JP2007112907A - Polymer electrolyte composition containing aromatic hydrocarbon-based resin - Google Patents
Polymer electrolyte composition containing aromatic hydrocarbon-based resin Download PDFInfo
- Publication number
- JP2007112907A JP2007112907A JP2005306085A JP2005306085A JP2007112907A JP 2007112907 A JP2007112907 A JP 2007112907A JP 2005306085 A JP2005306085 A JP 2005306085A JP 2005306085 A JP2005306085 A JP 2005306085A JP 2007112907 A JP2007112907 A JP 2007112907A
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- Japan
- Prior art keywords
- group
- polymer electrolyte
- polymer
- electrolyte composition
- resin
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000011347 resin Substances 0.000 title claims abstract description 67
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 63
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 4
- 239000012528 membrane Substances 0.000 claims abstract description 94
- 229920000642 polymer Polymers 0.000 claims abstract description 90
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 238000005342 ion exchange Methods 0.000 claims abstract description 52
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 47
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 47
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 44
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 30
- 239000000446 fuel Substances 0.000 claims description 37
- 239000003822 epoxy resin Substances 0.000 claims description 31
- 229920000647 polyepoxide Polymers 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001340 alkali metals Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 description 35
- -1 perfluoro proton Chemical group 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 29
- 239000002243 precursor Substances 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 125000000524 functional group Chemical group 0.000 description 21
- 239000010410 layer Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000004898 kneading Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 125000000542 sulfonic acid group Chemical group 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000010306 acid treatment Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000012779 reinforcing material Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920006295 polythiol Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229920003026 Acene Polymers 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 239000004693 Polybenzimidazole Substances 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920001643 poly(ether ketone) Polymers 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920002480 polybenzimidazole Polymers 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 229920005649 polyetherethersulfone Polymers 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920012287 polyphenylene sulfone Polymers 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
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- 159000000007 calcium salts Chemical class 0.000 description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N fumaric acid group Chemical group C(\C=C\C(=O)O)(=O)O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
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- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- MGAXYKDBRBNWKT-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC(=O)CC1 MGAXYKDBRBNWKT-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- XFSXUCMYFWZRAF-UHFFFAOYSA-N 2-(trityloxymethyl)oxirane Chemical compound C1OC1COC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XFSXUCMYFWZRAF-UHFFFAOYSA-N 0.000 description 1
- LWIOWIKKGKNURV-UHFFFAOYSA-N 2-[[5-nonyl-2-[4-nonyl-2-(oxiran-2-ylmethyl)phenoxy]phenyl]methyl]oxirane Chemical compound C1OC1CC1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1CC1CO1 LWIOWIKKGKNURV-UHFFFAOYSA-N 0.000 description 1
- PWOBDMNCYMQTCE-UHFFFAOYSA-N 2-chlorobenzenethiol Chemical compound SC1=CC=CC=C1Cl PWOBDMNCYMQTCE-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SZAIAWVGWTXVMB-UHFFFAOYSA-N 6-oxa-3$l^{6}-thiabicyclo[3.1.0]hexane 3,3-dioxide Chemical compound C1S(=O)(=O)CC2OC21 SZAIAWVGWTXVMB-UHFFFAOYSA-N 0.000 description 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- NOQXXYIGRPAZJC-UHFFFAOYSA-N oxiran-2-ylmethyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1OC1 NOQXXYIGRPAZJC-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
本発明は、高分子電解質組成物及びそれからなる固体高分子型燃料電池用のプロトン交換膜に関するものである。 The present invention relates to a polymer electrolyte composition and a proton exchange membrane for a polymer electrolyte fuel cell comprising the same.
燃料電池は、電池内で、水素、メタノール等を電気化学的に酸化することにより、燃料の化学エネルギーを、直接、電気エネルギーに変換して取り出すものであり、クリーンな電気エネルギー供給源として注目されている。特に、固体高分子形燃料電池は、他と比較して低温で作動することから、自動車代替動力源、家庭用コジェネレーションシステム、携帯用発電機等として期待されている。 A fuel cell is one that converts the chemical energy of fuel directly into electrical energy by electrochemically oxidizing hydrogen, methanol, etc. in the battery, and is attracting attention as a clean electrical energy supply source. ing. In particular, polymer electrolyte fuel cells are expected to be used as alternative power sources for automobiles, home cogeneration systems, portable generators, and the like because they operate at a lower temperature than others.
このような固体高分子形燃料電池は、電極触媒層とガス拡散層とが積層されたガス拡散電極がプロトン交換膜の両面に接合された膜電極接合体を少なくとも備えている。ここでいうプロトン交換膜は、高分子鎖中にスルホン酸基、カルボン酸基等の強酸性基を有し、プロトンを選択的に透過する性質を有する材料である。このようなプロトン交換膜としては、化学的安定性の高いナフィオン（登録商標、デュポン社製）に代表されるパーフルオロ系プロトン交換膜が好適に用いられる。 Such a polymer electrolyte fuel cell includes at least a membrane electrode assembly in which a gas diffusion electrode in which an electrode catalyst layer and a gas diffusion layer are laminated is bonded to both surfaces of a proton exchange membrane. The proton exchange membrane here is a material having a strong acidic group such as a sulfonic acid group and a carboxylic acid group in the polymer chain and a property of selectively transmitting protons. As such a proton exchange membrane, a perfluoro proton exchange membrane represented by Nafion (registered trademark, manufactured by DuPont) having high chemical stability is preferably used.
燃料電池の運転時においては、アノード側のガス拡散電極に燃料（例えば、水素）、カソード側のガス拡散電極に酸化剤（例えば、酸素や空気）をそれぞれ供給し、両電極間を外部回路で接続することにより作動する。具体的には、水素を燃料とした場合、アノード触媒上で水素が酸化されてプロトンが生じ、このプロトンがアノード触媒層内のプロトン伝導性ポリマーを通った後、プロトン交換膜内を移動し、カソード触媒層内のプロトン伝導性ポリマーを通ってカソード触媒上に達する。一方、水素の酸化によりプロトンと同時に生じた電子は、外部回路を通ってカソード側ガス拡散電極に到達し、カソード触媒上にて上記プロトンと酸化剤中の酸素と反応して水が生成され、このとき電気エネルギーを取り出すことができる。 During operation of the fuel cell, fuel (for example, hydrogen) is supplied to the gas diffusion electrode on the anode side, and an oxidant (for example, oxygen or air) is supplied to the gas diffusion electrode on the cathode side. Operates by connecting. Specifically, when hydrogen is used as a fuel, hydrogen is oxidized on the anode catalyst to generate protons, and after passing through the proton conductive polymer in the anode catalyst layer, the protons move in the proton exchange membrane, It reaches the cathode catalyst through the proton conducting polymer in the cathode catalyst layer. On the other hand, electrons generated simultaneously with protons by oxidation of hydrogen reach the cathode side gas diffusion electrode through an external circuit, and react with the protons and oxygen in the oxidant on the cathode catalyst to generate water, At this time, electric energy can be taken out.
この際、プロトン交換膜は、ガスバリアとしての役割も果たす必要があり、プロトン交換膜のガス透過率が高いと、アノード側水素のカソード側へのリークおよびカソード側酸素のアノード側へのリーク、すなわち、クロスリークが発生して、いわゆるケミカルショートの状態となって良好な電圧を取り出せなくなる。
このような固体高分子型燃料電池は、高出力特性を得るために８０℃近辺で運転するのが通常である。しかしながら、自動車用途として用いる場合には、夏場の自動車走行を想定して、高温低加湿条件下（運転温度１００℃付近で、５０℃加湿（湿度１２ＲＨ％に相当））でも燃料電池を運転できることが望まれている。ところが、従来のパーフルオロ系プロトン交換膜を用いて高温低加湿条件下で燃料電池を長時間運転すると、プロトン交換膜にピンホールが生じ、クロスリークが発生するという問題があり、十分な耐久性が得られていない。
At this time, the proton exchange membrane also needs to play a role as a gas barrier. When the gas permeability of the proton exchange membrane is high, leakage of anode-side hydrogen to the cathode side and leakage of cathode-side oxygen to the anode side, that is, A cross leak occurs, so that a so-called chemical short circuit occurs and a good voltage cannot be taken out.
Such a polymer electrolyte fuel cell is usually operated near 80 ° C. in order to obtain high output characteristics. However, when used for automobiles, the fuel cell can be operated even under high-temperature and low-humidification conditions (operating temperature near 100 ° C., 50 ° C. humidification (corresponding to a humidity of 12 RH%)) assuming that the vehicle is driven in summer. It is desired. However, when a fuel cell is operated for a long time under a high temperature and low humidity condition using a conventional perfluoro proton exchange membrane, there is a problem that pinholes are generated in the proton exchange membrane, and cross leaks occur. Is not obtained.
パーフルオロ系プロトン交換膜の耐久性を向上させる方法として、フィブリル状のポリテトラフルオロエチレン（ＰＴＦＥ）を用いた補強（特許文献１，２）、延伸処理したＰＴＦＥ多孔膜を用いた補強（特許文献３）、無機粒子を添加した補強（特許文献４，５，６）、芳香族環含有樹脂からなる多孔質体を用いた補強（特許文献７、８）による検討が開示されている。しかしながら、これらの方法では、上記問題を解決するに充分な耐久性を得ることは達成されていない。
本発明の目的は、高温低加湿条件下（例えば、運転温度１００℃で、５０℃加湿（湿度１２ＲＨ％に相当））でも高耐久性を有する高分子電解質組成物およびこの高分子電解質組成物からなるプロトン交換膜を提供することである。 An object of the present invention is to provide a polymer electrolyte composition having high durability even under high-temperature and low-humidity conditions (for example, at an operating temperature of 100 ° C. and 50 ° C. humidification (corresponding to a humidity of 12 RH%)), and the polymer electrolyte composition. It is providing the proton exchange membrane which becomes.
本発明者等は、前記課題を解決するため鋭意検討した結果、
イオン交換基を有する高分子化合物（Ａ）と、ポリフェニレンスルフィド樹脂（Ｂ）と、ポリスルホン樹脂（Ｃ）と、エポキシ基含有化合物（Ｄ）とからなる高分子電解質組成物が高い酸化安定性を示し、さらにその高分子電解質組成物からなるプロトン交換膜が高温低加湿下でも非常に良好な高耐久性を有し、かつ力学物性も向上することを見出した。
As a result of intensive studies to solve the above problems, the present inventors,
A polymer electrolyte composition comprising a polymer compound (A) having an ion exchange group, a polyphenylene sulfide resin (B), a polysulfone resin (C), and an epoxy group-containing compound (D) exhibits high oxidation stability. Furthermore, it has been found that a proton exchange membrane comprising the polymer electrolyte composition has very good high durability even under high temperature and low humidity, and also improves mechanical properties.
すなわち、本発明は以下のとおりである。
［１］イオン交換基を有する高分子化合物（Ａ）と、ポリフェニレンスルフィド樹脂（Ｂ）と、ポリスルホン樹脂（Ｃ）と、エポキシ基含有化合物（Ｄ）からなる高分子電解質組成物。
［２］エポキシ基含有化合物（Ｄ）がエポキシ基を有する不飽和モノマーの単独重合体または共重合体（Ｅ）である［１］に記載の高分子電解組成物。
［３］エポキシ基含有化合物（Ｄ）がエポキシ樹脂（Ｆ）である［１］に記載の高分子電解組成物。
That is, the present invention is as follows.
[1] A polymer electrolyte composition comprising a polymer compound (A) having an ion exchange group, a polyphenylene sulfide resin (B), a polysulfone resin (C), and an epoxy group-containing compound (D).
[2] The polymer electrolyte composition according to [1], wherein the epoxy group-containing compound (D) is a homopolymer or copolymer (E) of an unsaturated monomer having an epoxy group.
[3] The polymer electrolyte composition according to [1], wherein the epoxy group-containing compound (D) is an epoxy resin (F).
［４］［３］に記載の高分子電解質組成物であって、該高分子電解質組成物中のポリスルホン樹脂（Ｃ）とエポキシ樹脂（Ｆ）が反応してなるエポキシ変性ポリスルホン（Ｇ）を少なくとも含有している高分子電解質組成物。
［５］イオン交換基を有する高分子化合物（Ａ）が、イオン交換基を有するパーフルオロカーボン高分子化合物である［１］に記載の高分子電解質組成物。
[4] The polymer electrolyte composition according to [3], wherein at least an epoxy-modified polysulfone (G) obtained by reacting the polysulfone resin (C) and the epoxy resin (F) in the polymer electrolyte composition is at least Containing polyelectrolyte composition.
[5] The polymer electrolyte composition according to [1], wherein the polymer compound (A) having an ion exchange group is a perfluorocarbon polymer compound having an ion exchange group.
［６］イオン交換基を有するパーフルオロカーボン高分子化合物が、下記一般式（１）で表される構造単位を有することを特徴とする［５］に記載の高分子電解質組成物。
-[CF2CX1X2]a-[CF2-CF(-O-(CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (１)（式中、Ｘ１，Ｘ２およびＸ３はそれぞれ独立にハロゲン元素または炭素数１以上３以下のパーフルオロアルキル基、０≦ａ＜１、０＜ｇ≦１、ａ＋ｇ＝１、ｂは０以上８以下の整数、ｃは、０または１であり、ｄ、ｅおよびｆはそれぞれ独立に０以上６以下の整数（ただし、ｄ＋ｅ＋ｆは０に等しくない）、Ｒ１およびＲ２はそれぞれ独立にハロゲン元素、炭素数１以上１０以下のパーフルオロアルキル基またはフルオロクロロアルキル基であり、Ｘ４は、ＣＯＯＺ、ＳＯ３Ｚ、ＰＯ３Ｚ２、ＰＯ３ＨＺ（Ｚは水素原子、アルカリ金属原子、アルカリ土類金属原子、アミン類（ＮＨ４、ＮＨ３Ｒ、ＮＨ２Ｒ２、ＮＨＲ３、ＮＲ４（Ｒはアルキル基、又はアレーン基））
[6] The polymer electrolyte composition according to [5], wherein the perfluorocarbon polymer compound having an ion exchange group has a structural unit represented by the following general formula (1).
-[CF 2 CX 1 X 2 ] a- [CF 2 -CF (-O- (CF 2 -CF (CF 2 X 3 )) b -O c- (CFR 1 ) d- (CFR 2 ) e- ( CF 2 ) f -X 4 )] g- (1) (wherein X 1 , X 2 and X 3 are each independently a halogen element or a perfluoroalkyl group having 1 to 3 carbon atoms, 0 ≦ a <1 , 0 <g ≦ 1, a + g = 1, b is an integer of 0 or more and 8 or less, c is 0 or 1, and d, e and f are each independently an integer of 0 or more and 6 or less (where d + e + f is 0) R 1 and R 2 are each independently a halogen element, a perfluoroalkyl group or a fluorochloroalkyl group having 1 to 10 carbon atoms, and X 4 is COOZ, SO 3 Z, PO 3 Z 2. , PO 3 HZ (Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an amine (NH 4 , NH 3 R, NH 2 R 2 , NHR 3 , NR 4 (R is Alkyl group or arene group))
［７］前記［１］〜［６］のいずれか一項に記載の高分子電解質組成物からなるプロトン交換膜。
［８］前記［７］に記載のプロトン交換膜を有する膜電極接合体。
［９］前記［８］に記載の膜電極接合体を有する固体高分子型燃料電池。
[7] A proton exchange membrane comprising the polymer electrolyte composition according to any one of [1] to [6].
[8] A membrane electrode assembly having the proton exchange membrane according to [7].
[9] A polymer electrolyte fuel cell having the membrane electrode assembly according to [8].
