CN1297588C - 基于聚吡咯的聚合物膜及其应用 - Google Patents
基于聚吡咯的聚合物膜及其应用 Download PDFInfo
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- CN1297588C CN1297588C CNB038204274A CN03820427A CN1297588C CN 1297588 C CN1297588 C CN 1297588C CN B038204274 A CNB038204274 A CN B038204274A CN 03820427 A CN03820427 A CN 03820427A CN 1297588 C CN1297588 C CN 1297588C
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- acid
- polymeric film
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- 229920006254 polymer film Polymers 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 229920000128 polypyrrole Polymers 0.000 claims description 37
- 125000001072 heteroaryl group Chemical group 0.000 claims description 32
- 239000000835 fiber Substances 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 27
- 125000003367 polycyclic group Chemical group 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- -1 amino m-phthalic acid Chemical compound 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000004693 Polybenzimidazole Substances 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002480 polybenzimidazole Polymers 0.000 claims description 10
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000003205 fragrance Substances 0.000 claims description 9
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 9
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims description 4
- SQJQLYOMPSJVQS-UHFFFAOYSA-N 4-(4-carboxyphenyl)sulfonylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C=C1 SQJQLYOMPSJVQS-UHFFFAOYSA-N 0.000 claims description 4
- VNLYHYHJIXGBFX-UHFFFAOYSA-N 4-(trifluoromethyl)phthalic acid Chemical compound OC(=O)C1=CC=C(C(F)(F)F)C=C1C(O)=O VNLYHYHJIXGBFX-UHFFFAOYSA-N 0.000 claims description 4
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 claims description 4
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 claims description 4
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical compound CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 claims description 3
- FOMVFKTYQSZBMJ-UHFFFAOYSA-N 1,5-dihydroxycyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound OC(=O)C1C=CC(O)=CC1(O)C(O)=O FOMVFKTYQSZBMJ-UHFFFAOYSA-N 0.000 claims description 3
- UKGMFBZPIQCNPM-UHFFFAOYSA-N 1,6-dihydroxycyclohexa-3,5-diene-1,2-dicarboxylic acid Chemical compound OC(=O)C1C=CC=C(O)C1(O)C(O)=O UKGMFBZPIQCNPM-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical group C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 3
- QXGJCWSBOZXWOV-UHFFFAOYSA-N 3,4-dihydroxyphthalic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1C(O)=O QXGJCWSBOZXWOV-UHFFFAOYSA-N 0.000 claims description 3
- CCOAVTLOSPJPGO-UHFFFAOYSA-N C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.N3C=CC=CC=C3 Chemical class C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.N3C=CC=CC=C3 CCOAVTLOSPJPGO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 238000001728 nano-filtration Methods 0.000 claims description 3
- 229920002577 polybenzoxazole Polymers 0.000 claims description 3
- GMIOYJQLNFNGPR-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C=N1 GMIOYJQLNFNGPR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- WFNRNCNCXRGUKN-UHFFFAOYSA-N 2,3,5,6-tetrafluoroterephthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(C(O)=O)C(F)=C1F WFNRNCNCXRGUKN-UHFFFAOYSA-N 0.000 claims description 2
- NXRWBYFOLHCASC-UHFFFAOYSA-N 2-[carboxy-(carboxymethylamino)methyl]benzoic acid Chemical compound OC(=O)CNC(C(O)=O)C1=CC=CC=C1C(O)=O NXRWBYFOLHCASC-UHFFFAOYSA-N 0.000 claims description 2
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 2
- YJLVXRPNNDKMMO-UHFFFAOYSA-N 3,4,5,6-tetrafluorophthalic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1C(O)=O YJLVXRPNNDKMMO-UHFFFAOYSA-N 0.000 claims description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims description 2
- MMHLSHSAOIJBHI-UHFFFAOYSA-N 5-(3-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 MMHLSHSAOIJBHI-UHFFFAOYSA-N 0.000 claims description 2
- LQEZHWGJSWHXPJ-UHFFFAOYSA-N 5-(4-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C(O)=O)=CC(C(O)=O)=C1 LQEZHWGJSWHXPJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- NLNRQJQXCQVDQJ-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 NLNRQJQXCQVDQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229930016911 cinnamic acid Natural products 0.000 claims description 2
- 235000013985 cinnamic acid Nutrition 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229960004979 fampridine Drugs 0.000 claims description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical class C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000004448 titration Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims 2
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 claims 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims 1
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 claims 1
