CN1890300A - 用紫外线辐射交联的聚合物电解质 - Google Patents
用紫外线辐射交联的聚合物电解质 Download PDFInfo
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- CN1890300A CN1890300A CNA2004800368677A CN200480036867A CN1890300A CN 1890300 A CN1890300 A CN 1890300A CN A2004800368677 A CNA2004800368677 A CN A2004800368677A CN 200480036867 A CN200480036867 A CN 200480036867A CN 1890300 A CN1890300 A CN 1890300A
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- fluoropolymer
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- 239000005518 polymer electrolyte Substances 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 24
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 20
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 20
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 9
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
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- 229910006080 SO2X Inorganic materials 0.000 abstract 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 4
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- 125000001246 bromo group Chemical group Br* 0.000 description 3
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- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- MEAWBIDPFZUIJL-UHFFFAOYSA-N (diphenyl-$l^{3}-sulfanyl)benzene Chemical group C1=CC=CC=C1[S](C=1C=CC=CC=1)C1=CC=CC=C1 MEAWBIDPFZUIJL-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
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- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- VTSDGYDTWADUJQ-UHFFFAOYSA-N 2-bromoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Br)=CC=C3C(=O)C2=C1 VTSDGYDTWADUJQ-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
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- QCVMOSGPTRRUQZ-UHFFFAOYSA-N 2-nitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 QCVMOSGPTRRUQZ-UHFFFAOYSA-N 0.000 description 1
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920006169 Perfluoroelastomer Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000000320 amidine group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
