CN88100800A - 自由基聚合反应组合物 - Google Patents
自由基聚合反应组合物 Download PDFInfo
- Publication number
- CN88100800A CN88100800A CN88100800.1A CN88100800A CN88100800A CN 88100800 A CN88100800 A CN 88100800A CN 88100800 A CN88100800 A CN 88100800A CN 88100800 A CN88100800 A CN 88100800A
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- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 carbalkoxy Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229930192474 thiophene Natural products 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002850 poly(3-methoxythiophene) polymer Polymers 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 229920000128 polypyrrole Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GCXYLRUBYDEKBY-UHFFFAOYSA-N 4-bromo-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound BrC=1C(C(=C(C(C=1)=O)C#N)C#N)=O GCXYLRUBYDEKBY-UHFFFAOYSA-N 0.000 description 1
- AQZMINLSVARCSL-UHFFFAOYSA-N 4-chloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound ClC1=CC(=O)C(C#N)=C(C#N)C1=O AQZMINLSVARCSL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 101100020289 Xenopus laevis koza gene Proteins 0.000 description 1
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- YLJRCXSSKLWCDE-UHFFFAOYSA-N methyl ethanesulfonate Chemical class CCS(=O)(=O)OC YLJRCXSSKLWCDE-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-N perchloric acid;tetraethylazanium Chemical compound OCl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical compound N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明公开了一种自由基聚合组合物,其组成包括:(A)一种具有π电子共轭结构的化合物和(B)一种能进行自由基聚合的化合物。该组合物可模制成任意形状并具有导电性,因此在电气和电子工业中可作为非常有用的电极和电路的材料。
Description
本发明涉及一种自由基聚合组合物。这种组合物适合于用作电气和电子领域中的材料,例如,用作电容式录象激光盘、电池、电容器和显示器的电极材料,用作电致变色显示元件的材料,印刷电路板的电路材料等。
现今对各种用于电气和电子工业中的导电材料的规格要求越来越变得严格。长期以来已要求导电材料的研制能实现元件重量的减轻和体积的缩减,且同时又能显示出元件的长期稳定性和高效能特性。
为了能适应这些日益提高的规格要求,近来对于使用导电高聚合物以替代习用的碳质材料或金属材料已进行了广泛的研究。现已提出了许多关于应用这种高聚物的建议。到目前为止,已提出的导电高聚物有:杂环高聚物,例如美国专利4,543,402,4,547,270,4,552,927,4,548,696和4,657,985所述的聚噻吩、聚吡咯等,这些导电高聚物被建议用来作蓄电池或电致变色显示元件。