- XFFZVIRSYFJKEX-UHFFFAOYSA-N 4-phenylpyridine-2,5-dicarboxylic acid Chemical compound C1=NC(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O XFFZVIRSYFJKEX-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical class C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims 1
- HLRLQGYRJSKVNX-UHFFFAOYSA-N pyrimidine-2,4-dicarboxylic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=N1 HLRLQGYRJSKVNX-UHFFFAOYSA-N 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
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- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003233 pyrroles Chemical class 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 3
- 230000006353 environmental stress Effects 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
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- 229910021536 Zeolite Inorganic materials 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- LMAQRGNIWKAAFR-UHFFFAOYSA-N benzene;dicarboxy carbonate Chemical class C1=CC=CC=C1.OC(=O)OC(=O)OC(O)=O LMAQRGNIWKAAFR-UHFFFAOYSA-N 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
- 229920001577 copolymer Polymers 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical group O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
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- 238000007664 blowing Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- OEFVJAZWSLPDEP-UHFFFAOYSA-N n-(2,2-dimethylpropylidene)hydroxylamine Chemical compound CC(C)(C)C=NO OEFVJAZWSLPDEP-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052674 natrolite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- HJEYCIXFDZNPMJ-UHFFFAOYSA-N piperazine;quinoline Chemical compound C1CNCCN1.N1=CC=CC2=CC=CC=C21 HJEYCIXFDZNPMJ-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Abstract
本发明涉及基于聚吡咯的新聚合物膜、聚合物纤维和聚合物,由于其优异的化学和热性质而可用于各种目的,特别是用作气体净化和过滤的薄膜或膜。
Description
本发明涉及基于聚吡咯的新聚合物膜,由于其优异的化学和热性质而可用于各种目的,特别是用作气体净化和过滤的薄膜。
聚吡咯如聚苯并咪唑(Celazole)很久以前就为人们所知。此类聚苯并咪唑经常通过3,3’,4,4’-四氨基联苯与间苯二酸或二苯基间苯二酸或其酯在熔融状态下反应来制备。形成的预聚物在反应器中固化然后被机械粉碎。然后粉碎的聚合物在高至400℃温度下进行固相聚合以完全聚合得到所需聚苯并咪唑。
为制备聚合物膜,PBI在另外的步骤中溶解于极性非质子溶剂如二甲基乙酰胺(DMAc)中,并以经典方法制备膜。然而,完全除去溶剂不是简单的,需要相当大的费用。适用于此的方法公开于德国专利申请10109829.4中。
本发明的目的是提供基于聚吡咯的聚合物膜,首先其具有或超过基于聚吡咯的聚合物膜的使用性能,其次其可以简单的方式得到。
我们现已发现基于聚吡咯的聚合物膜可通过以下方法得到:将母单体悬浮或溶解于在多磷酸中,用刮刀分散形成薄层并在多磷酸中聚合。
本发明提供一种基于聚吡咯的聚合物膜,其可通过包括以下步骤的方法得到
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体中含有至少两个酸基的芳香羧酸和/或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸与多磷酸混合,以形成溶液和/或分散体,
B)用步骤A)中的混合物涂覆支撑体形成层,
C)将步骤B)中得到的薄片状结构/层在惰性气体中加热至高达350℃的温度,优选高达280℃,以形成聚吡咯聚合物,
D)处理步骤C)中形成的聚合物膜(直至其可自支撑),
E)将步骤D)中形成的聚合物膜与该支撑体分离,其中步骤E)不是绝对需要的(当制备复合膜/多层膜时),
F)除去多磷酸或磷酸并干燥。
本发明所用的芳香和杂芳香四氨基化合物优选是3,3’,4,4’-四氨基联苯,2,3,5,6-四氨基吡啶,1,2,4,5-四氨基苯,双(3,4-二氨基苯基)砜,双(3,4-二氨基苯基)醚,3,3’,4,4’-四氨基苯甲酮,3,3’,4,4’-四氨基二苯基甲烷和3,3’,4,4’-四氨基二苯基二甲基甲烷及其盐,特别是它们的单-,二-,三-及四盐酸盐衍生物。
本发明所用的芳香羧酸为二酸、三羧酸及四羧酸、或其酯、其酸酐或其酸氯化物。芳香二羧酸优选为间苯二酸,对苯二酸,邻苯二酸,5-羟基间苯二酸,4-羟基间苯二酸,2-羟基对苯二酸,5-氨基间苯二酸,5-N,N-二甲基氨基间苯二酸,5-N,N-二乙基氨基间苯二酸,2,5-二羟基对苯二酸,2,6-二羟基间苯二酸,4,6-二羟基间苯二酸,2,3-二羟基邻苯二酸,2,4-二羟基邻苯二酸,3,4-二羟基邻苯二酸,3-氟邻苯二酸,5-氟间苯二酸,2-氟对苯二酸,四氟邻苯二酸,四氟间苯二酸,四氟对苯二酸,1,4-萘二羧酸,1,5-萘二羧酸,2,6-萘二羧酸,2,7-萘二羧酸,联苯甲酸,1,8-二羟基萘-3,6-二酸,双(4-羧苯基)醚,苯甲酮-4,4’-二酸,双(4-羧苯基)砜,联苯-4,4’二酸,4-三氟甲基邻苯二酸,2,2-双(4-羧苯基)六氟丙烷,4,4’-芪二酸,4-羧基肉桂酸或其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物。芳香三羧酸、四羧酸或其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物优选为1,3,5-苯三羧酸(均苯三羧酸),1,2,4-苯三羧酸(偏苯三羧酸),(2-羧苯基)亚氨基二乙酸,3,5,3’-联苯三羧酸,3,5,4’-联苯三羧酸。
芳香四羧酸或其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物优选为3,5,3’,5’-联苯四羧酸,1,2,4,5-苯四羧酸,苯甲酮四羧酸,3,3’,4,4’-联苯四羧酸,2,2’,3,3’-联苯四羧酸,1,2,5,6-萘四羧酸,1,4,5,8-萘四羧酸。
本发明所用的杂芳香酸为杂芳香二羧酸、三羧酸及四羧酸、或其酯或其酸酐。对于本发明,杂芳香酸是在芳香部分含有至少一个氮、氧、硫或磷原子的芳香系统。优选为吡啶-2,5-二酸,吡啶-3,5-二酸,吡啶-2,6-二酸,吡啶-2,4-二酸,4-苯基-2,5-吡啶二酸,3,5-吡唑二酸,2,6-嘧啶二酸,2,5-吡嗪二酸,2,4,6-吡啶三羧酸,苯并咪唑-5,6-二酸,及其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物。
三羧酸或四羧酸的含量(按所用的二酸计)为0~30mol%,优选为0.1~20mol%,特别是0.5~10mol%。
本发明所用的芳香及杂芳香二氨基羧酸优选为二氨基苯甲酸及其单盐酸盐和二盐酸盐衍生物。
在步骤A)中优选使用至少两种不同芳香羧酸的混合物。特别优选使用含有芳香羧酸与杂芳香羧酸的混合物。芳香羧酸与杂芳香羧酸的混合比例为1∶99~99∶1,优选1∶50~50∶1。
特别地,这些混合物是N-杂芳香二羧酸与芳香二羧酸的混合物。非限制性实例是间苯二酸,对苯二酸,邻苯二酸,2,5-二羟基对苯二酸,2,6-二羟基间苯二酸,4,6-二羟基间苯二酸,2,3-二羟基邻苯二酸,2,4-二羟基邻苯二酸,3,4-二羟基邻苯二酸,1,4-萘二羧酸,1,5萘二羧酸,2,6-萘二羧酸,2,7-萘二羧酸,联苯甲酸,1,8-二羟基萘-3,6-二酸,双(4-羧苯基)醚,苯甲酮-4,4’-二酸,双(4-羧苯基)砜,联苯-4,4’-二酸,4-三氟甲基邻苯二酸,吡啶-2,5-二酸,吡啶-3,5-二酸,吡啶-2,6-二酸,吡啶-2,4-二酸,4-苯基-2,5-吡啶-二酸,3,5-吡唑二酸,2,6-嘧啶二酸,2,5-吡嗪二酸。
步骤A)中所用的多磷酸为市售多磷酸,如购自Riedel-de Haen。多磷酸Hn+2PnO3n+1(n>1)通常以P2O5量计算(酸滴定)的纯度至少为83%。还可能制备分散液/悬浮液来代替单体的溶液。步骤A)中所得混合物中多磷酸与所有单体的重量比为1∶10000~10000∶1,优选1∶1000~1000∶1,更优选1∶100~100∶1。
步骤B)中的薄层可由聚合物膜制备领域中公知的方法形成(浇铸、喷涂、刮涂)。适合的支撑体可以是在各条件下惰性的支撑体。除了这些惰性支撑体外,也可使用与步骤B)中形成的层结合以形成层压片的其他支撑体,如聚合物膜、织物及非织物。为调节粘度,如果需要可将磷酸(浓磷酸,85%)加到溶液中。通过此方法,粘度可调节至所需值且更易于形成膜。
步骤B)中制得的层其厚度与随后的应用相匹配,而没有任何限制。通常形成的层厚度为1~5000μm,优选为1~3500μm,特别是1~100μm。
步骤C)中形成的基于聚吡咯的聚合物包含通式(I)和/或(II)和/或(III)和/或(IV)和/或(V)和/或(VI)和/或(VII)和/或(VIII)和/或(IX)和/或(X)和/或(XI)和/或(XII)和/或(XIII)和/或(XIV)和/或(XV)和/或(XVI)和/或(XVII)和/或(XVIII)和/或(XIX)和/或(XX)和/或(XXI)和/或(XXII)所示的重复吡咯单元:
其中
基团Ar是相同的或不同的,每一个可以是单环或多环的四价芳基或杂芳基,
基团Ar1是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团Ar2是相同的或不同的,每一个可以是单环或多环的二价或三价芳基或杂芳基,
基团Ar3是相同的或不同的,每一个可以是单环或多环的三价芳基或杂芳基,