本発明の高分子電解質組成物からなるプロトン交換膜は、運転温度１００℃で、５０℃加湿（湿度１２ＲＨ％に相当）において、燃料電池運転を長期間行ってもクロスリークが発生せず、優れた耐久性を示すことから、高温低加湿条件下（例えば、運転温度１００℃で、５０℃加湿（湿度１２ＲＨ％に相当））でも高耐久性を有するプロトン交換膜を得ることが可能となった。
本発明により得られるプロトン交換膜は、ダイレクトメタノール型燃料電池を含めた各種燃料電池、水電解、ハロゲン化水素酸電解、食塩電解、酸素濃縮器、湿度センサー、ガスセンサー等に用いることも可能である。
The proton exchange membrane comprising the polymer electrolyte composition of the present invention is excellent in that no cross leak occurs even when the fuel cell is operated for a long period of time at an operating temperature of 100 ° C. and humidified at 50 ° C. (equivalent to a humidity of 12 RH%). Because of its high durability, it has become possible to obtain a proton exchange membrane having high durability even under high temperature and low humidification conditions (for example, at an operating temperature of 100 ° C. and 50 ° C. humidification (equivalent to a humidity of 12 RH%)). .
The proton exchange membrane obtained by the present invention can also be used in various fuel cells including direct methanol fuel cells, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors, etc. is there.
以下に、本発明について詳細に説明する。
本発明に用いられるイオン交換基を有する高分子化合物（Ａ）としては、特に限定はしないが、イオン交換基を有するパーフルオロカーボン高分子化合物や、分子内に芳香環を有する炭化水素系高分子化合物にイオン交換基を導入したものなどが好ましい。分子内に芳香環を有する炭化水素系高分子化合物としては、具体的には、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリチオエーテルエーテルスルホン、ポリチオエーテルケトン、ポリチオエーテルエーテルケトン、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリオキサジアゾール、ポリベンゾオキサジノン、ポリキシリレン、ポリフェニレン、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセン、ポリシアノゲン、ポリナフチリジン、ポリフェニレンスルフィドスルホン、ポリフェニレンスルホン、ポリイミド、ポリエーテルイミド、ポリエステルイミド、ポリアミドイミド、ポリアリレート、芳香族ポリアミド、ポリスチレン、ポリエステル、ポリカーボネートなどが挙げられるが、耐熱性や耐酸化性、耐加水分解性の観点からポリフェニレンスルフィド、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリチオエーテルエーテルスルホン、ポリチオエーテルケトン、ポリチオエーテルエーテルケトン、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリオキサジアゾール、ポリベンゾオキサジノン、ポリキシリレン、ポリフェニレン、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセン、ポリシアノゲン、ポリナフチリジン、ポリフェニレンスルフィドスルホン、ポリフェニレンスルホン、ポリイミド、ポリエーテルイミドが好ましい。これらに導入するイオン交換基は、好ましくはスルホン酸基、スルホンイミド基、スルホンアミド基、カルボン酸基、リン酸基などが挙げられ、特にスルホン酸基が好ましい。
The present invention is described in detail below.
The polymer compound (A) having an ion exchange group used in the present invention is not particularly limited, but is a perfluorocarbon polymer compound having an ion exchange group or a hydrocarbon polymer compound having an aromatic ring in the molecule. Those obtained by introducing an ion exchange group into are preferable. Specific examples of the hydrocarbon polymer compound having an aromatic ring in the molecule include polyphenylene sulfide, polyphenylene ether, polysulfone, polyether sulfone, polyether ether sulfone, polyether ketone, polyether ether ketone, and polythioether ether. Sulfone, polythioetherketone, polythioetheretherketone, polybenzimidazole, polybenzoxazole, polyoxadiazole, polybenzoxazinone, polyxylylene, polyphenylene, polythiophene, polypyrrole, polyaniline, polyacene, polycyanogen, polynaphthyridine, polyphenylene sulfide sulfone, Polyphenylenesulfone, polyimide, polyetherimide, polyesterimide, polyamideimide, polyester Examples include arylates, aromatic polyamides, polystyrenes, polyesters and polycarbonates. From the viewpoint of heat resistance, oxidation resistance and hydrolysis resistance, polyphenylene sulfide, polyphenylene ether, polysulfone, polyethersulfone, polyetherethersulfone, polyether Ketone, polyetheretherketone, polythioetherethersulfone, polythioetherketone, polythioetheretherketone, polybenzimidazole, polybenzoxazole, polyoxadiazole, polybenzoxazinone, polyxylylene, polyphenylene, polythiophene, polypyrrole, polyaniline, polyacene , Polycyanogen, polynaphthyridine, polyphenylene sulfide sulfone, polyphenylene sulfone, poly Imides, polyetherimides are preferred. Examples of the ion exchange group to be introduced into these include a sulfonic acid group, a sulfonimide group, a sulfonamide group, a carboxylic acid group, and a phosphoric acid group, and a sulfonic acid group is particularly preferable.
本発明に用いられるイオン交換基を有する高分子化合物（Ａ）としては、イオン交換基を有するパーフルオロカーボン高分子化合物が特に好適である。
イオン交換基を有するパーフルオロカーボン高分子化合物としては、パーフルオロカーボンのスルホン酸ポリマーをはじめカルボン酸ポリマー、スルホンイミドポリマー、スルホンアミドポリマー、リン酸ポリマー、もしくはこれらのアミン塩、金属塩等が好適に用いられ、具体例として一般式（１）で表される重合体が挙げられる。
-[CF2CX1X2]a-[CF2-CF(-O-(CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- （１）
（式中、Ｘ１，Ｘ２およびＸ３はそれぞれ独立にハロゲン元素または炭素数１以上３以下のパーフルオロアルキル基、０≦ａ＜１、０＜ｇ≦１、ａ＋ｇ＝１、ｂは０以上８以下の整数、ｃは、０または１であり、ｄ、ｅおよびｆはそれぞれ独立に０以上６以下の整数（ただし、ｄ＋ｅ＋ｆは０に等しくない）、Ｒ１およびＲ２はそれぞれ独立にハロゲン元素、炭素数１以上１０以下のパーフルオロアルキル基またはフルオロクロロアルキル基であり、Ｘ４は、ＣＯＯＺ、ＳＯ３Ｚ、ＰＯ３Ｚ２、ＰＯ３ＨＺ（Ｚは水素原子、アルカリ金属原子、アルカリ土類金属原子、アミン類（ＮＨ４、ＮＨ３Ｒ、ＮＨ２Ｒ２、ＮＨＲ３、ＮＲ４（Ｒはアルキル基、又はアレーン基））
As the polymer compound (A) having an ion exchange group used in the present invention, a perfluorocarbon polymer compound having an ion exchange group is particularly suitable.
As the perfluorocarbon polymer compound having an ion exchange group, a sulfonic acid polymer of perfluorocarbon, a carboxylic acid polymer, a sulfonimide polymer, a sulfonamide polymer, a phosphoric acid polymer, or an amine salt or a metal salt thereof is preferably used. Specific examples include a polymer represented by the general formula (1).
-[CF 2 CX 1 X 2 ] a- [CF 2 -CF (-O- (CF 2 -CF (CF 2 X 3 )) b -O c- (CFR 1 ) d- (CFR 2 ) e- ( CF 2 ) f -X 4 )] g- (1)
(Wherein X 1 , X 2 and X 3 are each independently a halogen element or a perfluoroalkyl group having 1 to 3 carbon atoms, 0 ≦ a <1, 0 <g ≦ 1, a + g = 1, b is 0 An integer of 8 or less, c is 0 or 1, d, e and f are each independently an integer of 0 or more and 6 or less (where d + e + f is not equal to 0), and R 1 and R 2 are each independently A halogen element, a perfluoroalkyl group or a fluorochloroalkyl group having 1 to 10 carbon atoms, and X 4 is COOZ, SO 3 Z, PO 3 Z 2 , PO 3 HZ (Z is a hydrogen atom, an alkali metal atom, Alkaline earth metal atoms, amines (NH 4 , NH 3 R, NH 2 R 2 , NHR 3 , NR 4 (R is an alkyl group or arene group))
中でも、一般式（２）或いは（３）で表されるパーフルオロカーボンスルホン酸ポリマーもしくはその金属塩が特に好ましい。
-[CF2CF2]a-[CF2-CF(-O-CF2-CF(CF3))b-O-(CF2)c-SO3X]]d- （２）
（式中、０≦ａ＜１、０≦ｄ＜１、ａ＋ｄ＝１、ｂは１以上８以下の整数、ｃは０以上１０以下の整数、Ｘは水素原子またはアルカリ金属原子）
-[CF2CF2]e-[CF2-CF(-O-(CF2)f-SO3Y)]g- （３）
（式中、０≦ｅ＜１、０≦ｇ＜１、ｅ＋ｇ＝１、ｆは０以上１０以下の整数、Ｙは水素原子またはアルカリ金属原子）
Among these, a perfluorocarbon sulfonic acid polymer represented by the general formula (2) or (3) or a metal salt thereof is particularly preferable.
-[CF 2 CF 2 ] a- [CF 2 -CF (-O-CF 2 -CF (CF 3 )) b -O- (CF 2 ) c -SO 3 X]] d- (2)
(Wherein 0 ≦ a <1, 0 ≦ d <1, a + d = 1, b is an integer of 1 to 8, c is an integer of 0 to 10, and X is a hydrogen atom or an alkali metal atom)
-[CF 2 CF 2 ] e- [CF 2 -CF (-O- (CF 2 ) f -SO 3 Y)] g- (3)
(Wherein 0 ≦ e <1, 0 ≦ g <1, e + g = 1, f is an integer of 0 to 10 and Y is a hydrogen atom or an alkali metal atom)
本発明のイオン交換基を有するパーフルオロカーボン高分子化合物は、例えば、一般式（４）に示される前駆体ポリマーを重合した後、アルカリ加水分解、酸処理等を行って製造することができる。
-[CF2CX1X2]a-[CF2-CF(-O-(CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X5)]g- （４）
（式中、Ｘ１、Ｘ２およびＸ３は、それぞれ独立に、ハロゲン元素または炭素数１以上３以下のパーフルオロアルキル基、０≦ａ＜１、０＜ｇ≦１、ａ＋ｇ＝１、ｂは、０以上８以下の整数、ｃは、０または１、ｄ、ｅおよびｆは、それぞれ独立に、０以上６以下の整数（但し、ｄ＋ｅ＋ｆは、０に等しくない）、Ｒ１およびＲ２は、それぞれ独立に、ハロゲン元素、炭素数１以上１０以下のパーフルオロアルキル基またはフルオロクロロアルキル基、Ｘ５は、ＣＯＯＲ３，ＣＯＲ４またはＳＯ２Ｒ４（Ｒ３は、炭素数１〜３の炭化水素系アルキル基、Ｒ４は、ハロゲン元素））
The perfluorocarbon polymer compound having an ion exchange group of the present invention can be produced, for example, by polymerizing a precursor polymer represented by the general formula (4) and then performing alkali hydrolysis, acid treatment, and the like.
-[CF 2 CX 1 X 2 ] a- [CF 2 -CF (-O- (CF 2 -CF (CF 2 X 3 )) b -O c- (CFR 1 ) d- (CFR 2 ) e- ( CF 2 ) f -X 5 )] g- (4)
(Wherein X 1 , X 2 and X 3 are each independently a halogen element or a perfluoroalkyl group having 1 to 3 carbon atoms, 0 ≦ a <1, 0 <g ≦ 1, a + g = 1, b Is an integer of 0 to 8, c is 0 or 1, d, e and f are each independently an integer of 0 to 6 (where d + e + f is not equal to 0), R 1 and R 2 Are each independently a halogen element, a perfluoroalkyl group or fluorochloroalkyl group having 1 to 10 carbon atoms, X 5 is COOR 3 , COR 4 or SO 2 R 4 (R 3 is a carbon number of 1 to 3) Hydrocarbon alkyl group, R 4 is a halogen element))
本発明に用いることが可能な前駆体ポリマーは、フッ化オレフィン化合物とフッ化ビニル化合物とを共重合させることにより製造される。
具体的なフッ化オレフィン化合物としては、ＣＦ２＝ＣＦ２，ＣＦ２＝ＣＦＣｌ，ＣＦ２＝ＣＣｌ２等が挙げられる。
又、具体的なフッ化ビニル化合物としては、
ＣＦ２＝ＣＦＯ（ＣＦ２）ｚ−ＳＯ２Ｆ，ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）Ｏ（ＣＦ２）ｚ−ＳＯ２Ｆ，ＣＦ２＝ＣＦ（ＣＦ２）ｚ−ＳＯ２Ｆ，ＣＦ２＝ＣＦ（ＯＣＦ２ＣＦ（ＣＦ３））ｚ−（ＣＦ２）ｚ−１−ＳＯ２Ｆ，ＣＦ２＝ＣＦＯ（ＣＦ２）ｚ−ＣＯ２Ｒ，ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）Ｏ（ＣＦ２）ｚ−ＣＯ２Ｒ，ＣＦ２＝ＣＦ（ＣＦ２）ｚ−ＣＯ２Ｒ，ＣＦ２＝ＣＦ（ＯＣＦ２ＣＦ（ＣＦ３））ｚ−（ＣＦ２）２−ＣＯ２Ｒ（Ｚは１〜８の整数、Ｒは炭素数１〜３の炭化水素系アルキル基を表す）等が挙げられる。
The precursor polymer that can be used in the present invention is produced by copolymerizing a fluorinated olefin compound and a vinyl fluoride compound.
Specific examples of the fluorinated olefin compound include CF 2 = CF 2 , CF 2 = CFCl, CF 2 = CCl 2 and the like.
Moreover, as a specific vinyl fluoride compound,
CF 2 = CFO (CF 2) z -SO 2 F, CF 2 = CFOCF 2 CF (CF 3) O (CF 2) z -SO 2 F, CF 2 = CF (CF 2) z -SO 2 F, CF 2 = CF (OCF 2 CF ( CF 3)) z - (CF 2) z-1 -SO 2 F, CF 2 = CFO (CF 2) z -CO 2 R, CF2 = CFOCF 2 CF (CF 3) O (CF 2) z -CO 2 R , CF 2 = CF (CF 2) z -CO 2 R, CF 2 = CF (OCF 2 CF (CF 3)) z - (CF 2) 2 -CO 2 R (Z Is an integer of 1 to 8, and R represents a hydrocarbon alkyl group having 1 to 3 carbon atoms).
前駆体ポリマーの重合方法としては、フッ化ビニル化合物をフロン等の溶媒に溶解した後、フッ化オレフィン化合物のガスと反応させ重合する溶液重合法、フロン等の溶媒を使用せずに重合する塊状重合法、フッ化ビニル化合物を界面活性剤とともに水中に仕込んで乳化させた後、フッ化オレフィン化合物のガスと反応させ重合する乳化重合法等の一般的な重合方法が挙げられる。
尚、本発明では、フッ化ビニル化合物、フッ化オレフィン化合物に加え、ヘキサフルオロプロピレン、クロロトリフルオロエチレン等のパーフルオロオレフィン、パーフルオロアルキルビニルエーテル等の第３成分を含む共重合体であってもよい。
As a polymerization method of the precursor polymer, a solution polymerization method in which a vinyl fluoride compound is dissolved in a solvent such as chlorofluorocarbon and then reacted with a gas of a fluorinated olefin compound to perform polymerization, or a block shape in which polymerization is performed without using a solvent such as chlorofluorocarbon General polymerization methods such as a polymerization method, an emulsion polymerization method in which a vinyl fluoride compound is mixed with a surfactant in water and emulsified, and then reacted with a gas of a fluorinated olefin compound for polymerization.
In the present invention, in addition to a vinyl fluoride compound and a fluorinated olefin compound, a copolymer containing a third component such as a perfluoroolefin such as hexafluoropropylene or chlorotrifluoroethylene or a perfluoroalkyl vinyl ether may be used. Good.
