cation and a melting point lower than 150xc2x0 C., in particular compounds of imidazolium, triazolium, pyridinium, 4-dimethylamino-pyridinium have a high intrinsic conductivity, even in the absence of solvents when they are in molten phase.
The properties of the ionically conductive material may also be modified by the choice of substituent Y or RD.
The choice of an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group for RD enable to provide in the ionically conductive material properties of the type mesogene, in particular alkyl groups containing 6 to 20 carbon atoms, arylalkyl groups, in particular both containing the biphenyl entity which form phases of the liquid crystal type. Properties of conduction in phases of the liquid crystal, nematic, cholesteric or discotic type are interesting for applications concerning optical postings or for reducing the mobility of anions in electrolytes, in particular in polymer electrolytes, without affecting the mobility of the cations. This characteristic is important for applications in electrochemical generators, in particular those utilizing lithium cations.
When the substituent RD contains mesomorphous group or a group to comprising at least one ethylenic unsaturation and/or a condensable group and/or a group which is dissociable by thermal means, by photochemical means or by ionic dissociation, the ionically conductive material easily forms polymers or copolymers which are polyelectrolytes, the latter being intrinsically polyelectrolytes when the polymer carries solvating groups, or becomes polyelectrolytes by addition of a is polar solvent of the liquid or polymer type, or by mixture with such a solvent. These products have a conductivity which is solely due to the cations, which constitutes a property which is very useful in applications of the electrochemical generator type. In low molar fraction in a copolymer, they give rise to stable antistatic properties which are hardly dependent on humidity and cause the fixation of cationic colorants, this property being useful for textile fibers and lasers with coloring materials.
The presence of a substituent RD which is a self-doped electronically conductive polymer improves the stability of the ionically conductive material with respect to outside agents. The conductivity is stable in time even at high temperatures. In contact with metals, these materials give very low interface resistances and protect in particular ferrous metal or aluminum from corrosion.
When the substituent RD is a hydrolyzable alkoxysilane, the ionically conductive material may form stable polymers by a simple mechanism of hydrolysis-condensation in the presence of water, thus enabling to treat surfaces of oxides, of silica, of silicates, in particular glass, to induce properties of surface conduction, antistatic properties, or to promote the adhesion of polar polymers.
When the substituent RD is a group comprising a free radical trap such as a hindered phenol, or a quinone, the ionically conductive material has the following advantages and properties: it acts as an antioxidant having no volatility and being compatible with polar monomers and polymers, to which it also gives antistatic properties.
When the substituent RD comprises a dissociating dipole such as an amide, a sulfonamide or a nitrile, the ionically conductive material has an improved conductivity in media of low or medium polarity, in particular in solvating polymers, which enables to minimize, even to prevent the addition of solvents or of volatile plasticizing agents.
The presence of a substituent RD which contains a redox couple such as a disulfide, a thioamide, a ferrocene, a pheno-thiazine, a bis(dialkylaminoaryl) group, a nitroxide, an aromatic imide, enables to induce in the ionically conductive material properties of redox shuttle useful as protective elements and charge equalization of electrochemical generators, in photoelectrochemical systems, in particular in systems of conversion of light into electricity, in systems of modulation of light of the electrochrome type.
The presence of a substituent RD which is a complexing ligand in an ionically conductive material enables to chelate metallic cations, in particular those which have an elevated charge (2, 3 and 4), in the form of soluble complex in organic media, including in aprotic media, and enables the transport of these cations in particular in the form of anionic complex, in solvating polymers. The metallic cations of elevated charge are indeed immovable in solvating polymers. This type of complexing agents gives with certain cations of transition metals (Fe, Co . . . ) or certain rare earths (Ce, Eu . . . ) redox couples which are particularly stable. ionically conductive materials containing a compound of the invention in which RD is an alkyl or alkenyl substituent which contains at least one heteroatom selected from O, N and S have a complexing and plasticizing capacity, in particular in polar polymers and especially polyethers. The heteroatoms N and S are selectively complexing for cations of transition metals Zn and Pb.
When an alkyl or alkenyl substituent RD additionally carries a hydroxy group, a carbonyl group, an amine group, a carboxyl group, the ionic compound of the invention may give by polycondensation a polymer or a copolymer and the ionically conductive material which contains such a polymer or copolymer have polyelectrolytic properties.
The presence, in a ionically conductive material of the invention, of a compound in which RD is selected from aryl, arylalkyl, alkylaryl or alkenylaryl radicals, in which the lateral chains and/or the aromatic nuclei comprise heteroatoms such as nitrogen, oxygen, sulfur, improves dissociation and increases the possibility of producing complexes depending on the position of the heteroatom (pyridine) or of giving by duplicative oxidation conjugated polymers or copolymers (pyrrol, thiophene).
When the ionically conductive material contains a compound of the invention in which RD represents a recurring unit of a polymer chain, the material constitutes a polyelectrolyte.
A compound of the invention in which the substituent Z is selected from the group consisting of xe2x80x94OCnF2n+1, xe2x80x94OC2F4H, xe2x80x94SCnF2n+1 and xe2x80x94SC2F4H, xe2x80x94OCFxe2x95x90CF2, xe2x80x94SCFxe2x95x90CF2, n being a whole number from 1 to 8, is a precursor of stable monomers and polymers, in particular towards oxygen even at elevated temperatures of 80xc2x0 C. when dealing with polymers. An ionically conductive material which contains such a compound is therefore particularly appropriate as an electrolyte of a combustible battery.