基团Ar4是相同的或不同的,每一个可以是单环或多环的三价芳基或杂芳基,
基团Ar5是相同的或不同的,每一个可以是单环或多环的四价芳基或杂芳基,
基团Ar6是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团Ar7是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团Ar8是相同的或不同的,每一个可以是单环或多环的三价芳基或杂芳基,
基团Ar9是相同的或不同的,每一个可以是单环或多环的二价、三价或四价芳基或杂芳基,
基团Ar10是相同的或不同的,每一个可以是单环或多环的二价或三价芳基或杂芳基,
基团Ar11是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团X是相同的或不同的,每一个是氧、硫或氨基,该氨基带有氢原子、含1~20个碳原子的基团,优选为作为进一步基团的支链的或非支链的烷基或烷氧基或芳基,
基团R是相同的或不同的,每一个是氢、烷基或芳基,条件是式XX中的R是二价基团,及
n、m每一个是大于或等于10、优选大于或等于100的整数。
优选的芳基或杂芳基衍生自苯、萘、联苯、二苯醚、二苯甲烷、二苯基二甲基甲烷、二苯酮、二苯砜、喹啉、吡啶、联吡啶、哒嗪、嘧啶、吡嗪、三嗪、吡咯、吡唑、蒽、苯并吡咯、苯并三唑、苯并氧杂噻二唑、苯并噁二唑、苯并吡啶、苯并吡嗪、苯并吡嗪烷、苯并嘧啶、苯并吡嗪、苯并三嗪、中氮茚、喹啉嗪、吡啶并吡啶、咪唑并嘧啶、吡嗪并嘧啶、咔唑、吖啶、吩嗪、苯并喹啉、吩噁嗪、吩噻嗪、吖啶嗪、苯并蝶啶、菲咯啉和菲,它们也可以是取代的。
Ar1、Ar4、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11可以是任何取代型的,在亚苯基情况下,例如Ar1、Ar4、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11可以是邻亚苯基、间亚苯基和对亚苯基。特别优选的基团衍生自苯和亚联苯基,它们也可以是取代的。
优选的烷基包括具有1~4个碳原子的短链烷基,如甲基、乙基、正丙基或异丙基及叔丁基。
优选的芳基包括苯基或萘基。烷基和芳基可以是取代的。
优选的取代基包括卤素原子例如氟、氨基、羟基或短链烷基如甲基或乙基。
具有式(I)的重复单元的聚吡咯是优选的,其中一个重复单元内的基团X是相同的。
聚吡咯一般也可以含不同的重复单元,例如,它们的基团X可以不同。然而优选地,重复单元中只含相同的基团X。
其他优选的聚吡咯聚合物是聚咪唑、聚苯并噻唑、聚苯并噁唑、聚噁二唑、聚喹喔啉、聚噻二唑、聚吡啶、聚嘧啶和聚四氮杂芘。
在本发明的另一个实施方案中,含重复吡咯单元的聚合物是含式(I)~(XXII)中至少两个彼此不同单元的共聚物或混合物。聚合物可以是嵌段共聚物(二嵌段、三嵌段)、无规共聚物、周期共聚物和/或交替聚合物的形式。
在本发明一个特别优选的实施方案中,含有重复吡咯单元的聚合物是仅含式(I)和/或式(II)单元的聚吡咯。
优选地,聚合物中重复吡咯单元的数目大于或等于10。特别优选的聚合物包含至少100个重复吡咯单元。
在本发明中,包含重复苯并咪唑单元的聚合物是优选的。以下式子表明了含重复苯并咪唑单元的最合适的聚合物的某些例子:
其中,n和m每一个是大于或等于10、优选为大于或等于100的整数。
通过所述方法制得的聚吡咯,特别是聚苯并咪唑具有高分子量。测得的固有粘度至少为1.4dl/g,因而显著高于市售聚苯并咪唑(IV<1.1dl/g)。
如果步骤A)中制得的混合物中含有三羧酸或四羧酸,那么会引起形成的聚合物支化/交联。这有助于机械性能的改进。在水份存在下在一定温度下处理步骤C)中制得的聚合物层,时间足以使该层具备在应用中所需的足够强度。处理可进行至膜是自支撑的,从而可从支撑体上脱离下来而不会损坏(步骤E)。
在本方法的一个变体中,低聚物和/或聚合物的形成可通过将步骤A)所得混合物加热至高达350℃,优选高至280℃来得到。取决于所选温度和时间,步骤C)中的热处理可部分或全部省去。这种变体也是本发明的主题。
另外,已发现当使用芳香二羧酸(或杂芳香二羧酸)如间苯二酸,对苯二酸,2,5-二羟基对苯二酸,4,6-二羟基间苯二酸,2,6-二羟基间苯二酸,联苯甲酸,1,8-二羟基萘-3,6-二酸,双(4-羧苯基)醚,苯甲酮-4,4’-二酸,双(4-羧苯基)砜,联苯-4,4’-二酸,4-三氟甲基苯二酸,吡啶-2,5-二酸,吡啶-3,5-二酸,吡啶-2,6-二酸,吡啶-2,4-二酸,4-苯基-2,5-吡啶-二酸,3,5-吡唑二酸,2,6-嘧啶二酸,2,5-吡嗪二酸时,或如果希望在此步骤中形成低聚物和/或聚合物,步骤C)或步骤A)中的温度范围高至300℃,优选为100-250℃是有利的。
步骤D)中膜的处理在高于0℃并低于150℃的温度下进行,优选温度为10~120℃,特别优选室温(20℃)~90℃,并存在水汽和/或水和/或水蒸汽和/或含水磷酸(高至85%)。处理优选在常压下进行,但也可在高压下进行。重要的是在足量水份下处理,多磷酸的存在可通过部分水解形成低分子量的多磷酸和/或磷酸而有助于增强膜。
步骤D)中多磷酸的部分水解有助于增强聚合物膜,从而使其自支撑并降低层厚度。
步骤B)中所得多磷酸薄层的分子内及分子间结构(穿插网络,IPN)导致在步骤C)中形成有序膜,其对应于所形成聚合物膜的特殊性质。
在步骤D)中处理温度的上限通常为150℃。如果水份作用的时间极短,例如在过热蒸汽时,蒸汽也可高于150℃。温度的上限取决于处理时间。
部分水解(步骤D)也可在温度和潮气可控制的室中进行,其中水解可在预定量水份作用下进行具体控制。可以通过温度或与聚合物膜接触的饱和环境如气体(例如空气、氮气、二氧化碳或其他适合的气体或水蒸汽)来具体设置湿度。处理时间取决于上述的参数。
处理时间也取决于膜的厚度。
一般地,处理时间为几秒至几分钟,例如在过热气流的作用下,或几整天,例如在空气中在室温下及低相对大气湿度下。处理时间优选为10秒至300小时,特别是1分钟至200小时。
如果部分水解在室温(20℃)下、使用环境空气、相对湿度为40~80%的条件下进行,那么处理时间为1~200小时。
步骤D)中得到的聚合物膜优选是自支撑的,即在步骤E)其可与支持物分离而不会损伤,并随后在需要时可直接进一步使用。
如果步骤C)中得到的聚合物膜在支撑体上进一步处理,例如制造复合膜,那么步骤D)可完全或部分省略。在这种情况下,如果多磷酸在随后的处理中不起作用,那么对步骤E)和步骤F)也相似。这种变体也是本发明的主题。
在步骤E)之后,在聚合物膜中存在的多磷酸或磷酸在步骤F)中被除去。这可利用处理液体在室温(20℃)至处理液体的沸点(大气压)间的温度下进行。
用于本发明并适用于步骤F)的处理液体是在室温(20℃)下为液体形式的溶剂,其选自醇、酮、烷烃(脂肪族和环脂肪族)、醚(脂肪族和环脂肪族)、二醇、酯、羧酸,其中上述基团可被卤化,也可使用水及其混合物。
优选使用C1~C10醇、C2~C5酮、C1~C10烷烃(脂肪族和环脂肪族)、C2~C6醚(脂肪族和环脂肪族)、C2~C5酯、C1~C3羧酸、二氯甲烷、水及其混合物。
随后再除去在步骤F)中引入的处理液体,优选通过干燥实现,其中温度和环境压力被选作为处理液体的蒸汽分压的函数。通常干燥在20~200的温度下在大气压下进行。也可在减压下进行更温和的干燥。可以不经干燥而轻拍薄膜,从而除去过量的处理液体。顺序不是关键的。
在步骤F)的处理后,可在氧气存在下对聚合物膜进行热交联。膜表面的这种硬化进一步提高了性能。这种处理可部分地或全部地代替上述的干燥,或与其混合使用。
交联也可在IR或NIR的作用下进行(IR=红外线,即波长超过700nm的光;NIR=近红外线,即波长约为700~2000nm或能量约为0.6~1.75eV的光)。另一种方法是用β射线。辐射量为5~200kGy。
此外,在步骤F)的处理后,也可用硫酸进行热后处理。这也进一步提高了表面性能。
本发明的聚合物膜与以前公知的聚合物膜相比表现出改进的材料性能。
此外,本发明的聚合物膜不仅表现出基于聚吡咯的分离膜的公知优点,例如高热稳定性及耐化学性,而且由于相对较高分子量的结果具有改进的机械性能。这使长期稳定性和寿命增大,并提高了分离性能。
然而,特别的是这些聚合物膜不含有仅能以高成本或不能彻底除去的杂质。
这种分离膜可生产成致密聚合物膜、多孔中空纤维膜或多孔聚合物膜,或需要时制成复合膜(包括具有不同开孔度的多层,部分带有薄的致密膜)。这些层由不同的聚合物层组成或可从另一种聚合物生产成一体的非对称膜。
为制备多孔膜,步骤A)的聚合物溶液可进一步包括孔形成剂,如甘油。
多孔膜可用甘油填充以在生产后稳定各孔。
在步骤F)的处理过程中,溶剂替换可形成公知的孔结构。取决于沉淀的组成,以这种方式可以得到不同形态的分离膜。对各别应用而言,优选的是下面的结构:i)对称多孔结构;ii)在接近于一个膜表面具有致密聚合物的非对称多孔结构,及iii)用薄选择性的聚合物层涂覆的i)和ii)的多孔膜。此外,各层也可由不同聚合物组成。这种特别有用的聚苯并咪唑膜的扫描电子显微图公开于Journal of MembraneScience,Vol 20,1984,p147-66中。
这种相转化膜和结构对于本领域所属技术人员是公知的。具有非对称或对称多孔结构的膜被用作分离或过滤膜,用于空气和气体过滤或微滤或超滤及液体的透析。由薄致密选择性层涂覆到具有非对称多孔结构或复合膜上而构成的膜可以各种方式用于反渗透、纳滤,特别是用于水的脱盐,或气体净化。致密膜也可用于电渗析或电解。
特别有利的应用是从气体混合物与多孔金属支撑体中分离氢及二氧化碳。由于聚合物膜的低热稳定性,另一种分离CO2的技术需要将气体冷却至150℃,从而降低了效率。本发明的聚吡咯基分离膜可在高达400℃的范围内操作,从而产率提高,成本降低。
对于基于聚吡咯的分离膜的进一步信息,可参考专门文献,尤其是专利WO 98/14505;US-A-4693815;US-A-4693824;US-A-375262;US-A-3737042;US-A-4512894;US-A-448687;US-A-38411492。本发明参考上述文献中对分离膜的结构和制备的说明,并引入本说明书作为参考。特别地,这种分离膜可以平面膜或中空纤维膜的形式制备。
为更进一步提高使用性能,可以向聚合物膜中加入填充剂。可以在步骤A)中或聚合之后加入。
这种填充剂非限制性的例子包括:
氧化物,如:Al2O3、Sb2O5、ThO2、SnO2、ZrO2、MoO3,
硅酸盐,如:沸石、沸石(NH4 +)、层状硅酸盐、网状硅酸盐、H-钠沸石、H-丝光沸石、NH4-方沸石(analcines)、NH4-方钠石、NH4-镓酸盐、H-蒙脱石,
填充剂,如:碳化物,特别是SiC、Si3N4;纤维,特别是玻璃纤维;玻璃粉和/或优选基于聚吡咯的聚合物纤维。
此外,聚合物膜还可含有可清除或破坏在气体过滤过程中形成的自由基的添加剂。这种添加剂非限制性的例子是:双(三氟甲基)硝基氧,2,2’-二苯基-1-苦味碱基偕腙肼,苯酚,烷基酚,立体位阻的烷基酚如Irganox,芳香胺,立体位阻的胺如Chimassorb;立体位阻的羟胺,立体位阻的烷基胺,立体位阻的羟胺,立体位阻的羟胺醚,亚磷酸盐如Irgafos,亚硝基苯,甲基-2-亚硝基丙烷,苯甲酮,苯甲醛叔丁基硝酮,半胱胺,三聚氰胺,铅氧化物,锰氧化物,镍氧化物,钴氧化物。
使用本发明聚合物膜的可能领域尤其包括作为气体过滤的过滤介质,气体分离或气体净化领域中的膜,及反渗透、纳滤、超滤、微滤、渗析、电渗析中的膜。它们也可作为柔性电路的基底、作为电池隔板、作为电解中的膜、作为电缆的保护膜、在电子元件和器件如电容器中作为绝缘体、作为金属和其他表面的保护膜。