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- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- XQYMIMUDVJCMLU-UHFFFAOYSA-N phenoxyperoxybenzene Chemical class C=1C=CC=CC=1OOOC1=CC=CC=C1 XQYMIMUDVJCMLU-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 229920001897 terpolymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
- 229910002007 uranyl nitrate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
-
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Abstract
本发明提供制备通常为膜形式的交联聚合物电解质的方法和由此制备的聚合物，所述交联聚合物电解质用作电解电池如燃料电池中的聚合物电解质膜，该方法包括向高度氟化的含氟聚合物施用紫外辐射，该含氟聚合物包括部分衍生自四氟乙烯单体的主链，含通式－SO2X的基团的第一侧基，其中X为F、Cl、Br、OH或－O－M+，其中M+为一价阳离子，和含Br、Cl或I的第二侧基。该膜的厚度通常为90微米或更低，更通常为60微米或更低，最通常为30微米或更低。
Description
技术领域
本发明涉及制备通常为膜形式的交联聚合物电解质的方法，该方法通过对高度氟化的含氟聚合物施加紫外线辐射，所述膜在电解电池如燃料电池中用作聚合物电解质膜，所述含氟聚合物包括：部分衍生自四氟乙烯单体的主链，含通式-SO2X的基团的第一侧基，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子，和含Br、Cl或I的第二侧基。
背景技术
美国专利No.4,470,889公开了由氟化的聚合物膜分隔成阳极室和阴极室的电解电池；其中所述的膜包含：(a)至少60摩尔％的[CFX-CF2]，其中X为F或Cl；(b)至少600的离子交换当量重；(c)侧链的磺酰基离子交换基团；和(d)基本氟化、不具有离子交换功能的侧链碳族。所述基本氟化、不具有离子交换功能的侧链碳族可包含Br。
美国专利公布No.US2003/0181615A1公开了某些氟磺化的含氟单体、某些溴化的含氟单体，且无四氟乙烯(TFE)单体的聚合物(‘615的234段和64-68段)。该参考文献公开了特定的交联方法。
美国专利No.5,260,351公开了在没有固化剂情况下辐射固化的全氟弹性体。该参考文献涉及固化完全氟化的聚合物，如从四氟乙烯、全氟烷基全氟乙烯基醚制备的那些聚合物，并且在生成的三聚物中固化位置或交联单元提供至少一个腈、全氟苯基、溴或碘。
发明简述
简要地，本发明提供一种制备交联聚合物的方法，包括以下步骤：
a)提供高度氟化的含氟聚合物，该含氟聚合物包括：部分衍生自四氟乙烯单体的主链，含通式-SO2X的基团的第一侧基，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子，和含Br、Cl或I的第二侧基，通常含Br；b)将所述含氟聚合物暴露于紫外线辐射下，以形成交联键。该方法可在所述步骤b)之前另包含步骤c)：使所述含氟聚合物形成膜。该膜的厚度通常为90微米或更低，更通常为60微米或更低，最通常为30微米或更低。通常所述高度氟化的含氟聚合物是全氟化的。通常所述第一侧基是通式为-O-(CF2)4-SO2X的基团，X通常为OH。
另一方面，本发明提供依照本发明的任一方法制备的交联聚合物和聚合物电解质膜。
本领域中没有描述过，而由本发明提供的是采用紫外线辐射对高度氟化的含氟聚合物进行交联的方法，所述含氟聚合物包括部分衍生自四氟乙烯单体的主链，含通式-SO2X的基团的第一侧基，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子，和含Br、Cl或I的第二侧基，该含氟聚合物通常为用作聚合物电解质膜的膜。
在本申请中：
“紫外线辐射”是波长范围起始于400nm、更通常为380nm、更通常为300nm，并向下延伸至通常180nm的电磁辐射。