An ionically conductive material of the present invention comprises an ionic compound of the invention in solution in a solvent.
The solvent may be an aprotic liquid solvent, a polar polymer or one of their mixtures.
The aprotic liquid solvent is selected for example from linear ethers and cyclic ethers, esters, nitriles, nitro derivatives, amides, sulfones, sulfolanes, alkylsulfamides and partially hydrogenated hydrocarbons. The solvents which are particularly preferred are diethylether, dimethoxyethane, glyme, tetrahydrofurane, dioxane, dimethyltetrahydrofurane, methyl or ethyl formate, propylene or ethylene carbonate, alkyl carbonates (such as dimethylcarbonate, diethylcarbonate and methylpropylcarbonate), butyrolactones, acetonitrile, benzonitrile, nitromethane, nitrobenzene, dimethylformamide, diethylformamide, N-methylpyrrolidone, dimethylsulfone, tetramethylene sulfone, tetramethylene sulfone and tetraalkylsulfonamides having 5 to 10 carbon atoms.
An ionically conductive material of the present invention may simultaneously comprise an aprotic liquid solvent selected from the aprotic liquid solvents mentioned above and a polar polymer solvent comprising units containing at least one heteroatom selected from sulfur, nitrogen, oxygen and fluorine. It may comprise from 2 to 98% liquid solvent. By way of example of such a polar polymer, polymers which mainly contain units derived from acrylonitrile, vinylidene fluoride, N-vinylpyrrolidone or methylmethacrylate may be mentioned. The proportion of aprotic liquid in the solvent may vary from 2% (corresponding to a plasticized solvent) to 98% (corresponding to a gelled solvent).
An ionically conductive material of the present invention may additionally contain a salt commonly used in the prior art to prepare an ionically conductive material. Among the salts which may be used in admixture with an ionic compound of the invention, a salt selected from perfluoroalcanesulfonates, bis(perfluoroalkylsulfonyl) imides, bis(perfluoroalkylsulfonyl) methanes and tris(perfluoroalkylsulfonyl) methanes are particularly preferred.
Of course, an ionically conductive material of the invention may additionally contain additives normally used in this type of material, such as mineral or organic charges in the form of a powder or fibers.
An ionically conductive material of the invention may be used as electrolyte in an electrochemical general. The present invention thus has as an object an electrochemical generator comprising a negative electrode and a positive electrode separated by an electrolyte, characterized in that the electrolyte is an ionically conductive material as defined above. According to a particular embodiment, such a generator comprises a negative electrode consisting of metallic lithium, or an alloy thereof, possibly in the form of a nanometric dispersion in lithium oxide, or a double nitride of lithium and a transition metal, or a low potential oxide having the general formula Li1+y+x/3Ti2xe2x88x92x/3O4 (0xe2x89xa6xxe2x89xa61, 0xe2x89xa6yxe2x89xa61), or carbon and the carbonated products resulting from the pyrolysis of organic materials. According to another embodiment, the generator comprises a positive electrode selected from vanadium oxides VOx (2xe2x89xa6xxe2x89xa62,5), LiV3O8, LiyNi1xe2x88x92xCoxO2, (0xe2x89xa6xxe2x89xa61; 0xe2x89xa6yxe2x89xa61), manganese spinels LiyMn1xe2x88x92xMxO2 (M=Cr, Al, V, Ni, 0xe2x89xa6xxe2x89xa60,5; 0xe2x89xa6yxe2x89xa62), organic polydisulfides, FeS, FeS2, iron sulfate Fe2(SO4)3, iron and lithium phosphates and phosphosilicates of olivine structure, or substituted products wherein iron is substituted by manganese, used alone or in admixtures. The collector of the positive is preferably made of aluminum.
An ionically conductive material of the present invention may also be used in a supercapacitance. Another object of the present invention is consequently to provide a supercapacitance utilizing at least one carbon electrode of high specific surface, or an electrode containing a redox polymer, in which the electrolyte is an ionically conductive material as defined above.
An ionically conductive material of the present invention may also be used for the p or n doping of an electronically conductive material and this use constitutes another object of the present invention.
In addition, an ionically conductive material of the present invention may be used as an electrolyte in an electrochrome device. An electrochrome device in which the electrolyte is an ionically conductive material according to the invention is another object of the present invention.
It was observed that the strong dissociation of ionic species of compounds of the invention results in a stabilization of carbocations, in particular those in which there is a conjugation with oxygen and nitrogen and, surprisingly, in a strong activity of the proton form of the compounds of the invention on certain monomers. The present invention therefore also has as an object the use of the ionic compounds as photoinitiators which constitute sources of Brxc3x8nsted acids, which are catalysts for the polymerization or cross-linking of monomers or polymers capable of cationic reaction, or as catalysts for the modification of polymers.
The process of polymerization or cross-linking of monomers or prepolymers capable of cationic reaction is characterized in that there is used a compound of the invention as photoinitiator constituting a source of acid catalyzing the polymerization reaction. The compounds according to the invention in which the cation is a group having a bond xe2x80x94Nxe2x95x90N+, xe2x80x94Nxe2x95x90Nxe2x80x94, a sulfonium group, an iodonium group, or an arene-ferrocenium cation which is substituted or non-substituted, possibly incorporated in a polymeric network, are particularly preferred.
The choice of substituent RD or substituent Z is made so as to increase the solubility of said compound in the solvents used for the reaction of monomers or prepolymers, and as a function of the desired properties for the final polymer. For example, the choice of non-substituted alkyl radicals gives a solubility in low polar media. The choice of radicals comprising an oxa group or a sulfone will give a solubility in polar media. The radicals including a sulfoxide group, a sulfone group, a phosphine oxide group, a phosphonate group, respectively obtained by the addition of oxygen on the atoms of sulfur or phosphorus, may give to the polymer obtained improved properties with respect to adhesion, shine, resistance to oxidation or to UV. The monomers and prepolymers which may be polymerized or cross-linked with the photoinitiators of the present invention are those which may undergo a cationic polymerization.