然而,这些杂环高聚物多数是不溶不熔的。因此,它们的模塑加工性能很差,以致实际上未被采用。为了克服这个问题,近来提出了各种工艺。例如,J.C.S.Chem.Commum.第817页(1984)披露了一种由聚吡咯和热塑性树脂如聚氯乙烯制备均匀复合膜的方法,在该方法中,先用一种热塑性树脂涂覆阳极基质的表面,然后再用电解聚合法产生聚吡咯。欧洲专利申请160207A披露,在具有阴离子表面特性的聚合物胶乳存在下使吡咯进行电解聚合可以制得一种加工性能有所改进的导电高聚物复合材料。美国专利4,582,575,4,604,427,4,617,353和4,617,228也揭示了类似的方法。此外,Synthetic Metals,第15卷,169页(1986)报导,在不溶不熔的杂环高聚物中引进长链烷基可得到能溶解于有机溶剂中的杂环高聚物,这种杂环高聚物可模制成在一适当的基质上的覆盖层膜。正如上述工艺所列举的那样,一般的建议都说明如何将预先聚合好的树脂和导电高聚物结合以获得一种复合膜。
然而,这种预先聚合好的树脂和导电高聚物组成的复合材料只不过是一种聚合物掺合料。难以形成微观地均匀的复合膜。换言之,难以获得具有优异的电气效能特性的复合膜。
在电气和电子工业中,近年来越来越广泛地采用能发生自由基聚合反应的化合物进行涂敷,然后通过例如采用紫外线辐照使其聚合,从而实现精密加工。然而,除非采用极其复杂的步骤,否则上述复合成型工艺在精密加工中仍有许多困难,而且所取得的分辨率也有其局限性。
本发明的一个目的是提供一种能模制成任意形状并具有导电性能的自由基聚合组合物。
本发明的上述目的可通过自由基聚合组合物来完成,该组合物含有:
(A)具有π电子共轭结构的化合物;
(B)能进行自由基聚合的化合物。
本发明的具有π电子共轭结构的化合物是一种具有式(Ⅰ)或(Ⅱ)所表示的重复单元的化合物:
式中,X代表NH,S,O,Se或Te;Y1、Y2、Y3及Y4可以相同,也可以不相同,各自可为氢原子,取代或未取代的1至12个碳原子的烷基,烷氧基,烷氧羰基,芳氧羰基,烷氧磺酰基,芳氧磺酰基,或酰氨基,括弧表示重复单元。
式(Ⅰ)和式(Ⅱ)中,Y1至Y4的烷基是带有取代基或不带有取代基的直链或支链烷基,其取代基可为烷氧羰基、芳氧羰基、烷氧磺酰基、芳氧磺酰基或酰氨基(如一烷基酰氨基、二烷基酰氨基和一芳基酰氨基)。烷基具有1至12个碳原子,以具有4至12个碳原子较好,而具有6至12个碳原子更好(如果有取代基的话,包括取代基中的碳原子数在内)。当烷基带有烷氧羰基或芳氧羰基、烷氧磺酰基或芳氧磺酰基、或酰氨基时,则该取代烷基最好具有3至8个碳原子。这些烷基的实例有:-C6H13、-C8H17、-C10H21、-CH2CH2COOCH3、-CH2CH2-SO3CH3及-CH2CH2CONHCH3。Y1至Y4的烷氧基最好是含有1至4个碳原子的直链或支链的烷基部分,如-OCH3和-OC2H5。Y1至Y4的其它基团的实例包括:-COOCH3、-SO3CH3等。Y1至Y4的这些基团中,较好的是氢原子、取代或未取代的烷基以及烷氧基。
式(Ⅰ)中X为-NH-和-S-较好。
具有π电子共轭结构的化合物可有由式(Ⅰ)或式(Ⅱ)所示的两个或多个重复单元。此外,具有式(Ⅰ)重复单元的化合物可和具有式(Ⅱ)重复单元的化合物作为混合物而加以使用。
具有π电子共轭结构的化合物的平均聚合度(重复单元的数目)以5至10,000为较好,以50至10,000为更好,而以100至1000为最好,倘若当式(Ⅰ)或式(Ⅱ)的重复单元中Y1、Y2、Y3和Y4为氢原子和/或具有1至3个碳原子的未取代的烷基时,则平均聚合度取5至小于50较好,取8至20更好。
具有式(Ⅰ)或式(Ⅱ)重复单元的化合物的端基比较理想的是分别由式(Ⅰ)或式(Ⅱ)所示基团衍生出来的单价基团,例如:
式中:X、Y1、Y2、Y3和Y4的定义如上所述。
在具有式(Ⅰ)或式(Ⅱ)所示的重复单元的化合物中,比较好的化合物是那些能溶于可进行自由基聚合的化合物或有机溶剂中的那些化合物,例如噻吩、吡咯、苯胺等的低聚物,具有各种取代基引进于其中的杂环高聚合物和具有各种取代基引进于其中的聚苯胺。这些化合物中最好的是聚〔2,5-噻吩-3-(2-乙磺酸甲酯)〕、聚(2,5-二甲氧基苯胺)、聚(3-己基-2,5-噻吩),聚(3-甲氧基噻吩)和聚〔2,5-吡咯-1-(2-丁磺酸甲酯)〕。
具有π电子共轭结构的化合物可采用常规方法制备,如采用美国专利4,552,927、4,548,696和4,582,575所述的电解聚合法以及美国专利4,604,427、4,617,353和4,617,228所述的化学聚合法制备。