聚合物的“当量重”(EW)意为中和一当量碱的聚合物重量。
聚合物的“水合积”(HP)指按膜中存在的每当量磺酸基团计，膜吸附的水的当量(摩尔)乘以聚合物的当量重的数值；和
“高度氟化”意为含氟量为40wt.％或以上，通常为50wt.％或以上，更通常为60wt.％或以上。
发明详述
本发明提供一种制备交联聚合物的方法，待交联的聚合物包括：部分衍生自四氟乙烯(TFE)单体的主链，含通式-SO2X的基团的第一侧基，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子，和含Br、Cl或I的第二侧基。这类聚合物可用于制备聚合物电解质膜(PEM’s)，例如用于电解电池，如燃料电池。
由依照本发明的交联聚合物制备的PEM’s可用来制备用于燃料电池的膜电极组件(MEA’s)。MEA是质子交换膜燃料电池(如氢燃料电池)的中心元件。燃料电池是通过将例如氢的燃料和例如氧的氧化剂催化化合产生可用电能的电化学电池。通常的MEA’s包括聚合物电解质膜(PEM)(也称为离子导电膜(ICM))，其功能是作为固体电解质。PEM的一侧与阳极电极层接触，相对侧和阴极电极层接触。每个电极层包括电化学催化剂，通常包括金属铂。气体扩散层(GDL’s)促使气体在阳极和阴极电极材料间传输，并传导电流。GDL还可被称为流体传输层(FTL)或扩散器/电流收集器(DCC)。阳极和阴极电极层可以催化剂油墨的形式用于GDL’s，形成的涂覆GDL’s插入PEM，形成五层MEA。可选择地，阳极和阴极电极层可以催化剂油墨形式用于PEM的两个相对侧，形成的涂覆有催化剂的膜(CCM)插到两层GDL’s间，形成五层MEA。该五层MEA的五层按顺序分别是：阳极GDL、阳极电极层、PEM、阴极电极层和阴极GDL。在通常的PEM燃料电池中，在阳极由氢的氧化产生质子，通过PEM传输到阴极和氧发生反应，在与电极相连的外部电路中产生电流。PEM在反应气体间形成稳定、非多孔、不导电的机械阻挡层，而H+容易通过。
待交联的聚合物包括主链，其可以是支链或非支链的，但通常是非支链的。该主链是高度氟化的，更通常为全氟的。该主链包括衍生自四氟乙烯(TFE)的单元即通常为-CF2-CF2单元和衍生自共聚单体的单元，其通常包括至少一个依照通式CF2＝CY-R的单元，其中Y通常为F，但也可以是CF3，其中R为第一侧基，该第一侧基包括依照通式-SO2X的基团，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子，通常是碱金属阳离子，例如Na+。X最通常为OH。在一个可选的实施方案中，第一侧基R可以通过接枝加到主链中。通常，第一侧基R是高度氟化的，更通常为全氟的。R可以是芳族或非芳族。通常，R是-R1-SO2X，其中R1是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基、全氟烷氧基或全氟聚醚基。R1通常为-O-R2-，其中R2是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基、全氟烷氧基或全氟聚醚基。R1更通常为-O-R3-，其中R3是包含1-15个碳原子的全氟烷基。R1的实例包括：
-(CF2)n-，其中n为1、2、3、4、5、6、7、8、9、10、11、12、13、14或15；
(-CF2CF(CF3)-)n，其中n为1、2、3、4或5；
(-CF(CF3)CF2-)n，其中n为1、2、3、4或5；
(-CF2CF(CF3)-)n-CF2-，其中n为1、2、3或4；
(-O-CF2CF2-)n，其中n为1、2、3、4、5、6或7；
(-O-CF2CF2CF2-)n，其中n为1、2、3、4或5；
(-O-CF2CF2CF2CF2-)n，其中n为1、2或3；
(-O-CF2CF(CF3)-)n，其中n为1、2、3、4或5；
(-O-CF2CF(CF2CF3)-)n，其中n为1、2或3；
(-O-CF(CF3)CF2-)n，其中n为1、2、3、4或5；
(-O-CF(CF2CF3)CF2-)n，其中n为1、2或3；
(-O-CF2CF(CF3)-)n-O-CF2CF2-，其中n为1、2、3或4；
(-O-CF2CF(CF2CF3)-)n-O-CF2CF2-，其中n为1、2或3；
(-O-CF(CF3)CF2-)n-O-CF2CF2-，其中n为1、2、3或4；
(-O-CF(CF2CF3)CF2-)n-O-CF2CF2-，其中n为1、2或3；
-O-(CF2)n-，其中n为1、2、3、4、5、6、7、8、9、10、11、12、13或14；