The monomers and prepolymers which may be polymerized or cross-linked with the photoinitiators of the present invention are those which may be subject to cationic polymerization.
Among the monomers, monomers which include a cyclic ether function, a cyclic thioether function or cyclic amine function vinyl compounds (more particularly vinyl ethers), oxazolines, lactones and lactames may be mentioned.
Among the polymers of the ether or cyclic thioether type, ethylene oxide, propylene oxide, oxetane, epichlorhydrin, tetrahydrofurane, styrene oxide, cyclohexene oxide, vinylcyclohexene oxide, glycidol, butylene oxide, octylene oxide, glycidyl ethers and esters (for example glycidyl methacrylate or acrylate, phenyl glycidyl ether, diglycidylether of bisphenol A or its fluorinated derivatives), cyclic acetals having 4 to 15 carbon atoms (for example dioxolane, 1,3-dioxane, 1,3-dioxepane) and spiro-bicyclo dioxolanes may be mentioned.
Among vinyl compounds, vinyl ethers constitute a very important family of monomers which are capable of cationic polymerization. By way of example, there may be mentioned ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, ethyleneglycol monovinyl ether, diethyleneglycol divinyl ether, butanediol monovinyl ether, butanediol divinyl ether, hexanediol divinyl ether, ethyleneglycol butyl vinyl ether, triethyleneglycol methyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether, 2-ethylhexyl vinyl ether, poly-THF-divinyl ether having a molecular weight between 150 and 5,000, diethyleneglycol monovinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether.
Other vinyl compounds may include, by way of example, 1,1-dialkylethylenes (for example isobutene), vinyl aromatic monomers (for example styrene, xcex1-alkylstyrenes, such as xcex1-methylstyrene, 4-vinylanisole, acenaphthene) N-vinyl compounds (for examples N-vinylpyrolidone or N-vinyl sulfonamides).
Among prepolymers, there may be mentioned compounds in which epoxy groups are carried by an aliphatic chain, an aromatic chain, or a heterocyclic chain, for example glycidicethers of bisphenol A which are ethoxylated by 3 to 15 ethylene oxide units, siloxanes having lateral groups of the epoxycyclohexene-ethyl type obtained by hydrosilylation of copolymers of dialkyl, alkylaryl or diaryl siloxane with methyl hydrogenosiloxane in the presence of vinylcyclohexene oxide, condensation products of the sol-gel type obtained from triethoxy or trimethoxy silapropylcyclohexene oxide, urethanes incorporating the reaction products of butanediol monovinylether and an alcohol of a functionality higher than or equal to 2 with an aliphatic or aromatic di- or tri-isocyanate.
The process of polymerization according to the invention consists in mixing at least one monomer or prepolymer capable of cationic polymerization and at least one ionic compound of the invention, and subjecting the mixture obtained to actinic or xcex2 radiation. Preferably, the reaction mixture is subjected to radiation having been formed into a thin layer having a thickness lower than 5 mm, preferably in the form of a thin layer having a thickness lower than or equal to 500 xcexcm. The duration of the reaction depends on the thickness of the sample and the power of the source at the active xcex wavelength. It is defined by the speed at which it passes in front of the source, which is between 300 mm/min and 1 cm/min. Layers of the final material having a thickness greater than 5 mm may be obtained by repeating many times the operation consisting in spreading a layer and treating it with the radiation.
Generally, the quantity of photoinitiator used is between 0.01 and 15% by weight with respect to the weight of the monomer or prepolymer, preferably between 0.1 and 5% by weight.
An ionic compounds of the present invention may be used as photoinitiator in the absence of solvent, for example when it is intended to polymerize liquid monomers in which the ionic compound used as photoinitiator is soluble or easily dispersible. This type of utilization is particularly interesting, since it enables to overcome the problems associated with solvents (toxicity, flammability).
An ionic compound of the present invention may also be used as photoinitiator in the form of a homogeneous solution in a solvent which is inert towards polymerization, ready to be used and easily dispersible, in particular in the case where the medium to be polymerized or cross-linked has a high viscosity.
As example of an inert solvent, there may be mentioned volatile solvents, such as acetone, methyl-ethyl ketone and acetonitrile. These solvents will be used simply to dilute the products to be polymerized or cross-linked (to make them less viscous, especially when dealing with a prepolymer). They will be removed by drying after polymerization or cross-linking. Non-volatile solvents may also be mentioned. A non-volatile solvent also serves to dilute the products that one wishes to polymerize or cross-link, and to dissolve the ionic compound of the invention used as photoinitiator, however, it will remain in the material formed and will thus act as plasticizing agent. By way of example, propylene carbonate, xcex3-butyrolactone, ether-esters of mono-, di-, tri-ethylene or propylene glycols, ether-alcohols of mono-, di-, tri-ethylene or propylene glycols, plasticizing agents such as esters of phthalic acid or citric acid, may be mentioned.
According to another embodiment of the invention, there may be used as solvent or diluent a compound which is reactive towards polymerization, which is a compound of low molecular weight and of low viscosity which will simultaneously act as polymerization monomer and solvent or diluent for more viscous polymers or prepolymers used in combination. After the reaction, these monomers having been used as solvent will be part of the macromolecular network finally obtained, their integration being wider when dealing with bi-functional monomers. The material obtained after irradiation is now free of products having a low molecular weight and a substantial vapour tension, or capable of contaminating objects with which the polymer is in contact. By way of example, a reactive solvent may be selected from mono and divinyl ethers of mono-, di-, tri-, tetra-ethylene and propylene glycols, N-methylpyrolidone, 2-propenylether of propylene carbonate commercially available for example under the commercial designation PEPC from ISP, New Jersey, United States.