通过将一部份具有π电子共轭结构的化合物氧化或还原,即掺杂,可使这些化合物具有导电性能。实现这种掺杂的适用的工艺已叙述在如“Kagaku Zokau》第87卷,“Gosei Kinzoku”,Kagaku Dojin K.K.和《Handbook of Conducting Polymers》第1卷,第2章,第45-79页,Marcel Dekker Inc.(1986)中。
可用化学方法或电化学方法来实现掺杂。在化学掺杂中,可用各种已知的电子受体或电子给体化合物作为掺杂物,例如(ⅰ)囟素,即碘、溴、和碘化溴,(ⅱ)金属囟化物,如五氟化砷、五氟化锑、四氟化硅、五氯化磷、五氟化磷、氯化铝、溴化铝和氟化铝,(ⅲ)质子酸,如硫酸、硝酸、氟磺酸、三氟甲磺酸和氯磺酸、(ⅳ)氧化剂,如三氧化硫、二氧化氮和过氧化二氟磺酰基,(ⅴ)AgClO4(ⅵ)四氰基乙烯,四氰基醌二甲烷、四氯苯醌、2,3-二氯-5,6-二氰基-对苯醌和2,3-二溴-5,6-二氰基-对苯醌,及(ⅶ)碱金属类,如Li,Na和K。在电化学掺杂中,掺杂物的实例包括(ⅰ)阴离子掺杂物,如Ⅴa或Ⅲa族元素的囟化物阴离子(如PF- 6,SbF- 6,AsF- 6,SbCl- 6,和BF- 4),囟素阴离子(如I-(I- 3),Br-和Cl-),和高氯酸盐阴离子(如ClO- 4),及(ⅱ)阳离子掺杂物,例如碱金属离子(如Li+、Na+、K+、Rb+和Cs+),和R4-XM+HX或R3M′+所表示的阳离子(式中R为1至10个碳原子的烷基或芳基〔如苯基、囟代苯基和烷基苯基),M代表N、P或As,M′代表O或S,x为0或1),(如四烷基铵、四烷基磷、四烷基砷、三烷基氧、和三烷基硫)。但是,在本发明中,掺杂物并不仅限于这些。
在具有π电子共轭结构的化合物中,掺杂剂的含量没有特殊的限制,但是每个重复单元所含的掺杂剂为0.05至1比较好,含0.1至0.4则更好。通过掺杂,具有π电子共轭结构的化合物的直流导电率大于10-5S/cm,较好为大于10-3S/cm。
可用于本发明的能进行自由基聚合的化合物包括各种乙烯衍生物,例如在Jugo Han-noron Koza,第1卷,“Radical Polymerization(Ⅰ)”(自由基聚合反应)第5-9页所述,诸如苯乙烯衍生物(如苯乙烯、二乙烯基苯和氯甲基苯乙烯),丙烯酸酯(如丙烯酸甲酯,环氧丙烯酸酯和三羟甲基丙烷三丙烯酸酯);甲基丙烯酸酯(如甲基丙烯酸甲酯和环氧甲基丙烯酸酯);烯丙基化合物和亚2-丙烯基化合物(如二亚2-丙烯基季戊四醇和烯丙基氯);乙烯基酰胺,乙烯基酰亚胺、乙烯基内酯和乙烯基咔唑(如N-乙烯基吡咯烷酮);以及丙烯酰胺类(如丙烯酰胺和甲基丙烯酰胺)。这些化合物中,丙烯酸酯较好,环氧丙烯酸酯特别好。这些能进行自由基聚合的化合物可单独使用,也可将其中的二种或多种结合使用。
具有π电子共轭结构的化合物与能进行自由基聚合的化合物的混合比没有特别的限制。但为了确保获得足够好的性能,以本发明的具有π电子共轭结构的化合物按重量计占具有π电子共轭结构的化合物和自由基聚合的化合物的总重量的5至50%较为理想,占10至30%更好。
各成分的混合方法也没有特别的限制。但以具有π电子共轭结构的化合物应尽可能地均匀地分散在组合物中较为理想。为此,可在加热下在熔融状态中进行混合或在适当溶剂存在下进行混合,后一种情况下,各组分可在溶剂中均匀混合,然后将溶剂除去。在后一种情况下也可不用除去溶剂而进行聚合反应。溶剂的实例包括氯仿、二氯甲烷、氯苯、四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基亚砜和碳酸亚丙酯。
自由基聚合组合物可含有常用的各种添加剂,例如,自由基聚合引发剂,如各种过氧化物(例如过氧化氢、过氧化苯甲酰、过硫酸铵和过氧化枯烯),偶氮化合物(例如偶氮二异丁腈和偶氮二苯甲酰);和羰基化合物(如二苯甲酮、苯偶烟异丙酯);以及自由基聚合促进剂,例如能促使过氧化物分解的胺类化合物(如N,N-二甲基氨基乙醇和N,N-二甲基苯胺)。
本发明的自由基聚合组合物可通过采用涂敷、喷涂、沉积等工艺技术施加到各种固体基底如金属、半导体、合成树脂、陶瓷、纸张、纤维等的表面上以形成一层覆盖薄膜。本发明的组合物也可在分批生产装置或连续生产装置中进行浇注和干燥以制成任意所需的厚度的薄膜。此外,本组合物还可在各种形状的模具中聚合以制成各种模制制品。
本发明的自由基聚合组合物可在完全没有任限制条件下采用各种能源进行聚合,如采用热能、紫外线、电子辐射线、X-射线等进行聚合。采用紫外线或电子辐射线进行聚合比较适宜,因为此种方法易于操作,而且形成的图案的分辨率令人满意。