本发明还提供一种基于具有上述特征且以固有粘度表达的分子量至少为1.4dl/g的聚吡咯的聚合物,其可通过包括以下步骤的方法得到
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体中含有至少两个酸基的芳香羧酸和/或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸与多磷酸混合,以形成溶液和/或分散体,
B)将步骤A)中得到的混合物在惰性气体中加热至高达350℃的温度,优选高达280℃,以形成聚吡咯聚合物,
C)沉淀步骤B)中形成的聚合物,分离并干燥得到的聚合物粉末。
步骤A)和B)的优选实施方案上面已有陈述,因此在这里没有重复。步骤C)中的沉淀可通过将步骤B)的材料加到沉淀浴中进行。这种加入在室温(20℃)至沉淀液体的沸点(大气压)间的温度下进行。
用于本发明并适用于步骤C)的沉淀液体是在室温(20℃)下为液体形式的溶剂,其选自醇、酮、烷烃(脂肪族和环脂肪族)、醚(脂肪族和环脂肪族)、酯、羧酸,其中上述基团可被卤化,也可使用水、无机酸(如H3PO4、H2SO4)及其混合物。
优选使用C1~C10醇、C2~C5酮、C1~C10烷烃(脂肪族和环脂肪族)、C2~C6醚(脂肪族和环脂肪族)、C2~C5酯、C1~C3羧酸、二氯甲烷、水及其混合物。
随后再使沉淀的聚合物不含沉淀液体,优选通过干燥实现,其中温度和环境压力被选作为处理液体的蒸汽分压的函数。通常干燥在20~200℃的温度下在大气压下进行。也可在减压下进行更温和的干燥。对干燥方法没有限制。
通过所述方法制得的聚吡咯,特别是聚苯并咪唑具有高分子量。测得的固有粘度至少为1.4dl/g,优选至少为1.5dl/g,因而显著高于市售聚苯并咪唑(IV<1.1dl/g)。
以这种方法得到的聚合物粉末尤其适合作为制备成形体的原料,特别是薄膜和纤维。
本发明还提供一种基于以固有粘度表达的分子量至少为1.4dl/g的聚吡咯的聚合物纤维,其可通过包括以下步骤的方法得到
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体中含有至少两个酸基的芳香羧酸和/或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸与多磷酸混合,以形成溶液和/或分散体,
B)将步骤A)中得到的混合物在惰性气体中加热至高达350℃的温度,优选高达280℃,以形成聚吡咯聚合物,
C)挤出步骤B)中形成的聚吡咯聚合物,以形成纤维,
D)将步骤C)中形成的纤维加到液体浴中,
E)分离并干燥得到的纤维。
步骤A)和B)的优选实施方案上面已有陈述,因此在这里没有重复。
步骤C)中的挤出通过公知的纤维形成方法进行。形成的纤维可以是连续丝,或如果通过相似于“熔吹法”的方法形成纤维,其具有人造短纤维的特性。对形成的纤维厚度没有任何限制,因此也可制备单纤丝,即线状纤维。此外,也可制备空心纤维。所需的厚度可根据纤维的用途确定。形成的纤维的总处理可通过公知的纤维技术进行。
在本发明的变体中,步骤C)中挤出的聚吡咯聚合物预先用气体饱和。所有在选定的条件下是惰性的气体都适于此目的。饱和优选在超临界状态下进行,从而气体经随后膨胀形成孔。这种技术以商标MuCell而公知。将MuCell的技术应用至本发明方法上从而首次得到聚吡咯聚合物的微泡沫,特别是基于如下聚合物的泡沫:聚咪唑、聚苯并噻唑、聚苯并噁唑、聚噁二唑、聚喹喔啉、聚噻二唑、聚吡啶、聚嘧啶和聚四氮杂芘。
步骤C)中的挤出后,形成的纤维加到沉淀浴。这种加入在室温(20℃)至沉淀液体的沸点(大气压)间的温度下进行。
用于本发明并适用于步骤C)的沉淀液体是在室温(20℃)下为液体形式的溶剂,其选自醇、酮、烷烃(脂肪族和环脂肪族)、醚(脂肪族和环脂肪族)、酯、羧酸,其中上述基团可被卤化,也可使用水、无机酸(如H3PO4、H2SO4)及其混合物。
优选使用C1~C10醇、C2~C5酮、C1~C10烷烃(脂肪族和环脂肪族)、C2~C6醚(脂肪族和环脂肪族)、C2~C5酯、C1~C3羧酸、二氯甲烷、水及其混合物。
随后再使纤维不含沉淀液体,优选通过干燥实现,其中温度和环境压力被选作为处理液体的蒸汽分压的函数。通常干燥在20~200℃的温度下在大气压下进行。也可在减压下进行更温和的干燥。对干燥方法没有限制。
沉淀浴中的处理也可形成多孔基底。取决于应用,这些在随后应用中可能需要。
在一个变体中,步骤C)挤出后形成的纤维可进行步骤D)所述的处理。纤维的处理在高于0℃并低于150℃的温度下进行,优选温度为10~120℃,特别优选室温(20℃)~90℃,并存在水汽和/或水和/或水蒸汽和/或含水磷酸(高至85%)。处理优选在常压下进行,但也可在高压下进行。重要的是在足量水份下处理,多磷酸的存在可通过部分水解形成低分子量的多磷酸和/或磷酸而有助于增强纤维。
多磷酸的部分水解有助于增强纤维,从而使其自支撑并降低纤维厚度。
多磷酸薄层中的分子内及分子间结构(穿插网络,IPN)导致形成有序的聚合物结构,其对应于所形成纤维的良好性质。
处理温度的上限通常为150℃。如果水份作用的时间极短,例如在过热蒸汽时,蒸汽也可高于150℃。温度的上限取决于处理时间。
部分水解(步骤D)也可在温度和潮气可控制的室中进行,其中水解可在预定量水份作用下进行具体控制。可以通过温度或与纤维接触的饱和环境如气体(例如空气、氮气、二氧化碳或其他适合的气体或水蒸汽)来具体设置湿度。处理时间取决于上述的参数。
处理时间也取决于纤维的厚度。
一般地,处理时间为几分之一秒至几秒,例如在过热气流的作用下,或加热的湿空气中。
一般地,也可在室温(20℃)下使用环境空气在相对湿度为40~80%的条件下进行处理。然而,这会增大处理时间。
Claims (39)
1.一种基于聚吡咯的聚合物膜,其可通过包括以下步骤的方法得到
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体中含有至少两个酸基的芳香羧酸或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸混入多磷酸中,以形成溶液和/或分散体,
B)用步骤A)中的混合物涂覆支撑体,
C)将步骤B)中得到的薄片状结构/层在惰性气体中在高达350℃的温度下加热,以形成聚吡咯聚合物,
D)处理步骤C)中形成的聚合物膜(直至其可自支撑),
E)将步骤D)中形成的聚合物膜与该支撑体分离,
F)除去存在的多磷酸或磷酸并干燥。
2.如权利要求1所述的聚合物膜,其特征在于C)步骤中将步骤B)中得到的薄片状结构层在高达280℃下加热。
3.如权利要求1所述的聚合物膜,其特征在于所用的芳香四氨基化合物是3,3’,4,4’-四氨基联苯,2,3,5,6-四氨基吡啶,1,2,4,5-四氨基苯,双(3,4-二氨基苯基)砜,双(3,4-二氨基苯基)醚,3,3’,4,4’-四氨基苯甲酮,3,3’,4,4’-四氨基二苯基甲烷和3,3’,4,4’-四氨基二苯基二甲基甲烷。
4.如权利要求1所述的聚合物膜,其特征在于所用的芳香二羧酸是间苯二酸,对苯二酸,邻苯二酸,5-羟基间苯二酸,4-羟基间苯二酸,2-羟基对苯二酸,5-氨基间苯二酸,5-N,N-二甲基氨基间苯二酸,5-N,N-二乙基氨基间苯二酸,2,5-二羟基对苯二酸,2,5-二羟基间苯二酸,2,3-二羟基间苯二酸,2,3-二羟基邻苯二酸,2,4-二羟基邻苯二酸,3,4-二羟基邻苯二酸,3-氟邻苯二酸,5-氟间苯二酸,2-氟对苯二酸,四氟邻苯二酸,四氟间苯二酸,四氟对苯二酸,1,4-萘二羧酸,1,5-萘二羧酸,2,6-萘二羧酸,2,7-萘二羧酸,联苯甲酸,1,8-二羟基萘-3,6-二羧酸,双(4-羧苯基)醚,苯甲酮-4,4’-二羧酸,双(4-羧苯基)砜,联苯-4,4’二羧酸,4-三氟甲基邻苯二酸,2,2-双(4-羧苯基)六氟丙烷,4,4’-芪二羧酸,4-羧基肉桂酸或其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物。
5.如权利要求1所述的聚合物膜,其特征在于所用的芳香羧酸是三羧酸或其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物。
6.如权利要求5所述的聚合物膜,其特征在于所用的芳香羧酸是1,3,5-苯三羧酸(均苯三酸),1,2,4-苯三羧酸(偏苯三酸),(2-羧苯基)亚氨基二乙酸,3,5,3’-联苯三羧酸,3,5,4’-联苯三羧酸和/或2,4,6-吡啶三羧酸。
7.如权利要求1所述的聚合物膜,其特征在于所用的芳香羧酸是四羧酸或其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物。
8.如权利要求7所述的聚合物膜,其特征在于所用的芳香羧酸是1,2,4,5-苯四羧酸,1,4,5,8-萘四羧酸,3,5,3’,5’-联苯四羧酸,苯甲酮四羧酸,3,3’,4,4’-联苯四羧酸,2,2’,3,3’-联苯四羧酸,1,2,5,6-萘四羧酸,1,4,5,8-萘四羧酸。
9.如权利要求4所述的聚合物膜,其特征在于(按所用的二酸计)三羧酸和/或四羧酸的含量为0~30mol%。
10.如权利要求6所述的聚合物膜,其特征在于(按所用的二酸计)三羧酸和/或四羧酸的含量为0.1~20mol%。
11.如权利要求6所述的聚合物膜,其特征在于(按所用的二酸计)三羧酸和/或四羧酸的含量为0.5~10mol%。
12.如权利要求1所述的聚合物膜,其特征在于所用的杂芳香酸是在芳香部分含有至少一个氮、氧、硫或磷原子的杂芳香二羧酸、杂芳香三羧酸和杂芳香四羧酸。
13.如权利要求12所述的聚合物膜,其特征在于所用的杂芳香酸是吡啶-2,5-二羧酸,吡啶-3,5-二羧酸,吡啶-2,6-二羧酸,吡啶-2,4-二羧酸,4-苯基-2,5-吡啶二羧酸,3,5-吡唑二羧酸,2,6-嘧啶二羧酸,2,5-吡嗪二羧酸,2,4,6-吡啶三羧酸,苯并咪唑-5,6-二羧酸,及其C1-C20烷基酯或其C5-C12芳基酯或其酸酐或其酸氯化物。
14.如权利要求1所述的聚合物膜,其特征在于步骤A)中所用多磷酸以P2O5量计算(酸滴定)的分析值至少为83%。
15.如权利要求1所述的聚合物膜,其特征在于步骤A)中制备溶液或分散体/悬浮液。
16.如权利要求1所述的聚合物膜,其特征在于步骤C)中形成的聚吡咯基聚合物包含通式(I)和/或(II)和/或(III)和/或(IV)和/或(V)和/或(VI)和/或(VII)和/或(VIII)和/或(IX)和/或(X)和/或(XI)和/或(XII)和/或(XIII)和/或(XIV)和/或(XV)和/或(XVI)和/或(XVII)和/或(XVIII)和/或(XIX)和/或(XX)和/或(XXI)和/或(XXII)所代表的重复吡咯单元:
其中
基团Ar是相同的或不同的,每一个可以是单环或多环的四价芳基或杂芳基,
基团Ar1是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团Ar2是相同的或不同的,每一个可以是单环或多环的二价或三价芳基或杂芳基,
基团Ar3是相同的或不同的,每一个可以是单环或多环的三价芳基或杂芳基,
基团Ar4是相同的或不同的,每一个可以是单环或多环的三价芳基或杂芳基,
基团Ar5是相同的或不同的,每一个可以是单环或多环的四价芳基或杂芳基,
基团Ar6是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团Ar7是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团Ar8是相同的或不同的,每一个可以是单环或多环的三价芳基或杂芳基,