To irradiate the reaction mixture, the irradiation may be selected from ultraviolet radiation, visible radiation, X-rays, xcex3 rays and xcex2 radiation. When ultraviolet light is used as actinic radiation, it may be advantageous to add to the photoinitiators of the invention photosensitizers intended to provide an efficient photolysis with wavelengths less energetic than those corresponding to the maximum of absorption of the photoinitiator, such as those produced by industrial devices, (I≈300 nm for mercury vapour lamps in particular). Such additives are known, and by way of non-limiting example, there may be mentioned anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine, tetracene, xanthone, thioxanthone, acetophenone, benzophenone, 1,3,5-triaryl-2-pyrazolines and derivatives thereof, in particular derivatives which are substituted on the aromatic nuclei by alkyl, oxa- or aza-alkyl radicals, enabling inter alia to change the absorption wavelength. Isopropylthioxantone is an example of preferred photosensitizer when an iodonium salt according to the invention is used as photoinitiator.
Among the different types of radiation mentioned, ultraviolet radiation is particularly preferred. On the one hand, it is more convenient to use than the other radiations mentioned. On the other hand, photoinitiators are in general directly sensitive towards UV rays and photosensitizers are more efficient when the difference of energy (xcex4xcex) is lower.
The ionic compounds of the invention may also be used in association with free radical initiators produced thermally or by action of actinic radiation. It is also possible to polymerize or cross-link mixtures of monomers or polymers containing functions in which the types of polymerization are different, for example, monomers or prepolymers which polymerize by free radical and monomers or prepolymers which polymerize by cationic polymerization. This possibility is particularly advantageous to produce interpenetrated networks having physical properties which are different from those which would be obtained by a simple mixture of polymers originating from corresponding monomers. Vinyl ethers are not or are very little active by free radical initiation. It is therefore possible, in a reaction mixture containing a photoinitiator according to the invention, a free radical initiator, at least one monomer of the vinyl ether type and at least one monomer comprising non-activated double bonds such as those of the allyl groups, to carry out a separate polymerization of each type of monomer. On the other hand, it is known that monomers which are lacking in electrons, such as esters or amides of furmaric acid, maleic acid, acrylic or methacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleimide and derivatives thereof, form in the presence of vinyl ethers which are enriched in electrons, complexes of transfer of charge giving alternated polymers 1:1 by free radical initiation. An initial excess of vinyl monomers with respect to this stoichiometry enables to preserve polymerizable functions by pure cationic initiation. The start of the activity of a mixture of free radical initiator and cationic initiator according to the invention may be carried simultaneously for the two reactants in the case for example of isolation by actinic radiation of a wavelength for which the photoinitiators of the invention and the selected radical initiators are active, for example at xcex=250 nm. By way of example, the following commercial products: Irgacure 184(copyright), Irgacure 651(copyright), Irgacure 261(copyright), Quantacure DMB(copyright), Quantacure ITX(copyright) may be mentioned as initiators.
It may also be advantageous to use the two types of polymerization in a sequential manner, to first form prepolymers which are easy to shape and in which hardening, adhesion, solubility as well as degree of cross-linking may be modified by initiating the activity of the cationic initiator. For example, a mixture of a thermo-dissociable radical initiator and a cationic photoinitiator according to the invention enables to provide sequential polymerizations or cross-linking, first under the action of heat, then under the action of actinic radiation. Similarly, if a free radical initiator and a cationic photoinitiator according to the invention are selected, the first being photosensitive at longer wavelengths than the one initiating the photoinitiator according to the invention, there is obtained a cross-linking in two controllable steps. Free radical initiators may for example be Irgacure(copyright) 651 enabling to initiate free radical polymerizations at wavelength of 365 nm.
The invention also has as an object the use of ionic compounds of the invention for chemical amplification reactions of photoresists in the field of microlithography. During such use, a film of a material comprising a polymer and an ionic compound of the invention is subject to irradiation. The irradiation causes the formation of the acid by replacement of the cation M with a proton, which catalyzes the decomposition or transformation of the polymer. After decomposition or transformation of the polymer on the parts of the film which have been irradiated, the monomers formed or the polymer which has been converted are removed and what remains is an image of the unexposed parts. For this particular application, it is advantageous to use a compound of the invention which is in the form of a polymer consisting essentially of styrenyl recurring units carrying an ionic substituent xe2x80x94C(CN)2xe2x88x92. These compounds enable to obtain after photolysis products which are not volatile, and therefore not odoriferous when dealing with sulfides. Among the polymers which may thus be modified in the presence of a compound of the invention, there may for example be cited polymers containing ester units or tertiaryalkyl arylether units, for example poly(phthaldehydes), polymers of bisphenol A and a diacid, polytertiobutoxycarbonyl oxystyrene, polytertiobutoxy-xcex1-methyl styrene, polyditertiobutylfumarate-co-allyltrimethylsilane and polyacrylates of a tertiary alcohol, in particular tertiobutyl polyacrylate. Other polymers are described in J. V. Crivello et al, Chemistry of Materials 8, 376-381, (1996).