在聚合前或聚合后可进行掺杂而使本发明的自由基聚合组合物具有导电性能。但是,必须注意到,许多具有π电子共轭结构的化合物在掺杂后,在溶剂中的溶解性能有变差的趋势,因此后一种方法即聚合后掺杂,对于获得具有令人满意的电气性能的聚合物来说是比较可取的。
本发明的自由基聚合组合物可用作电容式录象激光盘的电极材料。尽管录象激光盘的表面光洁度很高(即粗糙度很细),但由于本发明的组合物的流动性很好,所以仍可用该组合物来制造高度精密的录象激光盘的复制品。此外,本组合物由于采用光固化工艺使得与采用普通方法相比时,可大大提高生产率。
应用本发明的自由基聚合组合物还可使得利用光致抗蚀技术直接地由导电聚合物制备精密图案的电路变为可能。
此外,本发明的组合物用于制造电致变色显示元件时,图案容易形成,而且由于材料的淘析速率低,所以制成的显示元件的寿命有所提高。
本发明的自由基聚合物的特征是具有满意的加工性能并可用于需要利用本发明的组合物的各种特性的各种应用中。
现在参照实例更详细地说明本发明,但是必须指出,不能认为本发明只限于这些实例。在下列实例中,除非另有说明,否则所有的份数、百分数、比值等均按重量计。
实例1
将1克噻吩低聚物(平均聚合度约为12)在加热下溶解在由5克环氧丙烯酸酯树脂(Shown Kobunshi K.K.生产的“Ripoxy sp-1509”)、4克三羟甲基丙烷三丙烯酸酯(Shin-nakamura Kagaku Kogyo K.K.生产的“NK ESTER TMPT”)、1克N-乙烯基-2-吡咯烷酮、0.2克二苯甲酮(自由基聚合引发剂)和0.2克N,N-二甲基氨基乙醇(自由基聚合促进剂)所组成的混合物中,制成均匀的深红色溶液。
将制成的溶液涂敷在ITO玻璃(涂敷氧化铟锡的玻璃,由掺杂有锡掺杂物的氧化铟蒸气沉积在玻璃板上而制备)板上形成约10微米厚的薄膜并用高压水银灯(输出功率为75瓦/厘米)的紫外光在空气中进行辐照以制备涂层电极。
用涂层电极作为工作电极、铂板作为相反电极、银/银离子电极作为参考电极,和浓度为1.0摩尔/升的高氯酸四乙基铵的乙腈溶液制成一个电化学电解池。
将稳压器接到电解池,在基于参考电极的+0.8伏特电压下进行电化学掺杂,深红色的固化膜会变成深蓝色。然后将涂层电极从电解池中取出,用乙腈沏底洗涤后从ITO玻璃板上剥离掉。经测定固化膜的表面电阻率为530欧姆/平方厘米。
实例2
将1克聚〔2,5-噻吩-3(2-乙磺酸甲酯)〕(平均聚合度约为50)倾注入含有1.0克六氟磷酸亚硝酰酯和10毫升硝基甲烷的溶液中,以实现用PF- 6进行化学掺杂,从而制得深蓝色溶液。将此溶液与具有实例1中所用的相同组成的混合物均匀混合,但不用噻吩低聚物,然后减压蒸馏除去其中的硝基甲烷。
将所得混合物涂敷在玻璃板上以形成一层薄膜,并用与实例1相同的方法用紫外光进行辐照以制备固化膜。经测定该膜的表面电阻率为360欧姆/平方厘米。
实例3
将1克苯胺低聚物(平均聚合度约为8)溶解于10毫升N,N-二甲基甲酰胺中。将制成的溶液与具有实例1中相同组成的混合物混合,但没有噻吩低聚物,制成均匀溶液。然后减压蒸馏除去其中的二甲基甲酰胺。
将制成的组合物涂敷在玻璃板上,并以实例1相同的方法用紫外光进行辐照以制备固化膜。若将氯化氢气体施加到固化膜上时,则该膜将由黑蓝色变为绿色,其表面电阻率为2.3千欧姆/平方厘米。
实例4
将1克聚(2,5-二甲氧基苯胺)(平均聚合度为约50)溶解于10毫升乙腈中。所得溶液与具有实例1相同组成的混合物混合,但没有噻吩低聚物。将制成的组合物按实例3的方法进涂敷、固化,接着进行掺杂。制成的固化膜为蓝绿色,而其表面电阻率为5.0千欧姆/平方厘米。
实例5
在加热下,将5克聚(3-己基-2,5-噻吩)(平均聚合度约为500)溶解于由10克环氧丙烯酸酯树脂(Showa Kobunshi K.K.生产的Ripoxy R-806”)和20克苯乙烯组成的混合物中制成均匀的红色溶液。再将1.5克苯偶姻异丙基醚(自由基聚合引发剂)加入到该溶液中。
将制成的溶液涂敷在玻璃板上,其厚度为20微米,然后用一高压水银灯(输出功率为75瓦/厘米)的紫外光在空气中进行辐照以制备固化膜。再将固化膜暴露于碘蒸汽中以实现掺杂。经测定该膜的表面电阻率为150欧姆/平方厘米。
实例6
在加热下,将1.5克用对-甲苯磺酸掺杂过的聚(2,5-二甲氧基苯胺)(平均聚合度约为100)与螺缩醛树脂(Showa Kobunshi K.K.生产的“Spilac N-4N-7”)混合,然后再加入0.2克苯偶姻异丙基醚以制备均匀溶液。
用制成的溶液重复实例5中相同的程序以制得掺杂过的固化膜,其表面电阻率为750欧姆/平方厘米。
上面已参考具体实例对本发明进行了详细的说明,对于本技术领域中的技术人员来说,很明显,可对本发明作出各种改变或改进,然而却不背离本发明的实质精神和范围。