本発明に用いることが可能な前駆体ポリマーの、ＪＩＳ Ｋ−７２１０に基づいた２７０℃、荷重２１．２Ｎ、オリフィス内径２．０９ｍｍで測定されるメルトインデックスＭＩ（ｇ／１０分）は、０．００１以上１０００以下が好ましく、より好ましくは０．０１以上１００以下、最も好ましくは０．１以上１０以下である。 The melt index MI (g / 10 min) of the precursor polymer that can be used in the present invention, measured at 270 ° C., load 21.2 N, orifice inner diameter 2.09 mm based on JIS K-7210 is 0.00. 001 or more and 1000 or less are preferable, more preferably 0.01 or more and 100 or less, and most preferably 0.1 or more and 10 or less.
本発明に用いることが可能な前駆体ポリマーは、次に、塩基性反応液体に浸漬させてアルカリ加水分解処理を行う。反応液体は、水酸化カリウム、水酸化ナトリウム等のアルカリ金属またはアルカリ土類金属の水酸化物の水溶液が好ましい。アルカリ金属またはアルカリ土類金属の水酸化物の含有率は、１０重量％以上３０重量％以下であることが好ましい。上記反応液体は、ジメチルスルホキシド、メタノール等の膨潤性有機化合物を含有するのが好ましい。膨潤性有機化合物の含有率としては、１重量％以上３０重量％以下であることが好ましい。
前駆体ポリマーをアルカリ加水分解処理した後、さらに必要に応じて塩酸等で酸処理を行うことにより、イオン交換基を有するパーフルオロカーボン高分子化合物が製造される。
Next, the precursor polymer that can be used in the present invention is immersed in a basic reaction liquid and subjected to an alkali hydrolysis treatment. The reaction liquid is preferably an aqueous solution of an alkali metal or alkaline earth metal hydroxide such as potassium hydroxide or sodium hydroxide. The content of alkali metal or alkaline earth metal hydroxide is preferably 10% by weight or more and 30% by weight or less. The reaction liquid preferably contains a swellable organic compound such as dimethyl sulfoxide or methanol. The content of the swellable organic compound is preferably 1% by weight or more and 30% by weight or less.
After the precursor polymer is subjected to an alkali hydrolysis treatment, and further subjected to an acid treatment with hydrochloric acid or the like as necessary, a perfluorocarbon polymer compound having an ion exchange group is produced.
次に、本発明のポリフェニレンスルフィド樹脂（Ｂ）（以下ＰＰＳと略記することもある）は、所謂ポリフェニレンスルフィド樹脂であれば特に限定されないが、好ましくはパラフェニレンスルフィド骨格が７０モル％以上、さらに好ましくは９０モル％以上からなるポリフェニレンスルフィド樹脂である。 Next, the polyphenylene sulfide resin (B) of the present invention (hereinafter sometimes abbreviated as PPS) is not particularly limited as long as it is a so-called polyphenylene sulfide resin, but preferably has a paraphenylene sulfide skeleton of 70 mol% or more, more preferably. Is a polyphenylene sulfide resin comprising 90 mol% or more.
ＰＰＳの製造方法は、特に限定するものではなく、通常、ハロゲン置換芳香族化合物、例えばｐ−ジクロルベンゼンを硫黄と炭酸ソーダの存在下で重合させる方法、極性溶媒中でｐ−ジクロルベンゼンを硫化ナトリウムあるいは硫化水素ナトリウムと水酸化ナトリウムの存在下で重合させる方法、または極性溶媒中でｐ−ジクロルベンゼンを硫化水素と水酸化ナトリウムあるいはナトリウムアミノアルカノエートの存在下で重合させる方法、ｐ−クロルチオフェノールの自己縮合等が挙げられる。これらの中でもＮ−メチルピロリドン、ジメチルアセトアミド等のアミド系溶媒やスルホラン等のスルホン系溶媒中で硫化ナトリウムとｐ−ジクロルベンゼンを反応させる方法が好ましい。具体的には、米国特許第２５１３１８８号明細書、特公昭４４−２７６７１号公報、特公昭４５−３３６８号公報、特公昭５２−１２２４０号公報、特開昭６１−２２５２１７号公報、米国特許第３２７４１６５号明細書、英国特許第１１６０６６０号明細書、特公昭４６−２７２５５号公報、ベルギー特許第２９４３７号明細書、特開平５−２２２１９６号公報等に記載された方法やこれら特許等に例示された先行技術の方法で得ることが出来る。 The production method of PPS is not particularly limited. Usually, a halogen-substituted aromatic compound such as p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, and p-dichlorobenzene is polymerized in a polar solvent. A method of polymerizing in the presence of sodium sulfide or sodium hydrogen sulfide and sodium hydroxide, or a method of polymerizing p-dichlorobenzene in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate in a polar solvent, p- Examples include self-condensation of chlorothiophenol. Among these, a method of reacting sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is preferable. Specifically, US Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-3368, Japanese Patent Publication No. 52-12240, Japanese Patent Publication No. 61-225217, US Pat. No. 3,274,165. No. 1, British Patent No. 1160660, Japanese Patent Publication No. Sho 46-27255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 5-222196, etc. It can be obtained by technical methods.
本発明に用いられるポリフェニレンスルフィド樹脂（Ｂ）は、塩化メチレンによるオリゴマー抽出量が０．００１重量％以上０．９重量％以下であり、かつ−ＳＸ基（Ｓはイオウ原子、Ｘはアルカリ金属または水素原子である）が１０μｍｏｌ／ｇ以上１０，０００μｍｏｌ／ｇ以下であるポリフェニレンスルフィド樹脂が好ましい。
塩化メチレンによるオリゴマー抽出量に関しては、０．００１重量％以上０．８重量％以下がさらに好ましく、０．００１重量％以上０．７重量％以下が特に好ましい。塩化メチレンによるオリゴマー抽出量が上記範囲にあるということは、ＰＰＳ中におけるオリゴマー（約１０〜３０量体）の量が少ないことを意味する。上記オリゴマー抽出量が上記範囲を超えると製膜時にブリードアウトが発生しやすくなるので好ましくない。
The polyphenylene sulfide resin (B) used in the present invention has an oligomer extraction amount of 0.001 wt% or more and 0.9 wt% or less with methylene chloride, and a —SX group (S is a sulfur atom, X is an alkali metal or A polyphenylene sulfide resin having a hydrogen atom of 10 μmol / g or more and 10,000 μmol / g or less is preferable.
The amount of oligomer extracted with methylene chloride is more preferably 0.001 wt% or more and 0.8 wt% or less, and particularly preferably 0.001 wt% or more and 0.7 wt% or less. That the amount of oligomer extracted with methylene chloride is in the above range means that the amount of oligomer (about 10 to 30 mer) in PPS is small. If the amount of oligomer extraction exceeds the above range, bleeding out tends to occur during film formation, which is not preferable.
ここで、塩化メチレンによるオリゴマー抽出量の測定は以下の方法により行うことができる。すなわち、ＰＰＳ粉末５ｇを塩化メチレン８０ｍｌに加え、４時間ソクスレー抽出を実施した後、室温まで冷却し、抽出後の塩化メチレン溶液を秤量瓶に移す。更に、上記の抽出に使用した容器を塩化メチレン合計６０ｍｌを用いて、３回に分けて洗浄し、該洗浄液を上記秤量瓶中に回収する。次に、約８０℃に加熱して、該秤量瓶中の塩化メチレンを蒸発させて除去し、残渣を秤量し、この残渣量よりＰＰＳ中に存在するオリゴマー量の割合を求めることができる。 Here, the amount of oligomer extracted with methylene chloride can be measured by the following method. That is, 5 g of PPS powder is added to 80 ml of methylene chloride, Soxhlet extraction is performed for 4 hours, and then cooled to room temperature, and the methylene chloride solution after extraction is transferred to a weighing bottle. Further, the container used for the above extraction is washed in three portions with a total of 60 ml of methylene chloride, and the washing liquid is collected in the weighing bottle. Next, the methylene chloride in the weighing bottle is evaporated and removed by heating to about 80 ° C., the residue is weighed, and the ratio of the amount of oligomer present in the PPS can be determined from the amount of the residue.
また、−ＳＸ基（Ｓはイオウ原子、Ｘはアルカリ金属または水素原子である）の含有量に関しては、１５μｍｏｌ／ｇ以上１０，０００μｍｏｌ／ｇ以下がさらに好ましく、２０μｍｏｌ／ｇ以上１０，０００μｍｏｌ／ｇ以下が特に好ましい。−ＳＸ基濃度が上記範囲にあるということは、ポリフェニレンスルフィド樹脂の反応活性点が多いことを意味する。−ＳＸ基濃度が上記範囲を満たすポリフェニレンスルフィド樹脂（Ｂ）を用いることで、本発明の高分子電解質組成物においてイオン交換基を有する高分子化合物（Ａ）とポリフェニレンスルフィド樹脂との混和性が向上し、イオン交換基を有する高分子化合物（Ａ）中へのポリフェニレンスルフィド樹脂（Ｂ）の分散性が向上すると考えられる。 The content of the —SX group (S is a sulfur atom, X is an alkali metal or hydrogen atom) is more preferably 15 μmol / g or more and 10,000 μmol / g or less, more preferably 20 μmol / g or more and 10,000 μmol / g. The following are particularly preferred: The fact that the -SX group concentration is in the above range means that there are many reaction active sites of the polyphenylene sulfide resin. -By using the polyphenylene sulfide resin (B) in which the SX group concentration satisfies the above range, the miscibility between the polymer compound (A) having an ion exchange group and the polyphenylene sulfide resin is improved in the polymer electrolyte composition of the present invention. It is considered that the dispersibility of the polyphenylene sulfide resin (B) in the polymer compound (A) having an ion exchange group is improved.
ここで、−ＳＸ基の定量は以下の方法により行うことができる。すなわち、ＰＰＳ粉末を予め１２０℃で４時間乾燥した後、この乾燥ＰＰＳ粉末２０ｇをＮ−メチル−２−ピロリドン１５０ｇに加えて粉末凝集塊がなくなるように室温で３０分間激しく撹拌混合しスラリー状態にする。得られたスラリーを濾過した後、毎回約８０℃の温水１リットルを用いて７回洗浄を繰り返す。得た濾過ケーキを純水２００ｇ中に再度スラリー化した後、１Ｎの塩酸を加えて該スラリーのＰＨを４．５に調整する。次に、２５℃で３０分間撹拌して、濾過した後、約８０℃の温水１リットルを用いて６回洗浄を繰り返す。得られた濾過ケーキを純水２００ｇ中に再度スラリー化し、次いで、１Ｎの水酸化ナトリウムにより滴定し、消費した水酸化ナトリウム量よりＰＰＳ中に存在する−ＳＸ基の量を求める。 Here, quantification of the -SX group can be performed by the following method. That is, after the PPS powder was previously dried at 120 ° C. for 4 hours, 20 g of this dried PPS powder was added to 150 g of N-methyl-2-pyrrolidone, and vigorously stirred and mixed at room temperature for 30 minutes so as to eliminate the powder aggregate. To do. After the obtained slurry is filtered, washing is repeated 7 times using 1 liter of warm water of about 80 ° C. each time. The obtained filter cake is slurried again in 200 g of pure water, and 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Next, after stirring at 25 ° C. for 30 minutes and filtering, washing is repeated 6 times using 1 liter of hot water at about 80 ° C. The obtained filter cake is slurried again in 200 g of pure water, then titrated with 1N sodium hydroxide, and the amount of -SX groups present in the PPS is determined from the amount of sodium hydroxide consumed.
なお、塩化メチレンによるオリゴマー抽出量が０．００１重量％以上０．９重量％以下であり、かつ−ＳＸ基が１０μｍｏｌ／ｇ以上１０，０００μｍｏｌ／ｇ以下であるＰＰＳの具体的な製造方法としては、特開平８−２５３５８７号公報の実施例１および２に記載された製造方法（段落番号００４１〜００４４）や特開平１１−１０６６５６号公報の合成例１および２に記載された製造方法（段落番号００４６〜００４８）等が挙げられる。
さらに、本発明で用いるＰＰＳは３２０℃における溶融粘度（フローテスターを用いて、３００℃、荷重１９６Ｎ、Ｌ／Ｄ（Ｌ：オリフィス長、Ｄ：オリフィス内径）＝１０／１で６分間保持した値）は、好ましくは１〜１０，０００ポイズであることが好ましく、１００〜１０，０００ポイズであることがさらに好ましい。
As a specific method for producing PPS, the amount of oligomer extracted with methylene chloride is 0.001 wt% or more and 0.9 wt% or less, and the —SX group is 10 μmol / g or more and 10,000 μmol / g or less. The production methods described in Examples 1 and 2 (paragraph numbers 0041 to 0044) of JP-A-8-255357 and the production methods (paragraph numbers) described in synthesis examples 1 and 2 of JP-A-11-106656 0046 to 0048).
Further, the PPS used in the present invention has a melt viscosity at 320 ° C. (using a flow tester, 300 ° C., load 196 N, L / D (L: orifice length, D: orifice inner diameter) = 10/1 and held for 6 minutes. ) Is preferably 1 to 10,000 poise, and more preferably 100 to 10,000 poise.
また、本発明では、ポリフェニレンスルフィド樹脂（Ｂ）として、ポリフェニレンスルフィド樹脂に酸性官能基や反応性官能基を導入したものも好適に用いることが出来る。このような官能基を導入することで、本発明の高分子電解質組成物においてイオン交換基を有する高分子化合物（Ａ）とポリフェニレンスルフィド樹脂（Ｂ）との混和性が向上し、イオン交換基を有する高分子化合物（Ａ）中へのポリフェニレンスルフィド樹脂（Ｂ）の分散性が向上すると考えられる。また、特に酸性官能基を導入した場合、本発明の高分子電解質組成物からなるプロトン交換膜において、プロトン伝導度に関与する官能基が増加することを意味し、高いプロトン伝導度が発現できるので好ましい。導入する酸性官能基としては、例えば、スルホン酸基、リン酸基、スルホンイミド基、カルボン酸基、マレイン酸基，無水マレイン酸基，フマル酸基，イタコン酸基，アクリル酸基およびメタクリル酸基が好ましく、強酸性基であるスルホン酸基、リン酸基がさらに好ましく、スルホン酸基が最も好ましい。導入する反応性官能基としてはエポキシ基、オキサゾニル基、アミノ基、イソシアネート基およびカルボジイミド基などが好ましく、エポキシ基が特に好ましい。さらに、上記各種官能基を２種以上導入してもよい。 Moreover, in this invention, what introduce | transduced the acidic functional group and the reactive functional group into polyphenylene sulfide resin can be used suitably as polyphenylene sulfide resin (B). By introducing such a functional group, the miscibility between the polymer compound (A) having an ion exchange group and the polyphenylene sulfide resin (B) in the polymer electrolyte composition of the present invention is improved, and the ion exchange group is reduced. It is considered that the dispersibility of the polyphenylene sulfide resin (B) in the polymer compound (A) is improved. In particular, when an acidic functional group is introduced, the proton exchange membrane comprising the polymer electrolyte composition of the present invention means that the functional group involved in proton conductivity increases, and high proton conductivity can be expressed. preferable. Examples of acidic functional groups to be introduced include sulfonic acid groups, phosphoric acid groups, sulfonimide groups, carboxylic acid groups, maleic acid groups, maleic anhydride groups, fumaric acid groups, itaconic acid groups, acrylic acid groups, and methacrylic acid groups. Are preferred, sulfonic acid groups and phosphoric acid groups which are strongly acidic groups are more preferred, and sulfonic acid groups are most preferred. As the reactive functional group to be introduced, an epoxy group, an oxazonyl group, an amino group, an isocyanate group, a carbodiimide group and the like are preferable, and an epoxy group is particularly preferable. Further, two or more of the above various functional groups may be introduced.