基团Ar9是相同的或不同的,每一个可以是单环或多环的二价、三价或四价芳基或杂芳基,
基团Ar10是相同的或不同的,每一个可以是单环或多环的二价或三价芳基或杂芳基,
基团Ar11是相同的或不同的,每一个可以是单环或多环的二价芳基或杂芳基,
基团X是相同的或不同的,每一个是氧、硫或氨基,该氨基带有氢原子、含1~20个碳原子的基团,作为另外的基团,
基团R是相同的或不同的,每一个是氢、烷基或芳基,条件是式XX中的R是不是氢,及
n、m每一个是大于或等于10的整数。
17.如权利要求16所述的聚合物膜,其特征在于对于基团X,所述氨基带有支链的或非支链的烷基或烷氧基或芳基。
18.如权利要求16所述的聚合物膜,其特征在于n、m每一个是大于或等于100的整数。
19.如权利要求1所述的聚合物膜,其特征在于步骤C)中形成的聚合物选自聚苯并咪唑、聚吡啶、聚嘧啶、聚咪唑、聚苯并噻唑、聚苯并噁唑、聚噁二唑、聚喹喔啉、聚噻二唑和聚四氮杂芘。
21.如权利要求20所述的聚合物膜,其特征在于n和m每一个是大于或等于100的整数。
22.如权利要求1所述的聚合物膜,其特征在于通过在步骤A)之后及步骤B)之前加入磷酸来调节粘度。
23.如权利要求1所述的聚合物膜,其特征在于步骤C)中所得膜在水汽存在下在一定温度下处理足够的时间,直到膜可自支撑且可从支撑体上脱离下来而不会损坏。
24.如权利要求1所述的聚合物膜,其特征在于在水汽和/或水和/或水蒸汽存在下,在步骤D)中在高于0℃并低于150℃的温度下处理膜。
25.如权利要求24所述的聚合物膜,其特征在于在水汽和/或水和/或水蒸汽存在下,在步骤D)中在10~120℃的温度下处理膜。
26.如权利要求24所述的聚合物膜,其特征在于在水汽和/或水和/或水蒸汽存在下,在室温(20℃)~90℃的温下处理膜。
27.如权利要求1所述的聚合物膜,其特征在于步骤D)中膜的处理进行10秒至300小时。
28.如权利要求27所述的聚合物膜,其特征在于步骤D)中膜的处理进行1分钟至200小时。
29.如权利要求1所述的聚合物膜,其特征在于在步骤F)中通过处理液体从而除去多磷酸或磷酸。
30.如权利要求1所述的聚合物膜,其特征在于省略步骤D)中的处理。
31.如权利要求1所述的聚合物膜,其特征在于步骤D)处理后的聚合物膜不是自支撑的,并保留在支撑体上以进行进一步处理。
32.如权利要求1~31中任一项所述的聚合物膜作为气体过滤的过滤介质,气体分离和/或气体净化领域中的膜、及反渗透、纳滤、超滤、微滤、渗析、电渗析中的膜,作为电路的基底、作为电池隔板、作为电解中的膜、作为电缆的保护膜、在电子元件和器件如电容器中作为绝缘体、作为金属和其他表面的保护膜的用途。
33.一种基于如权利要求16~20中任一项所述且以固有粘度表达的分子量至少为1.4dl/g的聚吡咯基聚合物,其可通过包括以下步骤的方法得到
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体中含有至少两个酸基的芳香羧酸和/或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸混入多磷酸中,以形成溶液和/或分散体,
B)将步骤A)中得到的混合物在惰性气体中在高达350℃的温度下加热,以形成聚吡咯聚合物,
C)沉淀步骤B)中形成的聚合物,分离并干燥得到的聚合物粉末。
34.如权利要求33的聚吡咯基聚合物,其特征在于在步骤B)中将步骤A)中得到的混合物在惰性气体中在高达280℃的温度下加热。
35.一种基于如权利要求16~20中任一项所述且以固有粘度表达的分子量至少为1.4dl/g的聚吡咯基聚合物纤维,其可通过包括以下步骤的方法得到
A)将一种或多种芳香四氨基化合物与一种或多种每个羧酸单体中含有至少两个酸基的芳香羧酸和/或其酯混合,或将一种或多种芳香和/或杂芳香二氨基羧酸混入多磷酸中,以形成溶液和/或分散体,
B)将步骤A)中得到的混合物在惰性气体中在高达350℃的温度下加热,以形成聚吡咯聚合物,
C)挤出步骤B)中形成的聚吡咯聚合物,以形成纤维,
D)将步骤C)中形成的纤维引入液体浴中,
E)分离并干燥得到的纤维。
36.如权利要求35的聚吡咯基聚合物,其特征在于在步骤B)中将步骤A)中得到的混合物在惰性气体中在高达280℃的温度下加热。
37.如权利要求35所述的聚合物纤维,其特征在于步骤C)中形成的纤维引入到沉淀浴中。
38.如权利要求35所述的聚合物纤维,其特征在于步骤C)中挤出的聚吡咯聚合物用气体饱和,从而经随后的膨胀气体形成孔。
39.如权利要求38所述的聚合物纤维,其特征在于所述气体在超临界状态下。
Applications Claiming Priority (2)
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---|---|---|---|
DE10239701A DE10239701A1 (de) | 2002-08-29 | 2002-08-29 | Polymerfolie auf Basis von Polyazolen und deren Verwendung |
DE10239701.5 | 2002-08-29 |
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Families Citing this family (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10110752A1 (de) * | 2001-03-07 | 2002-09-19 | Celanese Ventures Gmbh | Verfahren zur Herstellung einer Membran aus verbrücktem Polymer und Brennstoffzelle |
DE10117686A1 (de) * | 2001-04-09 | 2002-10-24 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
TW573053B (en) * | 2001-09-10 | 2004-01-21 | Anelva Corp | Surface processing apparatus |
DE10235358A1 (de) * | 2002-08-02 | 2004-02-12 | Celanese Ventures Gmbh | Protonenleitende Polymermembran umfassend Phosphonsäuregruppen enthaltende Polymere und deren Anwendung in Brennstoffzellen |
DE10242708A1 (de) * | 2002-09-13 | 2004-05-19 | Celanese Ventures Gmbh | Protonenleitende Membranen und deren Verwendung |
DE10246461A1 (de) * | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Protonenleitende Polymermembran enthaltend Polyazolblends und deren Anwendung in Brennstoffzellen |
DE10246372A1 (de) * | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Mit einer Katalysatorschicht beschichtete protonenleitende Polymermembran enthaltend Polyazole und deren Anwendung in Brennstoffzellen |
DE10246373A1 (de) * | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Protonenleitende Polymermembran umfassend Sulfonsäuregruppen enthaltende Polyazole und deren Anwendung in Brennstoffzellen |
DE10246459A1 (de) * | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Protonenleitende Polymermembran umfassend Phosphonsäuregruppen enthaltende Polyazole und deren Anwendung in Brennstoffzellen |
EP1652259A2 (de) | 2003-07-27 | 2006-05-03 | Pemeas GmbH | Protonenleitende membran und deren verwendung |
DE602006019572D1 (de) | 2005-03-28 | 2011-02-24 | Du Pont | Heisse oberflächen-hydrolyse von polyphosphorsäure in spun-garnen |
DE602006008770D1 (de) | 2005-03-28 | 2009-10-08 | Du Pont | Verfahren zur hydrolyse von polyphosphorsäure in geformten artikeln |
KR101327632B1 (ko) | 2005-03-28 | 2013-11-12 | 마젤란 시스템즈 인터내셔날, 엘엘시 | 폴리아렌아졸 필라멘트 중 폴리인산의 가수분해 방법 |
US7683157B2 (en) | 2005-03-28 | 2010-03-23 | E.I. Du Pont De Nemours And Company | Process for the production of polyarenazole polymer |
US7754846B2 (en) | 2005-03-28 | 2010-07-13 | E. I. Du Pont De Nemours And Company | Thermal processes for increasing polyareneazole inherent viscosities |
EP1871933B1 (en) | 2005-03-28 | 2011-01-12 | Magellan Systems International, Inc. | Fusion-free hydrolysis of polyphosphoric acid in spun multifilament yarns |
JP4769293B2 (ja) | 2005-03-28 | 2011-09-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ポリアレーンアゾールヤーンの製造方法 |
WO2006105076A2 (en) | 2005-03-28 | 2006-10-05 | E.I. Du Pont De Nemours And Company | Processes for preparing monomer complexes |