Claims (15)
1、一种自由基聚合组合物,其组成包括:
(A)一种具有n电子共轭结构的化合物;
(B)一种能进行自由基聚合的化合物。
3、按权利要求2所述的自由基聚合组合物,其中所述的化合物(A)具有式(Ⅰ)所示的重复单元。
4、按权利要求3所述的自由基聚合组合物,其中所述化合物(A)是噻吩低聚物、吡咯低聚物、聚〔2,5-噻吩-3-(2-乙磺酸甲酯)〕、聚(3-己基-2,5-噻吩),聚(3-甲氧基噻吩),或聚〔2,5-吡咯-1-(2-丁磺酸甲酯)〕。
6、按权利要求2所述的自由基聚合组合物,其中所述的化合物(A)具有式(Ⅱ)所示的重复单元。
7、按权利要求6所述的自由基聚合化合物,其中所述一化合物(A)是苯胺低聚物或聚(2,5-二甲氧基苯胺)。
9、按权利要求2所述的自由基聚合组合物,其中X代表NH或S,Y1、Y2、Y3和Y4各自可代表氢原子、取代或未取代的含有3至12个碳原子的烷基,或含1至4个碳原子的烷氧基。
10、按权利要求2所述的自由基聚合组合物,其中所述的化合物(A)的重复单元数目取5至10,000。
11、按权利要求10所述的自由基聚合组合物,其中所述化合物(A)的重复单元的数目取50至10,000,但式(Ⅰ)中的重复单元中的Y1和Y2或式(Ⅱ)中的重复单元中的Y1、Y2、Y3和Y4为氢原子和/或未取代的含1至3个碳原子的烷基时,重复单元数目取5至小于50。
12、按权利要求11所述的自由基聚合组合物,其中所述的化合物(A)具有式(Ⅰ)所示的重复单元,Y1和Y2各自可代表氢原子,含有2个或3个碳原子的取代的烷基,和/或取代或未取代的含4至12个碳原子的烷基,但Y1和Y2不得同时为氢原子,X代表NH或S,重复单元数目取50至10,000。
13、按权利要求1所述的自由基聚合组合物,其中所述的化合物(B)是苯乙烯,环氧丙烯酸酯、二亚2-丙烯基季戊四醇、环氧甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、甲基丙烯酸甲酯、N-乙烯基吡咯烷酮或这些化合物的混合物。
14、按权利要求2所述的自由基聚合组合物,其中所述的化合物(A)的含量占所述的化合物(A)和(B)的总重量的5至50%。
15、按权利要求14所述的自由基聚合组合物,其中所述的化合物(A)的含量占所述化合物(A)和(B)的总重量的10至30%。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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JP41265/87 | 1987-02-25 | ||
JP4126587 | 1987-02-25 | ||
JP30583/88 | 1988-02-12 | ||
JP63030583A JP2578881B2 (ja) | 1987-02-25 | 1988-02-12 | ラジカル重合性組成物 |
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CN93100806A Division CN1028645C (zh) | 1987-02-25 | 1993-01-05 | 自由基聚合反应组合物 |
Publications (2)
Publication Number | Publication Date |
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CN88100800A true CN88100800A (zh) | 1988-09-21 |
CN1022759C CN1022759C (zh) | 1993-11-17 |
Family
ID=26368964
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Application Number | Title | Priority Date | Filing Date |
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CN88100800A Expired - Fee Related CN1022759C (zh) | 1987-02-25 | 1988-02-25 | 自由基聚合反应组合物 |
CN93100806A Expired - Fee Related CN1028645C (zh) | 1987-02-25 | 1993-01-05 | 自由基聚合反应组合物 |