酸性官能基や反応性官能基の導入方法は特に限定されず、一般的な方法を用いて実施される。例えばスルホン酸基の導入については、無水硫酸、発煙硫酸などのスルホン化剤を用いて公知の条件で実施することが出来る。例えば、Ｋ．Ｈｕ， Ｔ．Ｘｕ， Ｗ．Ｙａｎｇ， Ｙ．Ｆｕ， Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ， Ｖｏｌ．９１，や、 Ｅ．Ｍｏｎｔｏｎｅｒｉ， Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ： Ｐａｒｔ Ａ： Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ， Ｖｏｌ．２７， ３０４３−３０５１（１９８９）に記載の条件で実施できる。
また、導入した酸性官能基を金属塩またはアミン塩に置換したものも好適に用いられる。金属塩としてはナトリウム塩、カリウム塩等のアルカリ金属塩、カルシウム塩等のアルカリ土類金属塩が好ましい。
The method for introducing an acidic functional group or a reactive functional group is not particularly limited, and a general method is used. For example, introduction of a sulfonic acid group can be carried out under known conditions using a sulfonating agent such as sulfuric anhydride or fuming sulfuric acid. For example, K.K. Hu, T .; Xu, W .; Yang, Y. et al. Fu, Journal of Applied Polymer Science, Vol. 91, E.E. Montoneri, Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 27, 3043-3051 (1989).
Further, those in which the introduced acidic functional group is substituted with a metal salt or an amine salt are also preferably used. The metal salt is preferably an alkali metal salt such as sodium salt or potassium salt, or an alkaline earth metal salt such as calcium salt.
本発明で用いられるポリスルホン樹脂（Ｃ）は、所謂ポリスルホン樹脂であれば特に限定されないが、下記一般式（５）であらわされる構造が好ましくは８０モル％以上、より好ましくは９０モル％以上からなるポリスルホン樹脂である。 The polysulfone resin (C) used in the present invention is not particularly limited as long as it is a so-called polysulfone resin, but the structure represented by the following general formula (5) is preferably 80 mol% or more, more preferably 90 mol% or more. Polysulfone resin.
本発明で用いられるポリスルホン樹脂（Ｃ）は、その製造方法については特に限定されず、例えば、ビスフェノールＡのナトリウム塩と４，４‘−ジクロロジフェニルスルフォンとを反応させることにより容易に製造できる。
また、本発明では、ポリスルホン樹脂（Ｃ）として、ポリスルホン樹脂に酸性官能基や反応性官能基を導入したものも好適に用いることが出来る。このような官能基を導入することで、本発明の高分子電解質組成物においてイオン交換基を有する高分子化合物（Ａ）とポリスルホン樹脂（Ｃ）との混和性が向上し、イオン交換基を有する高分子化合物（Ａ）中へのポリスルホン樹脂（Ｃ）の分散性が向上すると考えられる。
The production method of the polysulfone resin (C) used in the present invention is not particularly limited, and can be easily produced, for example, by reacting bisphenol A sodium salt with 4,4′-dichlorodiphenylsulfone.
Moreover, in this invention, what introduce | transduced the acidic functional group and the reactive functional group into polysulfone resin can be used suitably as polysulfone resin (C). By introducing such a functional group, the miscibility between the polymer compound (A) having an ion exchange group and the polysulfone resin (C) is improved in the polymer electrolyte composition of the present invention, and the ion exchange group is contained. It is considered that the dispersibility of the polysulfone resin (C) in the polymer compound (A) is improved.
また、特に酸性官能基を導入した場合、本発明の高分子電解質組成物からなるプロトン交換膜において、プロトン伝導度に関与する官能基が増加することを意味し、高いプロトン伝導度が発現できるので好ましい。導入する酸性官能基としては、例えば、スルホン酸基、リン酸基、スルホンイミド基、カルボン酸基、マレイン酸基，無水マレイン酸基，フマル酸基，イタコン酸基，アクリル酸基およびメタクリル酸基が好ましく、強酸性基であるスルホン酸基、リン酸基がさらに好ましく、スルホン酸基が最も好ましい。導入する反応性官能基としてはエポキシ基、オキサゾニル基、アミノ基、イソシアネート基およびカルボジイミド基などが好ましく、エポキシ基が特に好ましい。さらに、上記各種官能基を２種以上導入してもよい。 In particular, when an acidic functional group is introduced, the proton exchange membrane comprising the polymer electrolyte composition of the present invention means that the functional group involved in proton conductivity increases, and high proton conductivity can be expressed. preferable. Examples of acidic functional groups to be introduced include sulfonic acid groups, phosphoric acid groups, sulfonimide groups, carboxylic acid groups, maleic acid groups, maleic anhydride groups, fumaric acid groups, itaconic acid groups, acrylic acid groups, and methacrylic acid groups. Are preferred, sulfonic acid groups and phosphoric acid groups which are strongly acidic groups are more preferred, and sulfonic acid groups are most preferred. As the reactive functional group to be introduced, an epoxy group, an oxazonyl group, an amino group, an isocyanate group, a carbodiimide group and the like are preferable, and an epoxy group is particularly preferable. Further, two or more of the above various functional groups may be introduced.
酸性官能基や反応性官能基の導入方法は特に限定されず、一般的な方法を用いて導入できる。例えばスルホン酸基の導入については、無水硫酸、発煙硫酸、クロロスルホン酸などのスルホン化剤を用いて公知の条件で実施することができる。
本発明で用いられるエポキシ基含有化合物（Ｄ）は、エポキシ基を有する化合物であれば特に限定されず、例えば、エポキシ基を含有する低分子化合物、エポキシ基を有する不飽和モノマーの単独重合体または共重合体（Ｅ）、およびエポキシ樹脂（Ｆ）などが挙げられる。高分子化合物の方が高温での取り扱いが容易なことから、エポキシ基を有する不飽和モノマーの単独重合体または共重合体（Ｅ）およびエポキシ樹脂（Ｆ）が好ましい。
The method for introducing an acidic functional group or a reactive functional group is not particularly limited, and can be introduced using a general method. For example, introduction of a sulfonic acid group can be carried out under known conditions using a sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid and the like.
The epoxy group-containing compound (D) used in the present invention is not particularly limited as long as it is a compound having an epoxy group. For example, a low molecular compound containing an epoxy group, a homopolymer of an unsaturated monomer having an epoxy group, or A copolymer (E), an epoxy resin (F), etc. are mentioned. Since the polymer compound is easier to handle at high temperature, a homopolymer or copolymer (E) of an unsaturated monomer having an epoxy group and an epoxy resin (F) are preferred.
上記のエポキシ基を含有する低分子化合物としては、２００℃で固体か液体であるものが好ましく、具体的には、１，２−エポキシ−３−フェノキシプロパン、Ｎ−（２，３−エポキシプロピル）フタルイミド、３，４−エポキシテトラヒドロチオフェン−１，１−ジオキサイド、グリシジル４−ノニルフェニルエーテル、グリシジルトシレート、グリシジルトリチルエーテルなどが挙げられる。 The low molecular weight compound containing an epoxy group is preferably a solid or liquid at 200 ° C., specifically, 1,2-epoxy-3-phenoxypropane, N- (2,3-epoxypropyl). ) Phthalimide, 3,4-epoxytetrahydrothiophene-1,1-dioxide, glycidyl 4-nonylphenyl ether, glycidyl tosylate, glycidyl trityl ether, and the like.
本発明で用いられるエポキシ基を有する不飽和モノマーの単独重合体または共重合体（Ｅ）を構成するエポキシ基を有する不飽和モノマーとしては、エポキシ基を有する不飽和モノマーであれば別に制限されず、例えば、グリシジルメタアクリレート、グリシジルアクリレート、ビニルグリシジルエーテル、ヒドロキシアルキル（メタ）アクリレートのグリシジルエーテル、ポリアルキレングリコール（メタ）アクリレートのグリシジルエーテル、グリシジルイタコネート等が挙げられる。これらの中でもグリシジルメタアクリレートが好ましい。 The unsaturated monomer having an epoxy group constituting the homopolymer or copolymer (E) of the unsaturated monomer having an epoxy group used in the present invention is not limited as long as it is an unsaturated monomer having an epoxy group. Examples thereof include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate and the like. Among these, glycidyl methacrylate is preferable.
エポキシ基を有する不飽和モノマーの共重合体の場合、上記エポキシ基を有する不飽和モノマーと共重合する他の不飽和モノマーとしては、スチレン等のビニル芳香族化合物、アクリロニトリル等のシアン化ビニルモノマー、酢酸ビニル、（メタ）アクリル酸エステル等が好ましい。これら共重合可能な不飽和モノマーを共重合して得られる共重合体の例として、例えば、スチレン-グリシジルメタクリレート共重合体、スチレン-グリシジルメタクリレート-メチルメタクリレート共重合体、スチレン-グリシジルメタクリレート-アクリロニトリル共重合体等が挙げられる。 In the case of a copolymer of an unsaturated monomer having an epoxy group, other unsaturated monomers copolymerized with the unsaturated monomer having an epoxy group include vinyl aromatic compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, Vinyl acetate, (meth) acrylic acid ester and the like are preferable. Examples of copolymers obtained by copolymerizing these copolymerizable unsaturated monomers include, for example, styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene-glycidyl methacrylate-acrylonitrile copolymer. A polymer etc. are mentioned.
本発明で用いられるエポキシ樹脂（Ｆ）は、例えば、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ヒンダトイン型エポキシ樹脂、ビフェニル型エポキシ樹脂、脂環式エポキシ樹脂、トリフェニルメタン型エポキシ樹脂およびフェノールノボラック型エポキシ樹脂が挙げられる。これらから選ばれる１種または２種以上を混合して用いることもできる。その中でもクレゾールノボラック型エポキシ樹脂およびビスフェノールＡ型エポキシ樹脂が好ましく、クレゾールノボラック型エポキシ樹脂が特に好ましい。 The epoxy resin (F) used in the present invention is, for example, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a hindered-in type epoxy resin, a biphenyl type epoxy resin, or an alicyclic ring. And epoxy epoxy resin, triphenylmethane type epoxy resin and phenol novolac type epoxy resin. One or more selected from these may be used in combination. Among them, cresol novolac type epoxy resins and bisphenol A type epoxy resins are preferable, and cresol novolac type epoxy resins are particularly preferable.
本発明では、ポリスルホン樹脂（Ｃ）とエポキシ樹脂（Ｆ）をあらかじめ混合、反応させて添加することができる。即ち、ポリスルホン樹脂（Ｃ）として、ポリフェニレンエーテル樹脂とエポキシ樹脂とが反応して得られたエポキシ変性ポリスルホン樹脂（Ｇ）を用いることができる。勿論、（Ａ）成分および（Ｂ）成分と共にポリスルホン樹脂（Ｃ）とエポキシ樹脂（Ｆ）を混合して本発明の組成物とした後に、後述するような条件下でポリスルホン樹脂（Ｃ）とエポキシ樹脂（Ｆ）とを反応させてもよい。
ポリスルホン樹脂（Ｃ）としてエポキシ変性ポリスルホン樹脂（Ｇ）を用いることにより、得られた高分子電解質組成物の分散性が向上し、その結果、高分子電解質組成物およびこの組成物からなるプロトン交換膜の耐久性はさらに向上する。
In the present invention, the polysulfone resin (C) and the epoxy resin (F) can be mixed and reacted in advance. That is, as the polysulfone resin (C), an epoxy-modified polysulfone resin (G) obtained by reacting a polyphenylene ether resin and an epoxy resin can be used. Of course, after the polysulfone resin (C) and the epoxy resin (F) are mixed together with the components (A) and (B) to obtain the composition of the present invention, the polysulfone resin (C) and the epoxy are used under the conditions described later. The resin (F) may be reacted.
By using the epoxy-modified polysulfone resin (G) as the polysulfone resin (C), the dispersibility of the obtained polymer electrolyte composition is improved. As a result, the polymer electrolyte composition and a proton exchange membrane comprising the composition are obtained. The durability is further improved.
エポキシ変性ポリスルホン樹脂（Ｇ）の製造方法は、反応温度が１００〜２５０℃であることが好ましい。より好ましくは１２０〜１９５℃、さらに好ましくは１４０〜１９０℃の範囲である。また反応時間は３時間未満が好ましく、より好ましくは２時間以内、特に好ましくは４０分以内である。
エポキシ変性ポリスルホン樹脂（Ｇ）の製造に用いる反応器は、ポリスルホン樹脂とエポキシ樹脂を均一に混合、攪拌または混練できるものが好ましく、粘度が高い場合は二軸押出機、ニーダー等の混練機を用いることができる。その製造方法は連続反応プロセス、バッチ反応プロセス、セミバッチ反応プロセスのいずれのプロセス形態を用いることができる。
As for the manufacturing method of an epoxy-modified polysulfone resin (G), it is preferable that reaction temperature is 100-250 degreeC. More preferably, it is 120-195 degreeC, More preferably, it is the range of 140-190 degreeC. The reaction time is preferably less than 3 hours, more preferably within 2 hours, particularly preferably within 40 minutes.
The reactor used for the production of the epoxy-modified polysulfone resin (G) is preferably one that can uniformly mix, stir or knead the polysulfone resin and the epoxy resin. If the viscosity is high, a kneader such as a twin screw extruder or kneader is used. be able to. The manufacturing method can use any process form of a continuous reaction process, a batch reaction process, and a semi-batch reaction process.
エポキシ変性ポリスルホン樹脂（Ｇ）の製造方法では、反応速度の向上や副反応抑制、反応組成物の構造制御の観点から、反応系に塩基性化合物を添加することができる。塩基性化合物の具体例としては、リチウム、ナトリウム、カリウム、ナトリウムメチラート、ナトリウムエチラート、トリエチルアミンやトリブチルアミン等の３級アミン、イミダゾール、ナトリウムフェノキシド、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸カリウム、炭酸ナトリウム等が挙げられる。これらの中でもナトリウムメチラート、トリエチルアミン、トリブチルアミン、水酸化ナトリウム等が好ましい。上記塩基性化合物の他にも４級アンモニウム塩も触媒として用いることができる。 In the production method of the epoxy-modified polysulfone resin (G), a basic compound can be added to the reaction system from the viewpoint of improving the reaction rate, suppressing side reactions, and controlling the structure of the reaction composition. Specific examples of basic compounds include lithium, sodium, potassium, sodium methylate, sodium ethylate, tertiary amines such as triethylamine and tributylamine, imidazole, sodium phenoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, Examples include potassium carbonate and sodium carbonate. Among these, sodium methylate, triethylamine, tributylamine, sodium hydroxide and the like are preferable. In addition to the above basic compounds, quaternary ammonium salts can also be used as catalysts.
本発明の高分子電解質組成物は、上述した、イオン交換基を有する高分子化合物（Ａ）、ポリフェニレンスルフィド樹脂（Ｂ）、ポリスルホン樹脂（Ｃ）およびエポキシ基含有化合物（Ｄ）からなる組成物である。このような本発明の高分子電解質組成物およびこの組成物からなるプロトン交換膜は、イオン交換基を有する高分子化合物（Ａ）単独の場合と比べても、ポリフェニレンスルフィド樹脂（Ｂ）、ポリスルホン樹脂（Ｃ）、およびエポキシ基含有化合物（Ｄ）をそれぞれ単独にイオン交換基を有する高分子化合物（Ａ）に含有させた場合に比べても、その耐久性が著しく向上する。さらに驚くべきことに、本発明の高分子電解質組成物は、イオン交換基を有する高分子化合物（Ａ）に本発明で用いた樹脂を含めた多くの樹脂を本発明以外の様々な組み合わせで含有させた場合と比べても、その耐久性が著しく向上する。 The polymer electrolyte composition of the present invention is a composition comprising the above-described polymer compound (A) having an ion exchange group, polyphenylene sulfide resin (B), polysulfone resin (C), and epoxy group-containing compound (D). is there. Such a polyelectrolyte composition of the present invention and a proton exchange membrane comprising the composition include a polyphenylene sulfide resin (B) and a polysulfone resin, as compared with the case of the polymer compound (A) having an ion exchange group alone. Even when (C) and the epoxy group-containing compound (D) are each contained alone in the polymer compound (A) having an ion exchange group, the durability is remarkably improved. Surprisingly, the polymer electrolyte composition of the present invention contains many resins including the resin used in the present invention in the polymer compound (A) having an ion exchange group in various combinations other than the present invention. The durability is remarkably improved as compared with the case of making them.