R通常为-O-CF2CF2CF2CF2-SO2X或-O-CF2-CF(CF3)-O-CF2-CF2-SO2X，最通常为-O-CF2CF2CF2CF2-SO2X，其中X为F、Cl、Br、OH或-O-M+，但最通常为OH。
提供第一侧基R的含氟单体可通过任何适合的方法来合成，包括美国专利No.6,624,328中所述的方法。
此外，该含氟聚合物包括含Br、Cl或I的第二侧基Q，通常为含Br。该第二侧基可衍生自通式CF2＝CY-Q的共聚单体，其中Y通常为F但也可为CF3，Q是含Br、Cl或I的第二侧基。在替换性实施方案中，第二侧基可通过接枝加到主链中。第二侧基Q除溴位外通常是高度氟化的，更通常是全氟化的。通常Q为-R1-Br，其中R1如上所述。可替换地，Q为Br、Cl或I，通常为Br。
Cl、Br或I的总含量通常为0.05-5wt.％，更通常为0.1-2wt.％。
所述含氟聚合物最通常为TFE、上述CF2＝CY-R和上述CF2＝CY-Q的三元共聚物。
待交联的聚合物可以用任何适当的方法制备，包括乳液聚合、挤出聚合、超临界二氧化碳中聚合、溶液或悬浮液聚合等，其可以是间歇的或连续的。
在一个实施方案中，可在聚合过程中使用链转移剂，用以提供带有Cl、Br或I端基的聚合物。当存在此类端基时，可将其视作用于本发明目的的侧基。链转移剂的实例包括具有通式RXn的试剂，其中R是含1-12个碳原子、氟化或非氟化的n价烷基，且其中的X独立选自Cl、Br或I。其他的链转移剂如美国专利No.4,000,356和6,380,337中所列举。另外，聚合可在Br-或I-盐存在下进行，从而引入末端的Br或I端基，如EP407937中所述。
酸官能侧基通常以足量存在，从而使水合积(HP)大于15,000，更通常大于18,000，更通常大于22,000，最通常大于25,000。通常，较高HP与较高离子电导相关。
酸官能侧基通常以足量存在，从而使当量重(EW)小于1200，更通常小于1100，更通常小于1000，更通常小于900。
在本发明的一个实施方式中，在交联前使聚合物与交联剂接触。任何合适的交联剂均可使用，从而使其与从侧基除去Cl、Br或I而产生的至少两个基团反应。可用于本发明实践的交联剂可包括聚芳族类或聚乙烯基类，其可以是非氟化的或者氟化至低水平的，但更通常是高度氟化的，更通常是全氟化的。本发明中有用的交联剂实例包括：三羟甲基丙基三丙烯酸酯(TMPTA)，二苯醚，二苯氧基烷烃，二苯氧基醚，二苯氧基聚醚，二-、三-和四烯丙基类，等等。交联剂和聚合物可通过任何适当的方式混合到一起，包括在溶液或悬浮液中混合、捏合、研磨等。可选择地，可将交联剂加入至成形的膜中，例如将膜浸渍入交联剂溶液中。可加入任何相对于第一侧基适当量的交联剂。如果加入过量，可在交联后除去过量的交联剂。可选择地，如果交联剂的加入量小于等摩尔量，那么预期仅有部分形成的交联键通过交联剂的分子。
在本发明的一个实施方式中，聚合物或聚合物/交联剂混合物在交联前形成膜。可使用任何适当的成膜方法。聚合物通常从悬浮液或溶液浇铸成膜。可使用任何适当的浇铸方法，包括棒涂法、喷涂法、狭缝涂覆法、刷涂法等。可选择地，该膜可在熔融过程中从纯聚合物形成，例如挤出法。形成后，可使膜退火。通常膜的厚度为90微米或更低，更通常60微米或更低，最通常30微米或更低。较薄的膜对离子通过的抵抗性较低。在燃料电池使用中，这样会导致较冷的操作和较大的有用能量输出。较薄的膜必须由在使用时可保持其结构完整性的材料制成。
在另一个实施方式中，该聚合物在交联之前被吸入多孔支撑基质中，通常以薄膜形式，所述膜厚度为90微米或更低，更通常为60微米或更低，最通常为30微米或更低。可使用任何适当的将聚合物吸入支撑基质孔中的方法，包括过压法、真空法、芯吸法、浸渍法等。通过脒基团的反应，混合物嵌到基质中。可使用任何适当的支撑基质。通常，支撑基质是非导电性的。通常，支撑基质由含氟聚合物构成，更通常其为全氟化的。通常的基质包括多孔聚四氟乙烯(PTFE)，例如双轴拉伸的PTFE料片。其他的实施方案可见于美国专利Nos.RE37,307，RE37,656，RE37,701和6,254,978中。