KR101324822B1 (ko) | 2005-03-28 | 2013-11-01 | 마젤란 시스템즈 인터내셔날, 엘엘시 | 높은 고유 점도 중합체 및 그로부터의 섬유 |
US7906615B2 (en) | 2005-03-28 | 2011-03-15 | Magellan Systems International, Llc | Process for hydrolyzing polyphosphoric acid in a spun yarn |
JP5302674B2 (ja) | 2005-03-28 | 2013-10-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 金属粉末を使用する固有粘度が高いポリアレンアゾールの製造法 |
DE602006019570D1 (de) | 2005-03-28 | 2011-02-24 | Du Pont | Verfahren zur entfernung von kationen aus polyarenazol-fasern |
US7683122B2 (en) | 2005-03-28 | 2010-03-23 | E. I. Du Pont De Nemours And Company | Processes for increasing polymer inherent viscosity |
US7888457B2 (en) | 2005-04-01 | 2011-02-15 | E. I. Du Pont De Nemours And Company | Process for removing phosphorous from a fiber or yarn |
DE102005020604A1 (de) * | 2005-05-03 | 2006-11-16 | Pemeas Gmbh | Brennstoffzellen mit geringerem Gewicht und Volumen |
CN101273484B (zh) * | 2005-07-01 | 2011-01-19 | 巴斯夫燃料电池有限责任公司 | 气体扩散电极、膜电极组件及其制造方法 |
US8945736B2 (en) | 2005-09-10 | 2015-02-03 | Basf Fuel Cell Gmbh | Method for conditioning membrane-electrode-units for fuel cells |
DE102005051887A1 (de) * | 2005-10-29 | 2007-05-03 | Pemeas Gmbh | Membran für Brennstoffzellen, enthaltend Polymere, die Phosphonsäure-und/oder Sulfonsäuregruppen umfassen, Membran-Elektroden-Einheit und deren Anwendung in Brennstoffzellen |
DE102005052378A1 (de) * | 2005-10-31 | 2007-05-03 | Pemeas Gmbh | Verbesserte Membran-Elektrodeneinheiten und Brennstoffzellen mit hoher Lebensdauer |
US20080317946A1 (en) * | 2007-06-21 | 2008-12-25 | Clearedge Power, Inc. | Fuel cell membranes, gels, and methods of fabrication |
EP2401066B1 (en) * | 2009-02-25 | 2017-10-25 | Council of Scientific & Industrial Research | A polybenzimidazole based premembrane for deacidification; a process for the preparation of the membrane from the premembrane and a process of deacidification |
US20100227250A1 (en) * | 2009-03-03 | 2010-09-09 | Clearedge Power, Inc. | Rigidity & Inplane Electrolyte Mobility Enhancement for Fuel Cell Eletrolyte Membranes |
EP2366729B1 (en) * | 2009-04-24 | 2015-01-07 | Samsung Electronics Co., Ltd. | Cross-linked polyazole, method of preparing the polyazole, electrode for fuel cell including the cross-linked polyazole, electrolyte membrane for fuel cell including the cross-linked polyazole, method of manufacturing the electrolyte membrane, and fuel cell including the cross-linked polyazole |
WO2010145827A2 (de) * | 2009-06-20 | 2010-12-23 | Basf Se | Polyazol-haltige zusammensetzung |
WO2011003538A1 (de) | 2009-07-09 | 2011-01-13 | Basf Se | Methode zur mechanischen stabilisierung von stickstoffhaltigen polymeren |
WO2011003539A1 (de) | 2009-07-09 | 2011-01-13 | Basf Se | Verfahren zur stabilisierung von stickstoffhaltigen polymeren |
JP5305162B2 (ja) * | 2009-08-20 | 2013-10-02 | 東洋紡株式会社 | 多孔質材料を用いた燃料電池用触媒 |
US20110189581A1 (en) * | 2010-02-04 | 2011-08-04 | Samsung Electronics Co., Ltd. | Compound, cross-linked material thereof, double cross-linked polymer thereof, and electrolyte membrane, electrode for fuel cell and fuel cell including same |
US9051433B2 (en) | 2010-02-04 | 2015-06-09 | Samsung Electronics Co., Ltd. | Polymer and cross-linked polymer composition, electrode and electrolyte membrane including cross-linked polymer, and fuel cell including electrode and electrolyte membrane |
US9112232B2 (en) * | 2010-02-05 | 2015-08-18 | Samsung Electronics Co., Ltd. | Composition, polymer thereof, electrode and electrolyte membrane for fuel cell, and fuel cell including the same |
KR101670966B1 (ko) * | 2010-02-09 | 2016-11-09 | 삼성전자주식회사 | 하이퍼브랜치 폴리머, 이를 포함한 연료전지용 전극과 전해질막 및 이를 채용한 연료전지 |
WO2011108861A2 (en) | 2010-03-03 | 2011-09-09 | Samsung Electronics Co., Ltd. | Composition, method of preparing the composition, electrode including the composition, and fuel cell including the electrode |
EP2363820B1 (en) * | 2010-03-04 | 2019-07-03 | Karlsruher Institut für Technologie | Method and system for determining the solvent accessible surface and its derivates of a molecule |
US8802318B2 (en) | 2010-05-14 | 2014-08-12 | Samsung Electronics Co., Ltd. | Compound and composition including compound, with fuel cell, fuel cell electrode and fuel cell electrolyte membrane using same |
CN104080842A (zh) * | 2010-05-31 | 2014-10-01 | 巴斯夫欧洲公司 | 机械稳定的聚唑 |
GB201012080D0 (en) | 2010-07-19 | 2010-09-01 | Imp Innovations Ltd | Asymmetric membranes for use in nanofiltration |
EP2466675B1 (en) | 2010-12-14 | 2013-10-02 | Samsung Electronics Co., Ltd. | Conductive composition and method of preparation, polymer thereof, and electrode, electrolyte membrane and fuel cell including the composition or polymer |
US9178237B2 (en) | 2010-12-14 | 2015-11-03 | Samsung Electronics Co., Ltd. | Conductive composition and method of preparation, polymer thereof, and electrode, electrolyte membrane and fuel cell including the composition or polymer |
US8461296B2 (en) | 2011-03-24 | 2013-06-11 | Basf Se | Method for mechanical stabilization of nitrogen-containing polymers |