次に、イオン交換基を有する高分子化合物（Ａ）とポリフェニレンスルフィド樹脂（Ｂ）とポリスルホン樹脂（Ｃ）とエポキシ基含有化合物（Ｄ）の組成比について説明する。
本発明の高分子電解質組成物は、上記した、ポリフェニレンスルフィド樹脂（Ｂ）とポリスルホン樹脂（Ｃ）との重量比がＢ／Ｃ＝１／９９〜９９／１であることが好ましい。さらに好ましくは、Ｂ／Ｃ＝２０／８０〜９５／５、最も好ましくはＢ／Ｃ＝３０／７０〜９０／１０の重量比である。
Next, the composition ratio of the polymer compound (A) having an ion exchange group, the polyphenylene sulfide resin (B), the polysulfone resin (C), and the epoxy group-containing compound (D) will be described.
In the polymer electrolyte composition of the present invention, the weight ratio of the polyphenylene sulfide resin (B) to the polysulfone resin (C) is preferably B / C = 1/99 to 99/1. More preferably, the weight ratio is B / C = 20/80 to 95/5, and most preferably B / C = 30/70 to 90/10.
また、ポリフェニレンスルフィド樹脂（Ｂ）、ポリスルホン樹脂（Ｃ）とイオン交換基を有する高分子化合物（Ａ）との重量比（（Ｂ＋Ｃ）／Ａ）は９９／１〜０．０１／９９．９９であることが好ましい。プロトン導電性と耐久性のバランスから、（Ｂ＋Ｃ）／Ａは９０／１０〜０．０５／９９．９５がより好ましく、７０／３０〜０．１／９９．９がさらに好ましく、５０／５０〜１／９９が特に好ましく、３０／７０〜５／９５が最も好ましい。 The weight ratio ((B + C) / A) of the polyphenylene sulfide resin (B), the polysulfone resin (C) and the polymer compound (A) having an ion exchange group is 99/1 to 0.01 / 99.99. Preferably there is. From the balance between proton conductivity and durability, (B + C) / A is more preferably 90/10 to 0.05 / 99.95, further preferably 70/30 to 0.1 / 99.9, and 50/50 to 1/99 is particularly preferable, and 30/70 to 5/95 is most preferable.
また、エポキシ基含有化合物（Ｄ）の含有量は、ポリフェニレンスルフィド樹脂（Ｂ）とポリスルホン樹脂（Ｃ）の合計重量に対して、Ｄ／（Ｂ＋Ｃ）＝１／１００〜２００／１００が好ましく、Ｄ／（Ｂ＋Ｃ）＝２／１００〜１００／１００がさらに好ましく、Ｄ／（Ｂ＋Ｃ）＝３／１００〜５０／１００が特に好ましい。
なお、本発明では（Ａ）〜（Ｇ）の各成分は、いずれも２種類以上の化合物で構成されていてもよい。例えば、ポリフェニレンスルフィド樹脂（Ｂ）として、ポリフェニレンスルフィドとスルホン化したポリフェニレンスルフィドの混合物を用いる例などが挙げられる。また、ポリスルホン樹脂（Ｃ）として、ポリスルホンとスルホン化したポリスルホンとの混合物を用いる例などが挙げられる。
Further, the content of the epoxy group-containing compound (D) is preferably D / (B + C) = 1/100 to 200/100 with respect to the total weight of the polyphenylene sulfide resin (B) and the polysulfone resin (C). / (B + C) = 2/100 to 100/100 is more preferable, and D / (B + C) = 3/100 to 50/100 is particularly preferable.
In the present invention, each of the components (A) to (G) may be composed of two or more kinds of compounds. For example, the polyphenylene sulfide resin (B) includes an example using a mixture of polyphenylene sulfide and sulfonated polyphenylene sulfide. Examples of the polysulfone resin (C) include a mixture of polysulfone and sulfonated polysulfone.
本発明の高分子電解質組成物については、必要に応じて酸化防止剤や老化防止剤、重金属不活性化剤、難燃剤等の各種添加剤を添加することができる。本発明の高分子電解質組成物と添加剤との重量比（電解質組成物／添加剤）は８０／２０〜９９．９９９／０．００１であることが好ましく、より好ましくは９０／１０〜９９．９９／０．０１、さらに好ましくは９５／５〜９９．９／０．１である。 About the polymer electrolyte composition of this invention, various additives, such as antioxidant, antioxidant, a heavy metal deactivator, a flame retardant, can be added as needed. The weight ratio of the polymer electrolyte composition of the present invention to the additive (electrolyte composition / additive) is preferably 80/20 to 99.999 / 0.001, more preferably 90/10 to 99.99. 99 / 0.01, more preferably 95/5 to 99.9 / 0.1.
次に、本発明の高分子電解質組成物の作製方法について説明する。前述の成分（Ａ）〜（Ｇ）の中から選ばれた成分を混合して本発明の高分子電解質組成物を得るわけであるが、その方法は特に限定されず、一般的な高分子組成物の混合方法が好適に適用できる。 Next, a method for producing the polymer electrolyte composition of the present invention will be described. The polymer electrolyte composition of the present invention is obtained by mixing the components selected from the aforementioned components (A) to (G), but the method is not particularly limited, and a general polymer composition The mixing method of the product can be suitably applied.
例えば、イオン交換基を有する高分子化合物（Ａ）またはその前駆体ポリマーと、（Ｂ）〜（Ｇ）成分から選ばれた成分を熱溶融して、混練押出機、ラボプラストミル、混練ロール、バンバリーミキサー等で混練する方法が挙げられる。また、あらかじめ（Ｂ）〜（Ｇ）成分から選ばれた成分を熱溶融して、混練押出機、ラボプラストミル、混練ロール、バンバリーミキサー等で混練して混合物を得てから、この混合物とイオン交換基を有する高分子化合物（Ａ）またはその前駆体ポリマーとを同様に混練して最終的な高分子電解質組成物を得ることも出来る。混練の組み合わせや順番は任意に行なうことが出来る。なお、イオン交換基を有する高分子化合物（Ａ）の代わりにその前駆体ポリマーを用いた場合は、混練後にアルカリ加水分解処理および酸処理を行ってイオン交換基を有する形態に変換することで本発明の高分子電解質組成物を得ることができる。 For example, a polymer compound (A) having an ion exchange group or a precursor polymer thereof, and a component selected from the components (B) to (G) are thermally melted, and a kneading extruder, a lab plast mill, a kneading roll, The method of kneading with a Banbury mixer etc. is mentioned. In addition, the components selected from the components (B) to (G) are thermally melted in advance and kneaded with a kneading extruder, a lab plast mill, a kneading roll, a Banbury mixer or the like to obtain a mixture. The polymer compound (A) having an exchange group or a precursor polymer thereof can be similarly kneaded to obtain a final polymer electrolyte composition. The combination and order of kneading can be performed arbitrarily. In addition, when the precursor polymer is used in place of the polymer compound (A) having an ion exchange group, it is converted into a form having an ion exchange group by performing an alkali hydrolysis treatment and an acid treatment after kneading. The polymer electrolyte composition of the invention can be obtained.
この時の混練の方法は、ブラベンダー、ニーダー、バンバリーミキサーおよび押出機などの従来公知の技術によって達成される。特に押出機を用いると、得られた高分子電解質組成物において、イオン交換基を有する高分子化合物（Ａ）中に他の成分を微分散させることが容易にできるので好ましい。 The kneading method at this time is achieved by a conventionally known technique such as a Brabender, a kneader, a Banbury mixer, and an extruder. In particular, it is preferable to use an extruder because the obtained polymer electrolyte composition can easily finely disperse other components in the polymer compound (A) having an ion exchange group.
本発明で用いられる高分子電解質組成物を工業的に容易に得る方法として最も好ましい実施態様としては、上記した各成分を溶融混練するための押出機が、ニーディングブロックをスクリューの任意の位置に組み込むことが可能な二軸以上の多軸押出機であり、用いるスクリューの全ニーディングブロック部分を実質的に（Ｌ／Ｄ）≧１．５、さらに好ましくは（Ｌ／Ｄ）≧５（ここで、Ｌはニーディングブロックの合計長さ、Ｄはニーディングブロックの最大外径を表す）に組み込み、かつ、（π・Ｄ・Ｎ／ｈ）≧５０〔ここで、π＝３．１４、Ｄ＝メタリングゾーンに相当するスクリュー外径、Ｎ＝スクリュー回転数（回転／秒）、ｈ＝メタリングゾーンの溝深さ〕を満たす態様である。これらの押出機は、原料の流れ方向に対し上流側に第一原料供給口、これより下流に第二原料供給口を有し、必要に応じて、第二原料供給口より下流にさらに１つ以上の原料供給口を設けてもよく、さらに必要に応じて、これら原料供給口の間に真空ベント口を設けてもよい。 As a most preferred embodiment as a method for industrially easily obtaining the polymer electrolyte composition used in the present invention, an extruder for melting and kneading each of the above-mentioned components has a kneading block at an arbitrary position of a screw. It is a multi-screw extruder having two or more screws that can be incorporated, and the entire kneading block portion of the screw used is substantially (L / D) ≧ 1.5, more preferably (L / D) ≧ 5 (here L is the total length of the kneading block, D is the maximum outside diameter of the kneading block), and (π · D · N / h) ≧ 50 (where π = 3.14, D = screw outer diameter corresponding to the metering zone, N = screw rotation speed (rotation / second), h = groove depth of the metering zone]. These extruders have a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a second raw material supply port on the downstream side, and if necessary, one more downstream on the downstream side of the second raw material supply port. The above raw material supply ports may be provided, and a vacuum vent port may be provided between these raw material supply ports as necessary.
また、イオン交換基を有する高分子化合物（Ａ）またはその前駆体ポリマーの溶液と、（Ｂ）〜（Ｇ）成分の各溶液を混合して溶液を作成した後に、溶媒を除去する方法も挙げられる。この場合も、イオン交換基を有する高分子化合物（Ａ）の溶液の代わりにその前駆体ポリマーの溶液を用いた場合は、溶媒を除去した後、アルカリ加水分解処理および酸処理を行ってイオン交換基を有する形態に変換することで本発明の高分子電解質組成物を得ることが出来る。 In addition, a method of removing the solvent after preparing a solution by mixing a solution of the polymer compound (A) having an ion exchange group or a precursor polymer thereof with each solution of the components (B) to (G) is also mentioned. It is done. Also in this case, when the precursor polymer solution was used in place of the polymer compound (A) solution having an ion exchange group, the solvent was removed, and then ion exchange was performed by alkali hydrolysis treatment and acid treatment. The polymer electrolyte composition of the present invention can be obtained by converting to a form having a group.
上記のような方法で本発明の高分子電解質組成物を得ることが出来るが、本発明ではイオン交換基を有する高分子化合物（Ａ）中に、他の成分が微分散している構造を少なくとも有することにより、高寿命化等の本発明の効果が増幅される。つまり、イオン交換基を有する高分子化合物（Ａ）中に、他の成分からなる粒子が円換算平均粒子径で０．０００１μｍ以上１μｍ以下、好ましくは０．０００１μｍ以上０．８μｍ以下、さらに好ましくは０．０００１μｍ以上０．５μｍ以下、特に好ましくは０．０００１μｍ以上０．３μｍ以下で分散している構造を有することが好適である。組成物の全ての領域で上記範囲を満たすことは必ずしも必要ではなく、組成物全領域の５０〜１００％が上記範囲を満たしていればよい。 The polymer electrolyte composition of the present invention can be obtained by the method as described above. In the present invention, at least a structure in which other components are finely dispersed in the polymer compound (A) having an ion exchange group is used. By having it, the effects of the present invention such as extending the life are amplified. That is, in the polymer compound (A) having an ion exchange group, the particles composed of other components have a circular average particle diameter of 0.0001 μm to 1 μm, preferably 0.0001 μm to 0.8 μm, more preferably It is preferable to have a structure in which it is dispersed in a range of 0.0001 μm to 0.5 μm, particularly preferably 0.0001 μm to 0.3 μm. It is not always necessary to satisfy the above range in all regions of the composition, as long as 50 to 100% of the entire region of the composition satisfies the above range.
また、（Ａ）成分が他の成分からなる分散粒子の内部に入り込んでいる構造を有してもかまわない。ただし、このときも分散粒子の粒子径は、高寿命化の観点から、円換算平均粒子径で好ましくは０．０００１μｍ以上１μｍ以下、より好ましくは０．０００１μｍ以上０．８μｍ以下、さらに好ましくは０．０００１μｍ以上０．５μｍ以下、特に好ましくは０．０００１μｍ以上０．３μｍ以下である。
そして、後述するプロトン交換膜中でも上記のような微分散構造を少なくとも有することが好適である。
このような微分散構造は、材料の組成、加工時の各種条件等によりコントロールすることができる。より具体的には、材料の組成では各成分の組み合わせと量比、相溶化剤の使用、溶媒使用時には溶媒の種類等が挙げられる。また、加工時の各種条件としては温度条件、攪拌・混練条件が挙げられ、特に押出加工時にはスクリューデザイン、スクリュー回転数の影響が大きい。
Moreover, you may have a structure where (A) component has penetrated the inside of the dispersion particle which consists of another component. However, at this time, the particle diameter of the dispersed particles is preferably 0.0001 μm or more and 1 μm or less, more preferably 0.0001 μm or more and 0.8 μm or less, and still more preferably 0 in terms of an average particle diameter in terms of a circle, from the viewpoint of extending the life. It is 0.0001 to 0.5 μm, particularly preferably 0.0001 to 0.3 μm.
And it is suitable to have at least the fine dispersion structure as described above even in the proton exchange membrane described later.
Such a finely dispersed structure can be controlled by the composition of the material, various conditions during processing, and the like. More specifically, the composition of the material includes the combination and amount ratio of each component, the use of a compatibilizing agent, and the type of solvent when using the solvent. Various conditions during processing include temperature conditions and stirring / kneading conditions, and the influence of screw design and screw rotation speed is particularly large during extrusion processing.
なお、本発明における円換算平均粒子径は以下のように定義する。本発明の高分子電解質組成物またはプロトン交換膜から薄切片を作製し、常法により四酸化ルテニウム等の染色剤で染色し、透過型電子顕微鏡で観察し、染色されている相の平均粒子径をとり、この値をもって粒子径とする。このときの平均粒子径は、薄切片の任意の２０×２０μｍの視野を直接、あるいはネガより写真に焼き付けた後、画像解析装置に読み込み、これから計算される各粒子の円換算径（面積を同じくする円の直径）の数平均値とする。ただし、写真から画像解析装置に入力する際に染色境界が不明瞭な場合には写真のトレースを行い、この図を用いて画像解析装置に入力を行う。 In addition, the circle conversion average particle diameter in this invention is defined as follows. A thin slice is prepared from the polymer electrolyte composition or proton exchange membrane of the present invention, dyed with a dye such as ruthenium tetroxide by a conventional method, observed with a transmission electron microscope, and the average particle diameter of the dyed phase And take this value as the particle size. The average particle diameter at this time is the circle-converted diameter (the same area for each particle) calculated from this, after reading an arbitrary 20 × 20 μm field of view of a thin slice directly or after printing it on a photo from a negative, and reading it into an image analyzer. Number average value). However, if the staining boundary is unclear when inputting from the photograph to the image analysis apparatus, the photograph is traced and input to the image analysis apparatus using this figure.