The ionic compounds of the present invention, which have an elevated thermal stability, give numerous advantages with respect to the known salts of the prior art. They have speeds of initiation and propagation which are comparable or higher than those obtained with coordination anions of the type PF6xe2x80x94, AsF6xe2x80x94 and especially SbF6xe2x80x94. In addition, the coefficient of diffusion of the anion xe2x80x94C(CN)2xe2x88x92 is higher than that of hexafluorometallate anions or tetrafluoroborate anions or phenylborate anions. These properties are explained by the delocalization of the negative charge and the weak repulsion between the partial charges carried by the nitrogen atoms of nitrile groups and removed from one another by 2xc3x85.
In the compounds of the present invention, the pairs of ions have a very high dissociation, which enables the expression of intrinsic catalytic properties of the cation Mm+, in which the active orbits are easily exposed to substrates of the reaction, especially in different media. Most of the important reactions of organic chemistry may thus be carried out under easy conditions, with excellent yields and the possibility of separating the catalyst from the reaction mixture. The demonstration of asymmetric induction by the use of an ionic compound according to the invention which carries a chiral group is particularly important in view of its generality and its ease of operation. The present invention consequently has as another object the use of compounds of the invention as catalysts in Friedel-Crafts reactions, Diels-Alder reactions, aldolization reactions, additions of Michael, reactions of allylation, reactions of pinacolic coupling, reaction of glycosilation, reaction of openings of the cycle of oxetanes, reactions of metathesis of alkenes, polymerizations of the Ziegler-Natta type, polymerizations of the metathesis type by cycle opening and polymerizations of the metathesis type of acyclic dienes. The preferred ionic compounds of the invention for utilization as catalyst for the above reactions are those in which the cation is selected from lithium, magnesium, copper, zinc, tin, trivalent metals, including rare earths, platinoids, and their organometallic couples, in particular metallocenes.
The compounds of the invention may also be used as solvent to carry out chemical, photochemical, electrochemical, photoelectrochemical reactions. For this particular use, the ionic compounds in which the cation is an imidazolium, triazolium, pyridinium or 4-dimethylamino-pyridinium, are preferred, said cation possibly carrying a substituent on the carbon atoms of the cycle. Among the compounds used in liquid form, those having a melting point lower than 150xc2x0 C., more particularly lower than 100xc2x0 C., are particularly preferred.
The inventors have also found that the ionic charge carried by the group xe2x80x94C(CN)2xe2x88x92 have a stabilizing effect on the electronic conductors of the conjugated polymer type, and that the use of the compound in which the substituent Z comprises a long alkyl chain enables to make these polymers soluble in known organic solvents even in doped state. Grafting of these charges on the polymer itself gives polymers with global cationic charge, which are soluble and present, in addition to their stability, anti-corrosion properties towards metal, such as aluminum and ferrous metals. It is an object of the present invention to provide materials with electronic conduction comprising an ionic compound of the present invention in which the cationic part is a polycation consisting of a doped xe2x80x9cpxe2x80x9d conjugated polymer. The preferred ionic compounds for this application are those in which the substituent Z or RD contains an alkyl chain having 6 to 20 carbon atoms.
The coloring materials of cationic type (cyanines) are used more and more frequently as sensitizers of photographic films, for storing optical information (optical disks accessible in writing), for lasers. The tendency of these conjugated molecules to pile over one another when they are in solid phase limits their utilization, because of the variation of the optical properties with respect to the isolated molecule. The use of ionic compounds of the invention for manufacturing cationic coloring materials including counter ions, possibly bound to this same molecule, correspond to functions of the invention enables to reduce phenomenons of aggregation, including in solid polymer matrices and to stabilize these coloring materials. It is another object of the present invention to provide a composition of cationic coloring material, characterized in that it contains an ionic compound according to the invention. The particularly preferred ionic compounds for this application are those in which the negative charge(s) of the anionic group xe2x80x94C(CN)2xe2x88x92 are either fixed to the molecule of the coloring material, or they constitute the counter-ion of the positive charges of the coloring material.
A few examples of compounds according to the invention are given hereinafter:
The present invention is explained more in detail with the following examples, which describe the preparation and various utilizations of compounds of the invention. The invention is, however, not limited to these examples.
All the compounds of the invention have been prepared from alkali metal salts of malononitrile. Said salts have been obtained from commercial malononitrile previously purified in a sublimation cell at 40xc2x0 C. under secondary vacuum, the malononitrile being recovered after 48 hours on the cold finger of the cell, in the form of white crystals which are thereafter kept under argon.
The lithium salt was obtained by dosing an aqueous solution of malononitrile with a titrated solution of lithium hydroxide LiOH, the neutralization point being determined by means of a pH-meter. The aqueous solution was thereafter lyophilized, and the product was dried under secondary vacuum at room temperature during 72 hours. There is obtained a lithium salt which, kept under argon, has a purity determined by a proton and carbon RMN higher than 99%.
By the same process, sodium and potassium salts were obtained by replacing lithium hydroxide respectively with sodium hydroxide and potassium hydroxide.