KR101840817B1 (ko) | 2011-03-25 | 2018-03-21 | 삼성전자 주식회사 | 연료전지용 전해질막, 연료전지용 전극 및 이를 채용한 연료전지 |
US9006339B2 (en) | 2011-05-10 | 2015-04-14 | Basf Se | Mechanically stabilized polyazoles comprising at least one polyvinyl alcohol |
WO2012153172A1 (de) * | 2011-05-10 | 2012-11-15 | Basf Se | Mechanisch stabilisierte polyazole enthaltend mindestens einen polyvinylalkohol |
KR101890741B1 (ko) | 2011-06-15 | 2018-09-28 | 삼성전자주식회사 | 연료전지용 복합 전해질막, 그 제조방법 및 이를 채용한 연료전지 |
KR20130020000A (ko) | 2011-08-18 | 2013-02-27 | 삼성전자주식회사 | 다공성막, 이를 포함하는 전해질막, 그 제조방법 및 이를 채용한 연료전지 |
KR101910577B1 (ko) | 2011-11-16 | 2018-12-31 | 삼성전자주식회사 | 조성물, 이로부터 형성된 복합체, 이를 이용한 전극과 복합막 및 이를 채용한 연료전지 |
WO2013111732A1 (ja) * | 2012-01-24 | 2013-08-01 | 公益財団法人名古屋産業科学研究所 | 気体分離膜 |
US9283523B2 (en) | 2012-05-25 | 2016-03-15 | Pbi Performance Products, Inc. | Acid resistant PBI membrane for pervaporation dehydration of acidic solvents |
KR101411464B1 (ko) * | 2013-02-12 | 2014-06-27 | 한국과학기술연구원 | 카르도 폴리벤즈이미다졸 공중합체, 기체분리막 및 그 제조방법 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775215A (en) * | 1986-10-31 | 1988-10-04 | Hoechst Celanese Corporation | Nonlinear optical devices |
US5633337A (en) * | 1995-01-26 | 1997-05-27 | The United States Of America As Represented By The Secretary Of The Air Force | Aromatic benzobisazole polymers and copolymers incorporating diphenylamino moieties |
CN1606585A (zh) * | 2001-04-09 | 2005-04-13 | 赛拉尼斯温特斯股份有限公司 | 质子导电膜及其应用 |
Family Cites Families (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL128296C (zh) | 1959-11-18 | |||
NL268724A (zh) | 1960-08-31 | |||
GB1000525A (en) | 1962-07-20 | 1965-08-04 | Teijin Ltd | Process for preparation of polybenzimidazoles |
JPS501707B1 (zh) | 1969-12-20 | 1975-01-21 | ||
US3808305A (en) | 1971-07-27 | 1974-04-30 | H Gregor | Crosslinked,interpolymer fixed-charge membranes |
US4187333A (en) | 1973-05-23 | 1980-02-05 | California Institute Of Technology | Ion-exchange hollow fibers |
DE2450670A1 (de) | 1974-10-25 | 1976-04-29 | Benckiser Gmbh Joh A | Verfahren zur abtrennung von citrat oder citronensaeure aus fermentationsloesungen |
US4012303A (en) | 1974-12-23 | 1977-03-15 | Hooker Chemicals & Plastics Corporation | Trifluorostyrene sulfonic acid membranes |
JPS5397988A (en) | 1977-02-08 | 1978-08-26 | Toyo Soda Mfg Co Ltd | Production of cation exchange membrane |
FR2485395B1 (fr) | 1980-06-24 | 1986-04-11 | Commissariat Energie Atomique | Membrane echangeuse de cations, son procede de fabrication et son application en tant qu'electrolyte solide |
US4634530A (en) | 1980-09-29 | 1987-01-06 | Celanese Corporation | Chemical modification of preformed polybenzimidazole semipermeable membrane |
US4622276A (en) | 1983-12-16 | 1986-11-11 | Stauffer Chemical Company | Fuel cell electrolyte |
US5098985A (en) | 1988-10-11 | 1992-03-24 | The Dow Chemical Company | Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties |
US5218076A (en) | 1989-08-31 | 1993-06-08 | The Dow Chemical Company | Branch polybenzazole polymer and method of preparation |
US5091500A (en) | 1990-09-21 | 1992-02-25 | The Dow Chemical Company | Polybenzazole polymer containing perfluorocyclobutane rings |
US5211984A (en) | 1991-02-19 | 1993-05-18 | The Regents Of The University Of California | Membrane catalyst layer for fuel cells |
CA2153973A1 (en) | 1993-01-15 | 1994-07-21 | Christopher Andreola | Process for producing ion exchange membranes, and the ion exchange membranes produced thereby |
US5312895A (en) | 1993-03-12 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Air Force | Benzobisazole copolymer system soluble in aprotic solvents |
JP3527740B2 (ja) | 1993-04-28 | 2004-05-17 | マゼラン システムズ インターナショナル,エルエルシー | ピリドビスイミダゾールに基く剛直なロッドポリマー |
CH691209A5 (de) | 1993-09-06 | 2001-05-15 | Scherrer Inst Paul | Herstellungsverfahren für einen Polmerelektrolyten und elektrochemische Zelle mit diesem Polymerelektrolyten. |
US5492996A (en) | 1995-02-21 | 1996-02-20 | The United States Of America As Represented By The Secretary Of The Air Force | Alcohol soluble benzazole polymers |
US5599639A (en) | 1995-08-31 | 1997-02-04 | Hoechst Celanese Corporation | Acid-modified polybenzimidazole fuel cell elements |
DE19548421B4 (de) | 1995-12-22 | 2004-06-03 | Celanese Ventures Gmbh | Verfahren zur kontinuierlichen Herstellung von Membranelektrodeneinheiten |
DE19650478A1 (de) | 1996-12-05 | 1998-06-10 | Daimler Benz Ag | Lackiertes metallisches Substrat mit einer korrosionsschützenden Haftschicht auf Basis von Polysäuren und Verfahren zum Aufbringen der Haftschicht |
DE19653484A1 (de) | 1996-12-20 | 1998-06-25 | Fraunhofer Ges Forschung | Verfahren zur Herstellung von Membran-Elektroden-Einheiten und eine so hergestellte Membran-Elektroden-Einheit |
EP0893165A3 (de) | 1997-06-28 | 2000-09-20 | Degussa-Hüls Aktiengesellschaft | Bioaktive Beschichtung von Oberflächen unter Verwendung von Makroinitiatoren |