次に、本発明の高分子電解質組成物からなるプロトン交換膜の作製方法について説明する。本発明の高分子電解質組成物は、製膜してプロトン交換膜として用いることが出来る。製膜手段は特に限定されず、一般的な高分子組成物の製膜方法が好適に適用できる。例えば、カレンダー成形、プレス成形、Ｔダイ成形およびインフレーション成形などの公知の製膜方法が挙げられる。これらの中でも、Ｔダイ成形およびインフレーション成形は本発明の高分子電解質組成物からプロトン交換膜を工業的に容易に得る方法として好ましい。特にインフレーション成形は、異方性の小さい膜を得るという観点からも好ましい。 Next, a method for producing a proton exchange membrane made of the polymer electrolyte composition of the present invention will be described. The polymer electrolyte composition of the present invention can be formed into a membrane and used as a proton exchange membrane. The film forming means is not particularly limited, and a general polymer composition film forming method can be suitably applied. For example, known film forming methods such as calendar molding, press molding, T-die molding, and inflation molding can be used. Among these, T-die molding and inflation molding are preferable as methods for easily industrially obtaining a proton exchange membrane from the polymer electrolyte composition of the present invention. Inflation molding is particularly preferable from the viewpoint of obtaining a film having small anisotropy.
また、本発明の高分子電解質組成物の前駆体、例えばイオン交換基を有する高分子化合物（Ａ）の前駆体ポリマーと（Ｂ）〜（Ｇ）成分から選ばれた成分とからなる高分子組成物を、前述の製膜方法を用いて製膜した後に、適当な後処理、例えばアルカリ加水分解処理や酸処理を行ってイオン交換基を有する形態に変換することで、本発明の高分子電解質組成物からなるプロトン交換膜を得ることも出来る。 Also, a polymer composition comprising a precursor of the polymer electrolyte composition of the present invention, for example, a precursor polymer of a polymer compound (A) having an ion exchange group, and a component selected from the components (B) to (G). After the product is formed using the above-described film forming method, the polymer electrolyte of the present invention is converted into a form having an ion exchange group by performing an appropriate post-treatment such as alkali hydrolysis treatment or acid treatment. A proton exchange membrane comprising the composition can also be obtained.
また、（Ａ）〜（Ｇ）成分の各溶液を混合して溶液を作成し、その溶液をキャストした後、溶媒を除去することによってもプロトン交換膜を得ることができる。キャスト方法としては、シャーレに流し込み製造する方法をはじめ、グラビアロールコータ−、ナチュラルロールコータ、リバースロールコータ、ナイフコータ−およびディップコータ−等の公知の塗工方法を用いることができる。キャスト法に用いる基材は、一般的なポリマーフィルム、金属箔、アルミナ、ケイ素等の基板、特開平８−１６２１３２号公報に記載のＰＴＦＥ膜を延伸処理した多孔質膜、および特開昭５３−１４９８８１号公報ならびに特公昭６３−６１３３７号公報に示されるフィブリル化繊維等を用いることができる。溶媒の除去の方法として、室温〜２００℃での熱処理および減圧処理等の方法を用いることができる。また熱処理をする場合、段階的に昇温させ溶媒を除去することも可能である。 Alternatively, the proton exchange membrane can be obtained by mixing each solution of the components (A) to (G) to prepare a solution, casting the solution, and then removing the solvent. As a casting method, a known coating method such as a method of casting into a petri dish, a gravure roll coater, a natural roll coater, a reverse roll coater, a knife coater and a dip coater can be used. The base material used for the casting method is a general polymer film, a metal foil, a substrate made of alumina, silicon or the like, a porous film obtained by stretching a PTFE film described in JP-A-8-162132, and JP-A-53- The fibrillated fibers disclosed in Japanese Patent No. 149881 and Japanese Patent Publication No. 63-61337 can be used. As a method for removing the solvent, methods such as heat treatment at room temperature to 200 ° C. and reduced pressure treatment can be used. When heat treatment is performed, the solvent can be removed by raising the temperature stepwise.
また、例えばイオン交換基を有する高分子化合物（Ａ）の溶液の代わりにその前駆体ポリマーの溶液を用いて、（Ｂ）〜（Ｇ）成分の各溶液を混合して溶液を作成し、その溶液をキャストした後、溶媒を除去してから、適当な後処理、例えばアルカリ加水分解処理や酸処理を行ってイオン交換基を有する形態に変換することで、本発明の高分子電解質組成物からなるプロトン交換膜を得ることも出来る。 Further, for example, instead of the solution of the polymer compound (A) having an ion exchange group, the solution of the precursor polymer is used, and the solutions of the components (B) to (G) are mixed to prepare a solution. After casting the solution, the solvent is removed, and then subjected to an appropriate post-treatment such as alkaline hydrolysis treatment or acid treatment to convert it into a form having an ion-exchange group, whereby the polymer electrolyte composition of the present invention is used. A proton exchange membrane can be obtained.
本発明のプロトン交換膜の製造において、上記記載の製法と併せて、横１軸延伸、同時２軸延伸または逐次２軸延伸を実施することによって延伸配向を付与することができる。このような延伸処理により、本発明のプロトン交換膜の力学物性を向上させることができるので好ましい。この延伸処理は、プロトン交換膜の状態で実施することができるし、あるいはプロトン交換基をナトリウム塩、カリウム塩およびカルシウム塩などの金属塩やアンモニウム塩等に置換した状態でも実施することができる。また、イオン交換基を有する高分子化合物（Ａ）の前駆体ポリマーと（Ｂ）〜（Ｇ）成分から選ばれた成分とからなる高分子組成物を製膜した場合は、製膜直後の状態でも実施することができるし、当該膜を適当な後処理、例えばアルカリ加水分解処理や酸処理を行ってイオン交換基を有する形態に変換してから実施することもできる。 In the production of the proton exchange membrane of the present invention, stretch orientation can be imparted by carrying out transverse uniaxial stretching, simultaneous biaxial stretching or sequential biaxial stretching in combination with the above-described production method. Such stretching treatment is preferable because the mechanical properties of the proton exchange membrane of the present invention can be improved. This stretching treatment can be carried out in the state of a proton exchange membrane, or can be carried out in a state in which the proton exchange group is replaced with a metal salt such as sodium salt, potassium salt and calcium salt, ammonium salt or the like. When a polymer composition comprising a precursor polymer of a polymer compound (A) having an ion exchange group and a component selected from the components (B) to (G) is formed, the state immediately after the film formation However, it can also be carried out, and it can be carried out after the membrane is converted into a form having an ion exchange group by performing an appropriate post-treatment such as alkali hydrolysis treatment or acid treatment.
上記の延伸処理は、横（ＴＤ）方向に１．１〜６．０倍、縦（ＭＤ）方向に１．０〜６．０倍で実施することが好ましく、より好ましくは横方向に１．１〜３．０倍、縦方向に１．０〜３．０倍、さらに好ましくは横方向に１．１〜２．０倍、縦方向に１．０〜２．０倍である。面積延伸倍率としては１．１〜３６倍が好ましい。 The stretching treatment is preferably carried out at a magnification of 1.1 to 6.0 in the transverse (TD) direction and 1.0 to 6.0 in the longitudinal (MD) direction, more preferably 1. 1 to 3.0 times, 1.0 to 3.0 times in the vertical direction, more preferably 1.1 to 2.0 times in the horizontal direction, and 1.0 to 2.0 times in the vertical direction. The area stretch ratio is preferably 1.1 to 36 times.
本発明のプロトン交換膜は、組成比が異なる少なくとも２種類以上のプロトン交換膜を積層した構造にすることができる。本発明の高分子電解質組成物からなるプロトン交換膜では、イオン交換基を有する高分子化合物（Ａ）以外の樹脂の含有率が高いほど力学強度および乾湿寸法変化に優れ、イオン交換基を有する高分子化合物（Ａ）含有率が高いほどプロトン伝導度などの電気特性が優れる。この特性を利用して、組成比が異なる２種類以上のプロトン交換膜を設計し、それらを組み合わせて積層することで、力学強度、乾湿寸法変化および電気特性の全てに優れたプロトン交換膜を単層膜の場合よりも容易に実現することができる。 The proton exchange membrane of the present invention can have a structure in which at least two types of proton exchange membranes having different composition ratios are laminated. In the proton exchange membrane comprising the polymer electrolyte composition of the present invention, the higher the content of the resin other than the polymer compound (A) having an ion exchange group, the better the mechanical strength and the wet / dry dimensional change, and the higher the content of the ion exchange group. The higher the molecular compound (A) content, the better the electrical properties such as proton conductivity. By utilizing these characteristics, two or more types of proton exchange membranes with different composition ratios are designed and combined to form a single layer of a proton exchange membrane that excels in mechanical strength, wet and dry dimensional changes, and electrical properties. This can be realized more easily than in the case of a layer film.
積層させる層数に制限はないが、層数が多くなると製造コストも増大するので２〜１０層程度が好ましい。さらに好ましくは２〜７層であり、３〜５層が特に好ましい。各層の、イオン交換基を有する高分子化合物（Ａ）、ポリフェニレンスルフィド樹脂（Ｂ）、ポリスルホン樹脂（Ｃ）およびエポキシ基含有化合物（Ｄ）の組成比は前述の範囲内で任意に変化させることができる。また各層の厚さも特性を考慮して任意に変化させることができる。 Although the number of layers to be laminated is not limited, since the manufacturing cost increases as the number of layers increases, about 2 to 10 layers are preferable. More preferably, it is 2-7 layers, and 3-5 layers are especially preferable. The composition ratio of the polymer compound (A) having an ion exchange group, the polyphenylene sulfide resin (B), the polysulfone resin (C), and the epoxy group-containing compound (D) in each layer can be arbitrarily changed within the aforementioned range. it can. Further, the thickness of each layer can be arbitrarily changed in consideration of characteristics.
例えば３層以上の多層構造のケースにおいて、内部層のイオン交換基を有する高分子化合物（Ａ）の含有率を少なくともいずれか一方の表面層のそれよりも少なくして、内部層で乾湿寸法変化を抑えた場合、内部層の厚さは、全体厚みの５〜９０％比が好ましく、さらに好ましくは７〜８０％比、特に好ましくは１０〜５０％比である。また、表面層のイオン交換基を有する高分子化合物（Ａ）の含有率を内部層のそれよりも少なくして、表面層で乾湿寸法変化を抑えた場合、表面層の総厚さは、全体厚みの５〜５０％比が好ましく、さらに好ましくは７〜４５％比、特に好ましくは１０〜４０％比である。 For example, in the case of a multilayer structure of three or more layers, the content ratio of the polymer compound (A) having an ion exchange group in the inner layer is made smaller than that of at least one of the surface layers, and the wet and dry dimensional changes in the inner layer When the thickness is suppressed, the thickness of the inner layer is preferably 5 to 90% of the total thickness, more preferably 7 to 80%, and particularly preferably 10 to 50%. In addition, when the content of the polymer compound (A) having an ion exchange group in the surface layer is made smaller than that in the inner layer and the change in the wet and dry dimensions is suppressed in the surface layer, the total thickness of the surface layer is A 5 to 50% ratio of the thickness is preferable, a 7 to 45% ratio is more preferable, and a 10 to 40% ratio is particularly preferable.
本発明のプロトン交換膜の製造において、上記記載の製法と併せて、無機材ないし有機材または有機無機ハイブリッド材からなる補強材料を添加することによる補強や、架橋による補強等を施すこともできる。補強材料は短繊維物質でもよいし、粒子状物質でもよいし、薄片状物質でもよい。また、多孔膜、メッシュおよび不織布などの連続した支持体でもよい。本発明のプロトン交換膜に補強材料の添加による補強を実施することで、力学強度および乾湿寸法変化を容易に向上させることができる。特に短繊維物質または上述の連続した支持体を補強材料に用いると補強効果が高い。 In the production of the proton exchange membrane of the present invention, in addition to the above-described production method, reinforcement by adding a reinforcing material made of an inorganic material, an organic material, or an organic-inorganic hybrid material, reinforcement by crosslinking, and the like can be performed. The reinforcing material may be a short fiber material, a particulate material, or a flaky material. Further, a continuous support such as a porous film, a mesh, and a nonwoven fabric may be used. By carrying out the reinforcement by adding a reinforcing material to the proton exchange membrane of the present invention, the mechanical strength and the change in wet and dry dimensions can be easily improved. In particular, when a short fiber substance or the above-mentioned continuous support is used as a reinforcing material, the reinforcing effect is high.
補強材料は、溶融混練時に同時に添加、混合してもよいし、製膜後の膜と積層してもよい。
補強材料として用いる無機材は補強効果のあるものであれば特に限定されず、例えばガラス繊維、炭素繊維、セルロース繊維、カオリンクレー、カオリナイト、ハロイサイト、パイロフィライト、タルク、モンモリロナイト、セリサイト、マイカ、アメサイト、ベントナイト、アスベスト、ゼオライト、炭酸カルシウム、ケイ酸カルシウム、ケイ藻土、ケイ砂、鉄フェライト、水酸化アルミニウム、酸化アルミニウム、酸化マグネシウム、酸化チタン、酸化ジルコニウム、酸化マンガン、グラファイト、フラーレン、カーボンナノチューブ、およびカーボンナノホーン等が挙げられる。補強材として用いる有機材もまた補強効果のあるものであれば特に限定されず、例えばポリフェニレンスルフィド、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリエーテルエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリチオエーテルスルホン、ポリチオエーテルエーテルスルホン、ポリチオエーテルケトン、ポリチオエーテルエーテルケトン、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリオキサジアゾール、ポリベンゾオキサジノン、ポリキシリレン、ポリフェニレン、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセン、ポリシアノゲン、ポリナフチリジン、ポリフェニレンスルフィドスルホン、ポリフェニレンスルホン、ポリイミド、ポリエーテルイミド、ポリエステルイミド、ポリアミドイミド、ポリアミド、芳香族ポリアミド、ポリスチレン、アクリロニトリル−スチレン樹脂、ポリスチレン−水素添加されたポリブタジエン−ポリスチレンブロック共重合体、アクリロニトリル−ブタジエン−スチレン樹脂、ポリエステル、ポリアリレート、液晶ポリエステル、ポリカーボネート、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリ塩化ビニル、ポリ塩化ビニリデン、メタクリル樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ウレタン樹脂、セルロース、ポリケトン、ポリアセタール、ポリプロピレンおよびポリエチレンなどが挙げられる。有機無機ハイブリッド材もまた補強材として用いることができ、例えば、ＰＯＳＳ（Ｐｏｌｙｈｅｄｒａｌ Ｏｌｉｇｏｍｅｒｉｃ Ｓｉｌｓｅｓｑｕｉｏｘａｎｅｓ）やシリコーンゴム等のシルセスキオキサン構造やシロキサン構造を有した有機ケイ素高分子化合物などが挙げられる。
The reinforcing material may be added and mixed at the same time during melt-kneading, or may be laminated with the film after film formation.
The inorganic material used as the reinforcing material is not particularly limited as long as it has a reinforcing effect. For example, glass fiber, carbon fiber, cellulose fiber, kaolin clay, kaolinite, halloysite, pyrophyllite, talc, montmorillonite, sericite, mica Americite, bentonite, asbestos, zeolite, calcium carbonate, calcium silicate, diatomaceous earth, silica sand, iron ferrite, aluminum hydroxide, aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide, manganese oxide, graphite, fullerene, Examples include carbon nanotubes and carbon nanohorns. The organic material used as the reinforcing material is not particularly limited as long as it has a reinforcing effect. For example, polyphenylene sulfide, polyphenylene ether, polysulfone, polyether sulfone, polyether ether sulfone, polyether ketone, polyether ether ketone, polythioether. Sulfone, polythioether ether sulfone, polythioether ketone, polythioether ether ketone, polybenzimidazole, polybenzoxazole, polyoxadiazole, polybenzoxazinone, polyxylylene, polyphenylene, polythiophene, polypyrrole, polyaniline, polyacene, polycyanogen, polynaphthyridine , Polyphenylene sulfide sulfone, polyphenylene sulfone, polyimide, polyetherimide, poly Ester imide, polyamide imide, polyamide, aromatic polyamide, polystyrene, acrylonitrile-styrene resin, polystyrene-hydrogenated polybutadiene-polystyrene block copolymer, acrylonitrile-butadiene-styrene resin, polyester, polyarylate, liquid crystal polyester, polycarbonate, Examples thereof include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, epoxy resin, phenol resin, melamine resin, urethane resin, cellulose, polyketone, polyacetal, polypropylene, and polyethylene. An organic-inorganic hybrid material can also be used as a reinforcing material, and examples thereof include an organic silicon polymer compound having a silsesquioxane structure or a siloxane structure such as POSS (Polyhedral Oligomeric Silsesquioxanes) or silicone rubber.