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Application Number | Title | Priority Date | Filing Date |
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CN93100806A Expired - Fee Related CN1028645C (zh) | 1987-02-25 | 1993-01-05 | 自由基聚合反应组合物 |
Country Status (6)
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---|---|
US (2) | US4962158A (zh) |
EP (1) | EP0280173B1 (zh) |
JP (1) | JP2578881B2 (zh) |
CN (2) | CN1022759C (zh) |
CA (1) | CA1327587C (zh) |
DE (1) | DE3886430T2 (zh) |
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CN108292568A (zh) * | 2015-11-27 | 2018-07-17 | 松下知识产权经营株式会社 | 电化学设备及其制造方法 |
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-
1988
- 1988-02-12 JP JP63030583A patent/JP2578881B2/ja not_active Expired - Fee Related
- 1988-02-17 DE DE88102293T patent/DE3886430T2/de not_active Expired - Fee Related
- 1988-02-17 EP EP88102293A patent/EP0280173B1/en not_active Expired - Lifetime
- 1988-02-25 CN CN88100800A patent/CN1022759C/zh not_active Expired - Fee Related
- 1988-02-25 CA CA000559856A patent/CA1327587C/en not_active Expired - Fee Related
- 1988-02-25 US US07/160,431 patent/US4962158A/en not_active Expired - Lifetime
-
1990
- 1990-05-18 US US07/525,810 patent/US5137993A/en not_active Expired - Lifetime
-
1993
- 1993-01-05 CN CN93100806A patent/CN1028645C/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108292568A (zh) * | 2015-11-27 | 2018-07-17 | 松下知识产权经营株式会社 | 电化学设备及其制造方法 |
CN108292568B (zh) * | 2015-11-27 | 2020-09-22 | 松下知识产权经营株式会社 | 电化学设备及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
US5137993A (en) | 1992-08-11 |
JPS6420202A (en) | 1989-01-24 |
EP0280173B1 (en) | 1993-12-22 |
CN1028645C (zh) | 1995-05-31 |
CA1327587C (en) | 1994-03-08 |
EP0280173A3 (en) | 1990-05-23 |
DE3886430T2 (de) | 1994-05-05 |
JP2578881B2 (ja) | 1997-02-05 |
CN1022759C (zh) | 1993-11-17 |
EP0280173A2 (en) | 1988-08-31 |
US4962158A (en) | 1990-10-09 |
DE3886430D1 (de) | 1994-02-03 |
CN1074918A (zh) | 1993-08-04 |
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