DE19727554A1 (de) | 1997-06-28 | 1999-01-07 | Huels Chemische Werke Ag | Verfahren zur Hydrophilierung der Oberfläche polymerer Substrate mit einem Makroinitiator als Primer |
US6248469B1 (en) | 1997-08-29 | 2001-06-19 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JP2001514431A (ja) | 1997-08-29 | 2001-09-11 | フオスター・ミラー・インコーポレイテツド | 複合固体ポリマー電解質膜 |
US6030718A (en) | 1997-11-20 | 2000-02-29 | Avista Corporation | Proton exchange membrane fuel cell power system |
US6110616A (en) | 1998-01-30 | 2000-08-29 | Dais-Analytic Corporation | Ion-conducting membrane for fuel cell |
US6087032A (en) | 1998-08-13 | 2000-07-11 | Asahi Glass Company Ltd. | Solid polymer electrolyte type fuel cell |
FI107932B (fi) | 1999-02-16 | 2001-10-31 | Mikael Paronen | Polymeerikalvo ja menetelmä sen valmistamiseksi |
AU2831000A (en) | 1999-03-08 | 2000-09-28 | Center For Advanced Science And Technology Incubation, Ltd. | Electrolytic membrane for fuel cell and its manufacturing method, and fuel cell and its manufacturing method |
DE60029731T8 (de) | 1999-11-29 | 2007-11-08 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Fester Polymerelektrolyt mit hoher Dauerhaftigkeit |
JP3656244B2 (ja) | 1999-11-29 | 2005-06-08 | 株式会社豊田中央研究所 | 高耐久性固体高分子電解質及びその高耐久性固体高分子電解質を用いた電極−電解質接合体並びにその電極−電解質接合体を用いた電気化学デバイス |
AU2907801A (en) | 1999-12-16 | 2001-06-25 | Proton Energy Systems, Inc. | Low gravity electrochemical cell |
WO2001094450A2 (en) | 2000-06-02 | 2001-12-13 | Sri International | Polymer membrane composition |
DE10052242A1 (de) | 2000-10-21 | 2002-05-02 | Celanese Ventures Gmbh | Mit Säure dotierte, ein- oder mehrschichtige Kunststoffmembran mit Schichten aufweisend Polymerblends umfassend Polymere mit wiederkehrenden Azoleinheiten, Verfahren zur Herstellung solche Kunststoffmembranen sowie deren Verwendung |
US7288603B2 (en) | 2000-11-13 | 2007-10-30 | Toyo Boseki Kabushiki Kaisha | Polybenzazole compound having sulfonic acid group and/or phosphonic acid group, resin composition containing the same, resin molding, solid polymer electrolyte membrane, solid polymer electrolyte membrane/electrode assembly and method of preparing assembly |
JP2002146014A (ja) | 2000-11-15 | 2002-05-22 | Toyobo Co Ltd | イオン伝導性ホスホン酸含有ポリアゾール |
JP4200224B2 (ja) * | 2000-11-15 | 2008-12-24 | 東洋紡績株式会社 | イオン伝導性スルホン酸含有ポリアゾール |
JP2002146013A (ja) * | 2000-11-15 | 2002-05-22 | Toyobo Co Ltd | イオン伝導性ホスホン酸含有ポリアゾール |
JP2002201269A (ja) * | 2001-01-09 | 2002-07-19 | Toyobo Co Ltd | 新規なイオン性基含有ポリベンズアゾール及びそれを主成分とする膜 |
DE10109829A1 (de) | 2001-03-01 | 2002-09-05 | Celanese Ventures Gmbh | Polymermembran, Verfahren zu deren Herstellung sowie deren Verwendung |
DE10117687A1 (de) * | 2001-04-09 | 2002-10-17 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
DE10129458A1 (de) | 2001-06-19 | 2003-01-02 | Celanese Ventures Gmbh | Verbesserte Polymerfolien auf Basis von Polyazolen |
JP2003022709A (ja) | 2001-07-09 | 2003-01-24 | Toyobo Co Ltd | ブレンドポリマー電解質、該電解質を主成分とする電解質膜、及び該電解質を用いた膜/電極接合体 |
DE10133738A1 (de) | 2001-07-11 | 2003-02-06 | Joerg Mueller | Verfahren zur Herstellung einer plasmapolymerisierten Polymer-Elektrolytmembran |
DE10144815A1 (de) * | 2001-09-12 | 2003-03-27 | Celanese Ventures Gmbh | Protonenleitende Membran und deren Verwendung |
DE10148131B4 (de) | 2001-09-28 | 2010-07-01 | Gkss-Forschungszentrum Geesthacht Gmbh | Verfahren zur Herstellung eines Polymers, Polymer und protonenleitfähige Membran für elektrochemische Anwendungen |
US7010716B2 (en) | 2002-07-10 | 2006-03-07 | Nortel Networks, Ltd | Method and apparatus for defining failover events in a network device |
-
2002
- 2002-08-29 DE DE10239701A patent/DE10239701A1/de not_active Withdrawn
-
2003
- 2003-08-14 JP JP2004535087A patent/JP2005537380A/ja active Pending
- 2003-08-14 US US10/525,590 patent/US7795372B2/en not_active Expired - Fee Related
- 2003-08-14 CA CA002496593A patent/CA2496593A1/en not_active Abandoned
- 2003-08-14 EP EP03794875A patent/EP1537165A1/de not_active Withdrawn
- 2003-08-14 WO PCT/EP2003/009020 patent/WO2004024797A1/de active Application Filing
- 2003-08-14 CN CNB038204274A patent/CN1297588C/zh not_active Expired - Fee Related
- 2003-08-14 KR KR1020057003473A patent/KR20050043924A/ko not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4775215A (en) * | 1986-10-31 | 1988-10-04 | Hoechst Celanese Corporation | Nonlinear optical devices |
US5633337A (en) * | 1995-01-26 | 1997-05-27 | The United States Of America As Represented By The Secretary Of The Air Force | Aromatic benzobisazole polymers and copolymers incorporating diphenylamino moieties |
CN1606585A (zh) * | 2001-04-09 | 2005-04-13 | 赛拉尼斯温特斯股份有限公司 | 质子导电膜及其应用 |
Also Published As
Publication number | Publication date |
---|---|
KR20050043924A (ko) | 2005-05-11 |
DE10239701A1 (de) | 2004-03-11 |
EP1537165A1 (de) | 2005-06-08 |
CA2496593A1 (en) | 2004-03-25 |
JP2005537380A (ja) | 2005-12-08 |
WO2004024797A1 (de) | 2004-03-25 |
US20050256296A1 (en) | 2005-11-17 |
CN1678663A (zh) | 2005-10-05 |
US7795372B2 (en) | 2010-09-14 |
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