また、本発明の高分子電解質組成物については、空気中あるいは酸素雰囲気下にて例えば１６０℃以上で加熱処理することによって力学物性を向上させることもできる。
本発明により製造されるプロトン交換膜の当量重量ＥＷ（プロトン交換基１当量あたりのプロトン交換膜の乾燥重量グラム数）には、２５０以上２０００以下が好ましく、より好ましくは４００以上１５００以下、最も好ましくは５００以上１２００以下である。より低いＥＷ、つまりプロトン交換容量の大きいプロトン伝導性ポリマーを用いることにより、高温低加湿条件下においても優れたプロトン伝導性を示し、燃料電池に用いた場合、運転時に高い出力を得ることができる。
Moreover, about the polymer electrolyte composition of this invention, a mechanical physical property can also be improved by heat-processing in 160 degreeC or more, for example in air or oxygen atmosphere.
The equivalent weight EW of the proton exchange membrane produced according to the present invention (dry weight gram of proton exchange membrane per equivalent of proton exchange group) is preferably 250 or more and 2000 or less, more preferably 400 or more and 1500 or less, most preferably. Is 500 or more and 1200 or less. By using a proton conductive polymer with a lower EW, that is, a large proton exchange capacity, it exhibits excellent proton conductivity even under high temperature and low humidity conditions, and when used in a fuel cell, a high output can be obtained during operation. .
本発明により製造されるプロトン交換膜の厚みは、１μｍ以上５００μｍ以下であることが好ましく、より好ましくは２μｍ以上１００μｍ以下、最も好ましくは５μｍ以上５０μｍ以下である。
本発明により製造されるプロトン交換膜の乾湿寸法変化は、好ましくは０％以上１００％以下、より好ましくは０％以上５０％以下、最も好ましくは０％以上１０％以下である。ここでいう乾湿寸法変化とは、２５℃２０ＲＨ％で１時間放置した時の寸法に対する８０℃水中で１時間放置した時の寸法の変化の割合のことをいう。寸法とは、プロトン交換膜の縦方向または横方向の長さのことであり、共に上記範囲を満たすことが好ましい。
The thickness of the proton exchange membrane produced according to the present invention is preferably 1 μm or more and 500 μm or less, more preferably 2 μm or more and 100 μm or less, and most preferably 5 μm or more and 50 μm or less.
The change in wet and dry dimensions of the proton exchange membrane produced according to the present invention is preferably 0% to 100%, more preferably 0% to 50%, and most preferably 0% to 10%. The term “wet and dry dimensional change” as used herein refers to the ratio of the change in dimension when left in water at 80 ° C. for 1 hour with respect to the dimension when left at 25 ° C. and 20 RH% for 1 hour. The dimension is the length in the vertical direction or the horizontal direction of the proton exchange membrane, and both preferably satisfy the above range.
本発明のプロトン交換膜を用いて以下の如く燃料電池を組み立て、耐久性の評価を行なった。
（膜電極接合体）
本発明により得られるプロトン交換膜を固体高分子型燃料電池に用いる場合、アノードとカソード２種類の電極触媒層が接合した膜電極接合体（以下「ＭＥＡ」と略称する）として使用される。電極触媒層のさらに外側に一対のガス拡散層を対向するように接合したものもＭＥＡと呼ぶ。
電極触媒層は、触媒金属の微粒子とこれを担持した導電剤とから構成され、必要に応じて撥水剤が含まれる。電極に使用される触媒としては、水素の酸化反応および酸素による還元反応を促進する金属であれば良く、白金、金、銀、パラジウム、イリジウム、ロジウム、ルテニウム、鉄、コバルト、ニッケル、クロム、タングステン、マンガン、バナジウム、これらの合金等が挙げられ、その中では、主として白金が好ましく用いられる。
A fuel cell was assembled as follows using the proton exchange membrane of the present invention, and durability was evaluated.
(Membrane electrode assembly)
When the proton exchange membrane obtained by the present invention is used in a polymer electrolyte fuel cell, it is used as a membrane electrode assembly (hereinafter abbreviated as “MEA”) in which two types of electrode catalyst layers are joined to an anode and a cathode. A structure in which a pair of gas diffusion layers are bonded to the outer side of the electrode catalyst layer so as to face each other is also called MEA.
The electrode catalyst layer is composed of fine particles of a catalytic metal and a conductive agent supporting the catalyst metal, and a water repellent is included as necessary. The catalyst used for the electrode may be any metal that promotes the oxidation reaction of hydrogen and the reduction reaction by oxygen. Platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, cobalt, nickel, chromium, tungsten , Manganese, vanadium, and alloys of these, among which platinum is preferably used.
ＭＥＡの製造方法としては、例えば、次のような方法が行われる。まず、イオン交換樹脂をアルコールと水の混合溶液に溶解したものに、電極物質となる白金担持カーボンを分散させてペースト状にする。これをＰＴＦＥシートに一定量塗布して乾燥させる。次に、ＰＴＦＥシートの塗布面を向かい合わせにして、その間に本発明のプロトン交換膜を挟み込み、１００℃〜２００℃で熱プレスにより転写接合してＭＥＡを得ることができる。 As the MEA manufacturing method, for example, the following method is performed. First, a platinum-supported carbon serving as an electrode material is dispersed in a solution obtained by dissolving an ion exchange resin in a mixed solution of alcohol and water to form a paste. A certain amount of this is applied to a PTFE sheet and dried. Next, the application surface of the PTFE sheet faces each other, the proton exchange membrane of the present invention is sandwiched therebetween, and transfer bonding is carried out by hot pressing at 100 ° C. to 200 ° C. to obtain an MEA.
（燃料電池）
上記で得られたＭＥＡ、場合によってはＭＥＡを介して一対のガス拡散電極が対向した構造のものは、さらにバイポーラプレート、バッキングプレート等の一般的な固体高分子型燃料電池に用いる構成成分と組み合わせて固体高分子型燃料電池を構成する。
バイポーラプレートは、その表面に燃料や酸化剤等のガスを流すための溝を形成させたグラファイトまたは樹脂との複合材料、金属製のプレート等のことであり、電子を外部負荷回路へ伝達する他に、燃料や酸化剤を電極触媒近傍に供給する流路としての機能を持っている。こうしたバイポーラプレートの間にＭＥＡを挿入して複数積み重ねることにより、燃料電池が製造される。
以上、本発明の燃料電池製造用の溶液から得られたプロトン交換膜の耐久性の評価方法について説明した。
(Fuel cell)
The MEA obtained above and, in some cases, a structure in which a pair of gas diffusion electrodes are opposed to each other via the MEA are further combined with components used for general solid polymer fuel cells such as bipolar plates and backing plates. Thus, a polymer electrolyte fuel cell is constructed.
Bipolar plates are graphite or resin composite materials, metal plates, etc. that have grooves on the surface for the flow of gas such as fuel and oxidant, and are used to transmit electrons to an external load circuit. In addition, it has a function as a flow path for supplying fuel and oxidant to the vicinity of the electrode catalyst. A fuel cell is manufactured by inserting and stacking a plurality of MEAs between such bipolar plates.
The method for evaluating the durability of the proton exchange membrane obtained from the solution for producing the fuel cell of the present invention has been described above.
以下、本発明を実施例により具体的に説明する。
尚、本発明に用いられる評価法および測定法は以下のとおりである。
（プロトン伝導度測定）
膜サンプルを湿潤状態にて切り出し、厚みＴを測定する。これを、幅１ｃｍ、長さ５ｃｍの膜長さ方向の伝導度を測定する２端子式の伝導度測定セルに装着する。このセルを８０℃のイオン交換水中に入れ、交流インピーダンス法により、周波数１０ｋＨｚにおける実数成分の抵抗値Ｒを測定し、以下の式からプロトン伝導度σを導出する。
σ＝Ｌ／（Ｒ×Ｔ×Ｗ）
σ：プロトン伝導度（Ｓ／ｃｍ）
Ｔ：厚み（ｃｍ）
Ｒ：抵抗値（Ω）
Ｌ（＝５）：膜長（ｃｍ）
Ｗ（＝１）：膜幅（ｃｍ）
Hereinafter, the present invention will be specifically described by way of examples.
The evaluation method and measurement method used in the present invention are as follows.
(Proton conductivity measurement)
A membrane sample is cut out in a wet state and the thickness T is measured. This is mounted on a two-terminal conductivity measuring cell that measures the conductivity in the film length direction having a width of 1 cm and a length of 5 cm. This cell is placed in ion exchange water at 80 ° C., and the resistance value R of the real component at a frequency of 10 kHz is measured by the AC impedance method, and the proton conductivity σ is derived from the following equation.
σ = L / (R × T × W)
σ: proton conductivity (S / cm)
T: Thickness (cm)
R: Resistance value (Ω)
L (= 5): film length (cm)
W (= 1): film width (cm)
（燃料電池評価）
（１）燃料電池の製造
まず、台紙上に塗布したガス拡散電極２枚の間にプロトン交換膜を挟み込み、１８０℃、圧力１０ＭＰａでホットプレスすることにより、プロトン交換膜にガス拡散電極を転写接合させてＭＥＡを製造する。
(Fuel cell evaluation)
(1) Manufacture of fuel cell First, a proton exchange membrane is sandwiched between two gas diffusion electrodes coated on a mount and hot pressed at 180 ° C. and a pressure of 10 MPa to transfer and bond the gas diffusion electrode to the proton exchange membrane. To produce an MEA.
ガス拡散電極としては、田中貴金属工業（株）製白金担持触媒ＴＥＣ１０Ｅ４０Ｅ（商品名、白金担持率４０重量％）に、パーフルオロスルホン酸ポリマー溶液ＳＳ−７００ｘ／０５（商品名、旭化成（株）製、ＥＷ：７２０、溶媒組成（重量比）：エタノール／水＝５０／５０）を１２重量％に濃縮した溶液とエタノールを添加し、混合、攪拌してインク状にしたものをＰＴＦＥシート上に塗布した後、大気雰囲気中、１５０℃で乾燥・固定化したものを使用する。このガス拡散電極の白金担持量は０．４ ｍｇ／ｃｍ２、ポリマー担持量は０．５ｍｇ／ｃｍ２である。
このＭＥＡの両側に撥水処理したカーボンペーパーまたはカーボンクロスを配置し、評価セルに組み込んで評価装置にセットする。燃料として水素ガス、酸化剤として空気ガスを用い、セル温度１００℃、０．１ＭＰａにて単セル特性試験を行う。ガス加湿には水バブリング方式を用い、水素ガス、空気ガスともに５０℃で加湿してセルへ供給する。
As a gas diffusion electrode, a platinum-supported catalyst TEC10E40E (trade name, platinum support ratio 40% by weight) manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., and a perfluorosulfonic acid polymer solution SS-700x / 05 (trade name, manufactured by Asahi Kasei Co., Ltd.) , EW: 720, solvent composition (weight ratio): ethanol / water = 50/50) and a solution concentrated to 12% by weight and ethanol were added, mixed and stirred to form an ink on a PTFE sheet. After that, dry and fixed at 150 ° C. in an air atmosphere. This gas diffusion electrode has a platinum loading of 0.4 mg / cm 2 and a polymer loading of 0.5 mg / cm 2 .
Carbon paper or carbon cloth subjected to water repellent treatment is disposed on both sides of the MEA, and is incorporated into an evaluation cell and set in an evaluation apparatus. A single cell characteristic test is performed using hydrogen gas as a fuel and air gas as an oxidizing agent at a cell temperature of 100 ° C. and 0.1 MPa. A water bubbling method is used for gas humidification, and both hydrogen gas and air gas are humidified at 50 ° C. and supplied to the cell.
（２）フッ素溶出速度の測定
単セル特性試験中のアノード排ガスおよびカソード排ガスと共に排出される排水を、それぞれ所定時間捕捉回収した後、秤量する。メディトリアル（株）製ベンチトップ型ｐＨイオンメーター９２０Ａｐｌｕｓ（商品名）に同フッ素複合電極９６０９ＢＮｉｏｎｐｌｕｓ（商品名）を取り付け、アノード排水中およびカソード排水中のフッ素イオン濃度を測定し、以下の式からフッ素溶出速度Ｇを導出する。
Ｇ＝（Ｗａ×Ｆａ＋Ｗｃ×Ｆｃ）／（Ｔ×Ａ）
Ｇ：フッ素溶出速度（μｇ／Ｈｒ／ｃｍ２）
Ｗａ：捕捉回収したアノード排水の重量（ｇ）
Ｆａ：アノード排水中のフッ素イオン濃度（ｐｐｍ）
Ｗｃ：捕捉回収したカソード排水の重量（ｇ）
Ｆｃ：カソード排水中のフッ素イオン濃度（ｐｐｍ）
Ｔ：排水を捕捉回収した時間（Ｈｒ）
Ａ：ＭＥＡの電極面積（ｃｍ２）
(2) Measurement of fluorine elution rate The waste water discharged together with the anode exhaust gas and the cathode exhaust gas during the single cell characteristic test is respectively collected for a predetermined time, and then weighed. The fluorine composite electrode 9609BNionplus (trade name) is attached to a bench top type pH ion meter 920Aplus (trade name) manufactured by Meditrial Co., Ltd., and the fluorine ion concentration in the anode drainage and the cathode drainage is measured. The elution rate G is derived.
G = (Wa × Fa + Wc × Fc) / (T × A)
G: Fluorine elution rate (μg / Hr / cm 2 )
Wa: Weight of anode wastewater collected and collected (g)
Fa: Fluorine ion concentration (ppm) in anode drainage
Wc: Weight of cathode drainage collected and collected (g)
Fc: Fluorine ion concentration in the cathode drainage (ppm)
T: Time for collecting and collecting wastewater (Hr)
A: MEA electrode area (cm 2 )
（３）クロスリーク量の測定
単セル特性試験中のカソード排ガスの一部を、ジーエルサイエンス製マイクロガスクロマトグラフＭｉｃｒｏ ＧＣ ＣＰ−４９００（商品名）に導入し、カソード排ガス中の水素ガス濃度を測定し、以下の式から水素ガス透過率を導出する。
Ｌ＝（Ｘ×Ｖ×Ｔ）×（５−Ｕ／１００）／（３×Ａ×Ｐ）×１０−８
Ｌ：水素ガス透過率（ｍｌ×ｃｍ／ｃｍ２／ｓｅｃ／Ｐａ）
Ｘ：カソード排ガス中の水素ガス濃度（ｐｐｍ）
Ｖ：カソードガス流量（ｍｌ／ｍｉｎ）
Ｔ：プロトン交換膜の膜厚（ｃｍ）
Ｕ：カソードガス利用率（％）
Ａ：プロトン交換膜の水素透過面積（ｃｍ２）
Ｐ：カソード−アノード間の水素分圧差（Ｐａ）
短セル特性試験中の水素ガス透過率が１．１×１０−１１ （ｍｌ×ｃｍ／ｃｍ２／ｓｅｃ／Ｐａ）以上になった時点をセル寿命とし、そこで試験を終了した。
(3) Measurement of cross leak amount Part of the cathode exhaust gas during the single cell characteristic test was introduced into GL Sciences' micro gas chromatograph Micro GC CP-4900 (trade name), and the hydrogen gas concentration in the cathode exhaust gas was measured. The hydrogen gas permeability is derived from the following equation.
L = (X × V × T) × (5-U / 100) / (3 × A × P) × 10 −8
L: Hydrogen gas permeability (ml × cm / cm 2 / sec / Pa)
X: Hydrogen gas concentration (ppm) in cathode exhaust gas
V: Cathode gas flow rate (ml / min)
T: thickness of proton exchange membrane (cm)
U: Cathode gas utilization rate (%)
A: Hydrogen permeation area of the proton exchange membrane (cm 2 )
P: Hydrogen partial pressure difference between the cathode and anode (Pa)
The time when the hydrogen gas permeability during the short cell characteristic test became 1.1 × 10 −11 (ml × cm / cm 2 / sec / Pa) or more was defined as the cell life, and the test was terminated there.