可在任何适当的阶段，例如在膜形成过程中向聚合物或膜中加入有效量的一种或多种光引发剂。任意合适的UV光引发剂均可使用，包括苄基缩酮如IrgacureTM651，α-羟基酮例如IrgacureTM2959，BAPO型光引发剂例如IrgacureTM819，二芳基碘鎓盐，三芳基碘鎓盐，偶氮化合物，过氧化物等。此类光引发剂包括二苯甲酮和其衍生物；安息香，α-甲基安息香，α-苯基安息香，α-烯丙基安息香，α-苄基安息香；安息香醚例如联苯酰二甲基缩酮(可购自Ciba-Geigy，Ardsley，N.Y.，商品名“IrgacureTM651”)，安息香甲醚，安息香乙醚，安息香正丁醚；苯乙酮和其衍生物如2-羟基-2-甲基-1-苯基-1-丙酮(可购自Ciba-Geigy，Ardsley，N.Y.，商品名“DAROCUR1173”)，和1-羟基环己基苯酮(HCPK)(也可购自Ciba-Geigy Corporation，商品名“IRGACURE184”)；2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮(也可购自Ciba-GeigyCorporation，商品名“IRGACURE 907”)；2-苄基-2-(甲氨基)-1-[4-(4-吗啉基)苯基]-1-丁酮(也可购自Ciba-Geigy Corporation，商品名“IRGACURE 369”)；其他可用的光引发剂包括pivaloin乙醚，茴香偶姻乙醚，蒽醌类如蒽醌，2-甲基蒽醌，2-乙基蒽醌，2-叔丁基蒽醌，1-氯蒽醌，2-溴蒽醌，2-硝基蒽醌，蒽醌-1-羧醛，蒽醌-2-硫醇，4-环己基蒽醌，1，4-二甲基蒽醌，1-甲氧基蒽醌，苯并蒽醌卤代甲基三嗪；鎓盐例如重氮盐如苯基重氮六氟磷酸盐等；二芳基碘鎓盐例如二甲苯基碘鎓六氟锑酸盐，硫鎓盐例如三苯基硫鎓四氟硼酸盐等；钛络合物例如同样购自Ciba-Geigy Corporation的商品“CGI784DC”)；铀酰盐例如硝酸铀酰，丙酸铀酰；卤代甲基硝基苯例如4-溴甲基硝基苯等；单-和双-酰基膦如购自Ciba-Geigy的商品“IRGACURE1700”、“IRGACURE1800”、“IRGACURE1850”和“DAROCUR4265”。
交联的步骤包括将含氟聚合物暴露于紫外辐射从而形成交联键的步骤。任意合适的设备和UV源均可使用，包括弧光灯，微波驱动的灯、汞灯、镓灯、激光、日光灯等等。通常，UV辐射的波长在300与180nm之间，更通常在280与200nm之间。UV辐射的剂量通常为1mJ/cm2或更高，更通常为5mJ/cm2或更高，更通常为10mJ/cm2或更高，最通常为50mJ/cm2或更高。可采用连续暴露方法，用以处理成卷的膜。
可以理解，依本发明制备的聚合物和膜在化学结构上，在交联的结构、交联的位置、酸官能基的位置、侧基上交联的存在或不存在或者交联上酸官能基的存在或不存在等方面可与其他方法制备的有所不同。
本发明可用于制备用在电解电池(例如燃料电池)中的增强聚合物电解质膜。
本发明的目的和优点可以通过下面的实施例做进一步说明，但这些实施例中的特定材料和用量，以及其它条件和细节，都不应当被解释为对本发明不适当的限制。
实施例
除非特别指出，所有试剂都来自或可获自Aldrich Chemical Co.，Milwaukee，WI，或者可由已知方法合成得到。
聚合物
用于本实施例的聚合物电解质由四氟乙烯(TFE)与用美国专利6,624,328中所述方法合成的CF2＝CF-O-(CF2)4-SO2F(MV4S)和CF2＝CF-O-(CF2)2-Br(MV2Br)乳液共聚制备而成。
使用ULTRA-TURRAXT25型分散器S25KV-25F(IKA-WerkeGmbH&Co.KG，Staufen，Germany)，在水中将130g MV4S和15gAPFO乳化剂(全氟辛酸铵，C7F15COONH4)以高剪切(24000转/分)预乳化2分钟。在带有叶片搅拌器的4升聚合釜中装入3.1kg去离子水。将该釜加热到50℃，然后将预制乳状液装到无氧的聚合釜中。在50℃下，向釜中进一步加入6g MV2Br和178g气态四氟乙烯(TFE)至8bar的绝对反应压力。在50℃和240转每分钟的搅拌速度下，通过加入15g亚硫酸氢钠和40g过氧化硫酸氢铵开始聚合。在反应过程中，反应温度保持在50℃。通过在气相中加入另外的TFE使反应压力保持在8.0bar绝对压力。采用427g MV4S，以如上所述方式和比例制备第二份MV4S-预乳化液。在反应过程中将第二份预乳化液连续加到液相中。在反应过程中将另外的26g MV2Br也连续加到反应器中。
在加入800g TFE之后，关闭单体阀，中断单体给料。连续聚合将单体气相压力降低到2.9bar。此时，将反应器排空，用氮气冲洗。所得聚合物具有25.8mol％的MV4S含量和1.2mol％的MV2-Br含量；MFI(265/5kg)为4.1g/10min。
将由此得到的聚合物分散液与3当量的LiOH和2当量的Li2CO3(基于磺酰氟的浓度)和足够的水混合，得到20％的聚合物固态混合物。将该混合物加热到250℃，保持4小时。绝大部分(＞95％)的聚合物在该条件下被分散。将分散液过滤，去除LiF和未分散的聚合物，然后用Mitsubishi Diaion SKT10L离子交换树脂进行离子交换，得到酸式离子聚合物。形成的聚合物电解质是全氟化聚合物，其酸性侧链依照通式：-O-(CF2)4-SO3H和通式-O-(CF2)2-Br。得到的混合物为含有18％-19％聚合物固体的酸分散液。将此分散液真空浓缩至约38％固体，然后与正丙醇混合，得到希望的在约40％水/60％正丙醇的水/正丙醇溶剂混合物中含20％固体分散液。此碱性分散液用于浇铸膜。