Malononitrile-derivative anion salts, and their uses as ionic conducting materials

Centre National de la Recherche Scientifique


An asphaltic mix batch apparatus which comprises a tower which mounts a number of aggregate storage bins, a weigh hopper underlying the storage bins, and a pugmill underlying the weigh hopper. Also, a screen assembly is positioned above the bins for segregating the aggregate by size, and such that the initial bin receives the more fine aggregate and the subsequent bins receive the more coarse aggregate. The initial bin has a relatively wide open top, and it receives a relatively broad gradation of the aggregate from its front to its back, with the front being disproportionately fine and the back being disproportionately coarse. A divider plate is positioned in the initial bin to prevent the gradation from interfering with the free discharge of the aggregate when the associated discharge port is opened, and to thereby provide a more uniform gradation being withdrawn through the discharge port.

The present invention relates to a storage apparatus adapted for separately storing several graded sizes of a particulate aggregate, and which is useful in the production of an asphaltic mix.
Conventional batch type plants for producing asphaltic mix typically comprise a drum dryer for heating and drying the stone aggregate, and a vertical bucket elevator for conveying the heated and dried aggregate from the dryer to the top of a tower. The tower includes an enclosed vibrating screen assembly at the top, for receiving and segregating the aggregate by size. The segregated aggregate then drops through individual chutes to a bin section which underlies the screen assembly, and which comprises a plurality of separate bins aligned in a transverse direction, and so that each bin receives an aggregate of a predetermined average size from the screen assembly. A weigh hopper is positioned below the bins, which permits the aggregate from one or more bins to be weighed out to provide a desired mixture, as required for example for a roadway base coat or a finish coat. A mixing pugmill is positioned below the weigh hopper for mixing the weighed quantity of aggregate with hot liquid asphalt, and the bottom of the pugmill includes a gate opening, such that the contents may be dropped into an underlying truck.
The initial bin in the transverse line of bins, and which is commonly referred to as the "fines" bin, receives the relatively fine aggregate, and the aggregate becomes progressively more coarse as it is delivered into the subsequent bins at the downstream end of the screen assembly. Also, the initial fines bin typically has an open top of substantially greater dimension than that of the remaining bins, and thus the initial fines bin receives a much broader range of aggregate size than does the other bins. A longstanding problem is the fact that the finer portion of this range of aggregate size which is destined for the initial fines bin tends to find its way quickly through the associated screen while the more coarse portion takes a longer time. This results in a gradation of the aggregate within the initial fines bin, with a more fine portion of the aggregate being received in the front end of the bin and a more coarse portion of the aggregate being received in the rear end of the bin. This gradation in turn creates a problem in withdrawing the aggregate from the discharge port at the bottom of the bin, in that the coarse aggregate tends to crowd out the fine aggregate and prevents it from flowing out uniformly. Thus, when the discharge port is opened, the discharge includes surges of coarse and fine aggregate, and the discharge is not uniform. As a result, it is not possible to accurately control the size of the aggregate in the asphaltic mix being produced.
It is accordingly an object of the present invention to provide an apparatus for producing asphaltic mix and which avoids or at least significantly alleviates the above noted problem associated with conventional plants.
It is a more particular object of the present invention to provide an apparatus for producing asphaltic mix which achieves a substantially uniform discharge of both the relatively fine and the relatively coarse aggregate in the initial fines bin upon opening of the discharge port thereof, and so that the size of the aggregate in the resulting asphaltic mix can be accurately controlled.

Aggregate storage apparatus for use in producing asphaltic mix


An electronic device such as an AC adaptor includes a cable spool. A cable connector is provided on a housing for the AC adaptor. A cable extends from the connector. The cable may be wrapped around the housing in a spool-like manner for storing the cable on the housing. The cable is confined in a spool by a pair of spaced-apart guide members which extend from the housing.

The disclosures herein relate generally to cable storage and more particularly to a cable spool for an AC power adaptor.
Electronic devices such as AC adaptors are provided in a housing. The housing includes an AC connector and a DC connector so that both AC and DC cables can be attached to the housing when the adaptor is to be used. The adaptor and the cables must be stored when not in use. Storage of the cables needs to be accomplished in a non-bulky and tangle-free manner.
As AC power adaptors have become smaller and smaller, the size of the AC and DC cables has become a larger portion of the overall travel space required. The cables tend to be very bulky and tangle while stored in carrying cases. A clean way of wrapping both AC and DC cables is needed.
It would be a time saver to be able to wrap the cables around the housing so that the cables do not have to be removed from the housing and coiled separately for storage. Therefore, a cable management device is desirable for AC adaptors. Most AC adaptors have no cable management designed in. Some AC adaptors have cable managers that have folding pieces that tend to break easily. Some AC adaptors have molded-in cable managers that do not have the flexibility to be removed.
Therefore, what is needed is a cable management apparatus and method provided on an electronic device such as an AC adaptor such that a removable cable management device is provided for the adaptor housing.
One embodiment, accordingly, provides a cable manager on the AC adaptor which can be used as a guide to wrap both the AC and DC cables around the adaptor housing. To this end, an electronic housing has a cable connector therein and a cable spool for a cable. The spool includes spaced apart guide members extending from the housing, whereby a cable is wrapped around the housing between the guide members.
A principal advantage of this embodiment is that it provides for non-bulky cable storage in a tangle-free manner.


Model evaluation and circuit simulation/verification is performed in a graphical processing unit (GPU). A multitude of first texture data corresponding to size parameters of devices are stored. A multitude of second texture data corresponding to instance parameters of the devices are stored. A multitude of third texture data corresponding to models of the devices are stored. A multitude of fourth texture data corresponding to terminal voltages received by the device are stored. A multitude of links linking each device instance to an associated device model, size parameters and instance parameters are stored. A quad having a size defined by the multitude of links is drawn by the quad in the GPU. Each thread in the quad is assigned to a different one of the multitude of links. The computations are carried out in each thread using the linked data to perform the model evaluation.