（４）引っ張り弾性率の測定
プロトン交換膜を幅５ｍｍ、長さ４０〜５０ｍｍに切り出したものをサンプルとする。これを８０℃水中に３０分以上浸漬させてから、８０℃恒温水槽付引っ張り試験機（島津製作所：ＡＧＳ−１ｋＮＧ（商品名））にサンプルをチャック間２０ｍｍとなるように素早くセットする。サンプルを恒温水槽に浸漬してから３分後に引っ張り速度１０％／秒で引っ張り試験を行い、５％伸び時点での引っ張り強度から引っ張り弾性率（Ｎ／ｃｍ２）を求める。
(4) Measurement of tensile elastic modulus A proton exchange membrane cut into a width of 5 mm and a length of 40 to 50 mm is used as a sample. After immersing this in 80 ° C. water for 30 minutes or more, the sample is quickly set in a tensile tester with an 80 ° C. constant temperature water bath (Shimadzu Corporation: AGS-1kNG (trade name)) so that the distance between chucks is 20 mm. A tensile test is performed at a tensile rate of 10% / second 3 minutes after the sample is immersed in a constant temperature water bath, and the tensile elastic modulus (N / cm 2 ) is determined from the tensile strength at the time of 5% elongation.
［実施例１］
テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマー（ＭＩ：３．０、アルカリ加水分解・酸処理後のＥｗ：７３０）９０重量部と、ポリフェニレンスルフィド（溶融粘度（フローテスターを用いて、３００℃、荷重１９６Ｎ／ｃｍ２、Ｌ／Ｄ（Ｌ：オリフィス長、Ｄ：オリフィス内径）＝１０／１で６分間保持した後測定した値。）が５０Ｐａ・ｓ、塩化メチレンによる抽出量が０．７重量％、−ＳＸ基量が２５μｍｏｌ／ｇ）７重量部と、ポリスルホン（シグマアルドリッチジャパン（株）製、数平均分子量２６，０００）３重量部と、エポキシ樹脂（大日本インキ化学工業（株）製クレゾールノボラック型エポキシ樹脂Ｎ−６６０（商品名））１重量部とを、温度２８０〜３１０℃、スクリュー回転数２００ｒｐｍに設定した二軸押出機（ＺＳＫ−４０（商品名）；ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製、ドイツ国）を用い、押出機の第一原料供給口より供給して溶融混練した後、Ｔダイ押出機を用いて溶融押出して５０μｍ厚のフィルムに成形した。このフィルムを、水酸化カリウム（１５重量％）とジメチルスルホキシド（３０重量％）を溶解した水溶液中に、６０℃で４時間接触させて、アルカリ加水分解処理を行った。その後、６０℃水中に４時間浸漬した。次に６０℃の２Ｎ塩酸水溶液に３時間浸漬した後、イオン交換水で水洗、乾燥してプロトン交換膜（Ｅｗ：７９５）を得た。
[Example 1]
90 parts by weight of a precursor polymer (MI: 3.0, Ew after alkali hydrolysis and acid treatment: 730) obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F, and polyphenylene Sulfide (melt viscosity (measured using a flow tester at 300 ° C., load 196 N / cm 2 , L / D (L: orifice length, D: orifice inner diameter) = 10/1 after holding for 6 minutes)). 50 Pa · s, 7 parts by weight extracted with methylene chloride, 0.7 parts by weight, -SX group amount 25 μmol / g) and 3 parts by weight of polysulfone (manufactured by Sigma-Aldrich Japan, number average molecular weight 26,000) And 1 part by weight of an epoxy resin (cresol novolac type epoxy resin N-660 (trade name) manufactured by Dainippon Ink and Chemicals, Inc.), a temperature of 280 to 310 ° C, Using a twin screw extruder (ZSK-40 (trade name); manufactured by WERNER & PFLIDEERER, Germany) set at a clew speed of 200 rpm, it is supplied from the first raw material supply port of the extruder and melt-kneaded, and then T-die extrusion The film was melt extruded using a machine to form a film having a thickness of 50 μm. This film was contacted with an aqueous solution in which potassium hydroxide (15% by weight) and dimethyl sulfoxide (30% by weight) were dissolved at 60 ° C. for 4 hours to perform an alkali hydrolysis treatment. Then, it was immersed in 60 degreeC water for 4 hours. Next, it was immersed in a 2N hydrochloric acid aqueous solution at 60 ° C. for 3 hours, then washed with ion-exchanged water and dried to obtain a proton exchange membrane (Ew: 795).
このプロトン交換膜のプロトン伝導度は０．２４（Ｓ／ｃｍ）と高く、燃料電池評価を行ったところ、開始時から２００時間までの排水中のフッ素溶出速度の平均値は０．０１３（μｇ／Ｈｒ／ｃｍ２）と非常に低い値を示した。セル寿命は１０００時間を越え、非常に優れた耐久性を示すことが判明した。
しかも、このプロトン交換膜の引っ張り弾性率は、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマーを単独で用いた比較例１のプロトン交換膜の１．４倍以上、この膜の成分からエポキシ樹脂を除いた組成である比較例２のプロトン交換膜の１．６倍以上強く、耐久性だけでなく、膜強度も向上していることが判明した。
The proton conductivity of this proton exchange membrane is as high as 0.24 (S / cm). When the fuel cell was evaluated, the average value of the fluorine elution rate in the waste water from the start to 200 hours was 0.013 (μg / Hr / cm 2 ) and a very low value. It has been found that the cell life exceeds 1000 hours and exhibits extremely excellent durability.
Moreover, the tensile elastic modulus of the proton exchange membrane is that of the proton exchange membrane of Comparative Example 1 using a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F alone. 1.4 times or more, 1.6 times stronger than the proton exchange membrane of Comparative Example 2, which is a composition obtained by removing the epoxy resin from the components of this membrane, and it was found that not only durability but also membrane strength was improved. did.
［実施例２］
実施例１の組成比を、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマー８０重量部と、ポリフェニレンスルフィド１５重量部と、ポリスルホン５重量部と、エポキシ樹脂５重量部とに変更した。
このプロトン交換膜のプロトン伝導度は０．２１（Ｓ／ｃｍ）と高く、燃料電池評価を行ったところ、開始時から２００時間までの排水中のフッ素溶出速度の平均値は０．０１６（μｇ／Ｈｒ／ｃｍ２）と非常に低い値を示した。セル寿命は１０００時間を越え、非常に優れた耐久性を示すことが判明した。
[Example 2]
The composition ratio of Example 1 was changed to 80 parts by weight of a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F, 15 parts by weight of polyphenylene sulfide, and 5 parts by weight of polysulfone. The epoxy resin was changed to 5 parts by weight.
The proton conductivity of this proton exchange membrane is as high as 0.21 (S / cm). When the fuel cell was evaluated, the average value of the elution rate of fluorine in waste water from the start to 200 hours was 0.016 (μg / Hr / cm 2 ) and a very low value. It has been found that the cell life exceeds 1000 hours and exhibits extremely excellent durability.
しかも、このプロトン交換膜の引っ張り弾性率は、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマーを単独で用いた比較例１のプロトン交換膜の１．３倍以上、この膜の成分からエポキシ樹脂を除いた組成である比較例３のプロトン交換膜の約１．７倍強く、耐久性だけでなく、膜強度も向上していることが判明した。 Moreover, the tensile elastic modulus of the proton exchange membrane is that of the proton exchange membrane of Comparative Example 1 using a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F alone. 1.3 times more than the proton exchange membrane of Comparative Example 3, which is a composition obtained by removing the epoxy resin from the components of this membrane, was found to be about 1.7 times stronger and not only durable but also improved in membrane strength. did.
［比較例１］
テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマー（ＭＩ：３．０、アルカリ加水分解・酸処理後のＥｗ：７３０）を単独で用いた以外は実施例１と同様にして、プロトン交換膜（ＥＷ：７３０， ＭＩ：３．０）を得た。
このプロトン交換膜のプロトン伝導度は０．２３（Ｓ／ｃｍ）と高かった。このプロトン交換膜の燃料電池評価を行ったところ、開始時からセル寿命までの排水中のフッ素溶出速度の平均値が０．５０６（μｇ／Ｈｒ／ｃｍ２）と非常に高く、しかもセル寿命は２００時間未満で、十分な耐久性が得られなかった。
[Comparative Example 1]
A precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F (MI: 3.0, Ew after alkali hydrolysis / acid treatment: 730) was used alone. Produced a proton exchange membrane (EW: 730, MI: 3.0) in the same manner as in Example 1.
The proton conductivity of this proton exchange membrane was as high as 0.23 (S / cm). When this proton exchange membrane was evaluated for a fuel cell, the average value of the fluorine elution rate in the waste water from the start to the cell lifetime was as high as 0.506 (μg / Hr / cm 2 ), and the cell lifetime was In less than 200 hours, sufficient durability was not obtained.
［比較例２］
実施例１の組成比を、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマー９０重量部と、ポリフェニレンスルフィド７重量部と、ポリスルホン３重量部と、エポキシ樹脂０重量部とに変更した。
このプロトン交換膜のプロトン伝導度は０．２３（Ｓ／ｃｍ）と高く、燃料電池評価を行ったところ、開始時から２００時間までの排水中のフッ素溶出速度の平均値は０．０１８（μｇ／Ｈｒ／ｃｍ２）と非常に低い値を示した。セル寿命は１０００時間を越え、非常に優れた耐久性を示すことが判明した。
[Comparative Example 2]
The composition ratio of Example 1 is 90 parts by weight of a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F, 7 parts by weight of polyphenylene sulfide, and 3 parts by weight of polysulfone. The epoxy resin was changed to 0 part by weight.
The proton conductivity of this proton exchange membrane is as high as 0.23 (S / cm). When the fuel cell was evaluated, the average value of the fluorine elution rate in the waste water from the start to 200 hours was 0.018 (μg / Hr / cm 2 ) and a very low value. It has been found that the cell life exceeds 1000 hours and exhibits extremely excellent durability.
しかし、このプロトン交換膜の引っ張り弾性率は、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマーを単独で用いた比較例１のプロトン交換膜の０．８倍程度で、耐久性は向上しているが、膜強度は低下していることが判明した。 However, the tensile elastic modulus of this proton exchange membrane is that of the proton exchange membrane of Comparative Example 1 using a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F alone. It was found that the durability was improved at about 0.8 times, but the film strength was lowered.
［比較例３］
実施例２の組成比を、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマー８０重量部と、ポリフェニレンスルフィド１５重量部と、ポリスルホン５重量部と、エポキシ樹脂０重量部とに変更した。
このプロトン交換膜のプロトン伝導度は０．２１（Ｓ／ｃｍ）と高く、燃料電池評価を行ったところ、開始時から２００時間までの排水中のフッ素溶出速度の平均値は０．０２１（μｇ／Ｈｒ／ｃｍ２）と非常に低い値を示した。セル寿命は１０００時間を越え、非常に優れた耐久性を示すことが判明した。
[Comparative Example 3]
The composition ratio of Example 2 was changed to 80 parts by weight of a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F, 15 parts by weight of polyphenylene sulfide, and 5 parts by weight of polysulfone. The epoxy resin was changed to 0 part by weight.
The proton conductivity of this proton exchange membrane is as high as 0.21 (S / cm). When the fuel cell was evaluated, the average value of the fluorine elution rate in the waste water from the start to 200 hours was 0.021 (μg / Hr / cm 2 ) and a very low value. It has been found that the cell life exceeds 1000 hours and exhibits extremely excellent durability.
しかし、このプロトン交換膜の引っ張り弾性率は、テトラフルオロエチレンとＣＦ２＝ＣＦＯ（ＣＦ２）２−ＳＯ２Ｆとから得られた前駆体ポリマーを単独で用いた比較例１のプロトン交換膜の０．８倍程度で、耐久性は向上しているが、膜強度は低下していることが判明した。 However, the tensile elastic modulus of this proton exchange membrane is that of the proton exchange membrane of Comparative Example 1 using a precursor polymer obtained from tetrafluoroethylene and CF 2 ═CFO (CF 2 ) 2 —SO 2 F alone. It was found that the durability was improved at about 0.8 times, but the film strength was lowered.
本発明の高分子電解質組成物から得られるプロトン交換膜は、高温下でも高耐久性を有するプロトン交換膜であり、イオン交換膜および燃料電池の分野で好適に用いられる。本発明により得られるプロトン交換膜は、ダイレクトメタノール型燃料電池を含めた各種燃料電池、水電解、ハロゲン化水素酸電解、食塩電解、酸素濃縮器、湿度センサー、ガスセンサー等に用いることが可能である。 The proton exchange membrane obtained from the polymer electrolyte composition of the present invention is a proton exchange membrane having high durability even at high temperatures, and is suitably used in the fields of ion exchange membranes and fuel cells. The proton exchange membrane obtained by the present invention can be used in various fuel cells including direct methanol fuel cells, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors and the like. is there.
Claims (9)
-[CF2CX1X2]a-[CF2-CF(-O-(CF2-CF(CF2X3))b-Oc-(CFR1)d-(CFR2)e-(CF2)f-X4)]g- (１)（式中、Ｘ１，Ｘ２およびＸ３はそれぞれ独立にハロゲン元素または炭素数１以上３以下のパーフルオロアルキル基、０≦ａ＜１、０＜ｇ≦１、ａ＋ｇ＝１、ｂは０以上８以下の整数、ｃは、０または１であり、ｄ、ｅおよびｆはそれぞれ独立に０以上６以下の整数（ただし、ｄ＋ｅ＋ｆは０に等しくない）、Ｒ１およびＲ２はそれぞれ独立にハロゲン元素、炭素数１以上１０以下のパーフルオロアルキル基またはフルオロクロロアルキル基であり、Ｘ４は、ＣＯＯＺ、ＳＯ３Ｚ、ＰＯ３Ｚ２、ＰＯ３ＨＺ（Ｚは水素原子、アルカリ金属原子、アルカリ土類金属原子、アミン類（ＮＨ４、ＮＨ３Ｒ、ＮＨ２Ｒ２、ＮＨＲ３、ＮＲ４（Ｒはアルキル基、又はアレーン基）） 6. The polymer electrolyte composition according to claim 5, wherein the perfluorocarbon polymer compound having an ion exchange group has a structural unit represented by the following general formula (1).
-[CF 2 CX 1 X 2 ] a- [CF 2 -CF (-O- (CF 2 -CF (CF 2 X 3 )) b -O c- (CFR 1 ) d- (CFR 2 ) e- ( CF 2 ) f -X 4 )] g- (1) (wherein X 1 , X 2 and X 3 are each independently a halogen element or a perfluoroalkyl group having 1 to 3 carbon atoms, 0 ≦ a <1 , 0 <g ≦ 1, a + g = 1, b is an integer of 0 or more and 8 or less, c is 0 or 1, and d, e and f are each independently an integer of 0 or more and 6 or less (where d + e + f is 0) R 1 and R 2 are each independently a halogen element, a perfluoroalkyl group or a fluorochloroalkyl group having 1 to 10 carbon atoms, and X 4 is COOZ, SO 3 Z, PO 3 Z 2. , PO 3 HZ (Z is a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an amine (NH 4 , NH 3 R, NH 2 R 2 , NHR 3 , NR 4 (R is Alkyl group or arene group))
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| JP2009193682A (en) * | 2008-02-12 | 2009-08-27 | Mitsubishi Gas Chem Co Inc | Manufacturing method of membrane-electrode assembly |
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| US10351684B2 (en) | 2013-12-02 | 2019-07-16 | Dexerials Corporation | Ion exchange membrane, polymer element, electronic apparatus, camera module, and imaging device |
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