The present invention relates to electronic design automation (EDA) software, and more particularly, to implementing such software in a graphical processing unit.
Integrated circuits continue to advance rapidly and are being widely used in many applications such as computers, consumer electronics, networking, and telecommunications. There are many types of integrated circuits including microprocessors, microcontrollers, application specific integrated circuits (ASICs), gate arrays, programmable logic devices (PLDs), field programmable gate arrays (FPGAs), dynamic random access memories (DRAMs), static random access memories (SRAMs), erasable programmable read only memories (EPROMs), electrically erasable programmable read only memories (EEPROMs), and Flash memories.
Design automation tools are needed to simplify and expedite the task of designing an integrated circuit. It is important to be able to accurately predict and estimate the performance of an integrated circuit before the integrated circuit is fabricated. Techniques are needed to provide accurate, fast estimates of the performance of an integrated circuit. It is often desirable in the microelectronics industry to be able to implement physical solutions in as little time as possible for coping with new market opportunities and/or emerging problems. Computer-aided simulations are often used to predict the behaviors of the electrical circuits before they are manufactured. This is done so that design errors are corrected and design parameters are optimized prior to production. It is well known, for example, to use computers and software simulators such as SPICE for obtaining fairly accurate predictions of the analog behaviors of complex circuitry. A number of logic design tools are also commercially available.
In conventional systems, computations required by circuit/logic design automation tools are implemented by one or more central processing units (CPUs). However, as model evaluation times continue to dominate the total simulation time for most Integrated circuit designs, improved systems for performing the required computations are needed.


An underwater drainage apparatus is provided with an underwater seal formed by fluid from the pleural cavity of the patient. The dead air space within the underwater drainage apparatus is reduced to a minimum by dividing the collection chamber into a plurality of compartments and providing seals between the compartments which are dissolved when liquid from the preceding compartment reaches the dissolvable seal. A passageway is provided in the air space directly above the underwater seal chamber to connect to the outlet to suction and a one way valve is provided in this passageway.

This invention relates to a surgical drainage system and more particularly, to an apparatus designed to drain fluids from a body cavity.
It is essential for normal breathing that the space within the pleural cavity surrounding the lungs be free of liquid and be subject to a negative pressure so as to draw the lungs outwardly to fill the pleural cavity. Any invasion of the pleural cavity such as lung surgery, foreign objects piercing the ribcage or pleurisy, generate fluids in the pleural cavity which obstruct normal breathing and it is necessary to provide means for removing these fluids and at the same time to maintain the desired degree of negative pressure within the pleural cavity.
The basic apparatus which has been used for this purpose is an apparatus such as shown in U.S. Pat. Nos. 3,363,626 and 3,363,627. This apparatus is known as an underwater drainage apparatus and provides basically three chambers, one chamber comprising a collection chamber for collecting the fluids drained from the pleural cavity, a second chamber known as an underwater seal chamber which protects the pleural cavity from being subject to atmospheric pressure, and a third chamber known as a pressure manometer chamber which regulates the degree of negative pressure within the pleural cavity. This type of apparatus has been highly successful in both removing fluids from the pleural cavity and in maintaining the desired degree of negativity within the pleural cavity. However, the attachment of an underwater drainage apparatus to a patient's pleural cavity in effect enlarged the pleural cavity to the extent of the size of the collection chamber. This so called "dead air space" within the collection chamber caused the patient additional effort in breathing. While under ordinary circumstances this additonal effort would not be a problem but, in the case of a patient in a weakened condition or a child, the additional air space imposed by the collection chamber may cause severe difficulties in breathing.
The drainage system disclosed in U.S. Pat. No. 4,015,603 was developed to provide a solution to the problems outlined above. Specifically, the underwater drainage apparatus disclosed in Patent No. 4,015,603 limits the dead air space created by attachment of a drainage apparatus by locating the underwater seal directly at the end of the thoracotomy tube. Thus, the volume of the collection chamber itself did not constitute an additional volume in the pleural cavity. This device has proven highly successful but, the location of the underwater seal chamber at the lower end of the thoracotomy tube created a further problem in certain unusual circumstances. In the case of a patient having a blockage in the bronchial tubes, such that the patient was having severe problems in getting air into the lungs, exceedingly high negativity was being created in the pleural cavity. Such high negativity caused the fluid in the underwater seal to be drawn upwardly through the thoracotomy tube and, if the degree of negativity was sufficiently high, it was possible for fluid to reenter the pleural cavity. This condition of fluid from the underwater seal chamber reentering the pleural cavity could cause infection or otherwise create problems for the patient. In addition, it was possible to entirely lose the seal provided by the underwater seal chamber during periods of high negativity in the pleural cavity. The loss of the water seal has the potential for serious damage in the event the suction becomes disconnected or the device is used as a two bottle system with the collection chamber open to atmosphere.

Underwater drainage apparatus with reduced dead air space


Techniques are described for penetrating protective vehicle armor. In one example, a penetrator round assembly comprises a main penetrator rod comprising a tungsten alloy and a solid nose engaged to the main penetrator rod.

Explosive reactive armor is a type of vehicle armor that is designed to reduce the amount of penetration of projectiles, e.g., anti-tank rounds. In general, explosive reactive armor includes an explosive material sandwiched between two plates, e.g., metal plates. The plates and explosive material form a block-like module. Numerous modules are distributed over the base armor of a vehicle, e.g., tank, in order to form a protective layer of explosive reactive armor.
Generally speaking, in operation the explosive reactive armor is designed to deflect a projectile by altering the angle of incidence of the projectile to prevent the projectile from perforating the base armor of the vehicle. More particularly, as the projectile impacts the outermost plate of an explosive reactive armor module, the explosive material ignites. The ignition of the explosive material causes the two plates of the module to be driven apart. As the outer (or cover) plate is driven outward into the projectile, the outer plate damages, e.g., breaks or bends, the penetrator rod of the projectile. As the inner plate is driven inward away from the projectile, a longer path-length is created for the projectile, thereby reducing the chance that the projectile will perforate the vehicle's base armor.


A safety lighter includes a lever adjustable pivotally mounted on a top formed frame above a cover sealed on an upper portion of a lighter container filled with liquid petroleum gas, the lever being slidably thrusted to be locked on a stopper extension formed on the top frame for preventing a depression of the lever for preventing any unexpected sparking and gas ignition operation of the lighter, thereby ensuring a fire protection safety in using the lighter.

A conventional gas lighter, especially a disposable lighter, includes a plastic container filled with liquid petroleum gas, a lever, a striker wheel, a flint, a burner and a gas valve, whereby upon a depression of the lever to open the gas valve and rotate the striker wheel for sparking the flint, a gas stream from the burner will be ignited and burned for producing a lighter flame. However, it is very easy to depress the lever to ignite the lighter gas to cause an accident fire especially when "played" by an innocent child without being cared by his or her parents, possibly causing fire hazard such as burning injury or death to humanbeing or damage to properties.
It is therefore expected to disclose a safety lighter provided with a locking mechanism for preventing an unexpected striking of the lighter for ensuring a safety living.

c/o Hung Hsing Patent Service Center, P.O. Box 55-1670


A vacuum driven pill counter includes a counter housing with a pill discharge aperture formed therein. An integrally formed vacuum drum is rotatably positioned in the housing and the vacuum drum includes a front wall, a rear wall, and a perimeter wall. The front wall of the vacuum drum has a plurality of pill apertures formed therein. A vacuum source communicates with the housing such that the vacuum sources is capable of drawing a vacuum through the pill apertures formed in the vacuum drum and a torque source is operatively connected to the vacuum drum in order to rotate the vacuum drum. A pill shelf is positioned adjacent to the front wall of the vacuum drum and a pill separator removes pills retained on the pill apertures while a pill sensor detects pills which are removed by the pill separator and exit the discharge aperture. Additionally, the pill counter may include a pill feeder. The pill feeder has a frame with a top and bottom aperture and with the bottom aperture being positioned over an opening in the counter housing. A pill reservoir is positioned on the frame to allow pills to flow into the top aperture of the frame. A feed gate positioned within the frame is slidably movable between the top and bottom apertures.

The present invention relates to pill or tablet counting machines. In particular, the present invention relates to counting machines which handle and dispense the pills or tablets by use of a vacuum source.
The prior art includes attempts to utilize a vacuum source to move pills within a pill counting machine; for example U.S. Pat. No. 4,018,358 to Johnston, et al (the xe2x80x9c""358 patentxe2x80x9d). The ""358 patent includes a flat disk with apertures formed along the perimeter of the disk. The disk is placed against a dish-like vacuum drive wheel and a vacuum applied to the drive wheel such that suction is created at each of the apertures in the disk. The disk is positioned such that a collection of loose pills will rest against the disk. The suction force moves pills toward and hold pills against the apertures in the disk. As the disk rotates, the pills are carried with the apertures. At some point along the rotational path of the apertures in the disk, the pills are dislodged from the aperture by a surface adjacent to the disk.
However, there are several disadvantages associated with the device disclosed in the ""358 Patent. For example, the disk is a separate piece from the drive wheel and therefore, must form at least a minimal seal along the entire perimeter of the drive wheel. Additionally, the ""358 Patent teaches the use of a continuously feeding pill cassette to position pills against its flat disk. This can result in an excessive number of pills collecting against the disk which can in turn adversely affect the consistent retention of pills on the disk""s pill apertures. To help alleviate this problem, the ""358 Patent discloses a series of spokes radially extending from the hub on which the disk rotates. The purpose of these spokes is to agitate the pills and prevent them from bridging together. However, these spokes have the undesirable tendency to chip, break, or otherwise damage the pills. Additionally, when striking pills, especially soft or uncoated pills, these spokes tend to create large amounts of dust which create a cross-contamination hazard, degrade the operation of sensors, and clog air filters associated with the vacuum source.
An effective vacuum driven pill counter which overcomes these disadvantages would be a significant improvement in the art.
The present invention provides a vacuum driven pill counter. The counter includes a counter housing with a pill discharge aperture formed therein. An integrally formed vacuum drum is rotatably positioned within the housing and the vacuum drum includes a front wall, a rear wall, and a perimeter wall. The front wall of the vacuum drum has a plurality of pill apertures formed therein. A vacuum source communicates with the housing such that the vacuum source is capable of drawing a vacuum through the pill apertures formed in the vacuum drum and a torque source is operatively connected to the vacuum drum in order to rotate the vacuum drum. A pill shelf is positioned adjacent to the front wall of the vacuum drum and a pill separator removes pills retained on the pill apertures while a pill sensor detects pills which are removed by the pill separator and exit the discharge aperture.
A second embodiment does not have an integrally formed vacuum drum, but does include a pill feeder. The pill feeder has a frame with a top and bottom aperture, with the bottom aperture being positioned over an opening in the counter housing. A pill reservoir is positioned on the frame to allow pills to flow into the top aperture of the frame. A feed gate positioned within the frame is slidably movable between the top and bottom apertures.