在不脱离本发明范围和主旨的前提下，本领域的技术人员可对本发明进行各种修改和变化，应当理解为在此提出的示例性实施方式不是对本发明不适当的限制。
Claims (10)
1.一种制备交联聚合物的方法，其包括如下步骤：
a)提供高度氟化的含氟聚合物，该含氟聚合物包括：部分衍生自四氟乙烯单体的主链，含通式-SO2X的基团的第一侧基，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子，以及含选自Br、Cl和I的卤素原子的第二侧基；和
b)将所述含氟聚合物暴露于紫外辐射，从而形成交联键。
2.权利要求1的方法，其中所述高度氟化的含氟聚合物是全氟化的。
3.权利要求1或2的方法，其中所述侧基是通式为-R1-SO2X的基团，其中R1是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基或全氟醚基，且X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子。
4.权利要求1-3任一项的方法，其中所述侧基是通式为-O-(CF2)4-SO2X的基团，其中X为F、Cl、Br、OH或-O-M+，其中M+为一价阳离子。
5.权利要求1-4任一项的方法，其中所述侧基是通式为-O-(CF2)4-SO3H的基团。
6.权利要求1-5任一项的方法，其中所述第二侧基中包含的所述卤素原子是Br。
7.权利要求1-6任一项的方法，其中所述方法在所述步骤b)之前另包含如下步骤：
c)使所述含氟聚合物形成膜。
8.权利要求7的方法，其中所述膜厚度为90微米或更低。
9.一种聚合物电解质膜，其包含由权利要求1-6任一项方法制得的交联聚合物。
10.一种聚合物电解质膜，其由权利要求7或8的方法制得。
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| PCT/US2004/039173 WO2005061593A1 (en) | 2003-12-11 | 2004-11-22 | Polymer electrolytes crosslinked by ultraviolet radiation |
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| IT1318593B1 (it) * | 2000-06-23 | 2003-08-27 | Ausimont Spa | Ionomeri fluorurati. |
| IT1318669B1 (it) | 2000-08-08 | 2003-08-27 | Ausimont Spa | Ionomeri fluorurati solfonici. |
| CN1318398C (zh) | 2001-02-01 | 2007-05-30 | 旭化成株式会社 | 具有磺酰胺基的全氟乙烯基醚单体 |
| ITMI20010383A1 (it) | 2001-02-26 | 2002-08-26 | Ausimont Spa | Membrane idrofiliche porose |
| US6503378B1 (en) * | 2001-04-23 | 2003-01-07 | Motorola, Inc. | Polymer electrolyte membrane and method of fabrication |
| US7045571B2 (en) | 2001-05-21 | 2006-05-16 | 3M Innovative Properties Company | Emulsion polymerization of fluorinated monomers |
| TW587351B (en) * | 2001-10-15 | 2004-05-11 | Du Pont | Fuel cell membranes |
| US6727386B2 (en) * | 2001-10-25 | 2004-04-27 | 3M Innovative Properties Company | Aromatic imide and aromatic methylidynetrissulfonyl compounds and method of making |
| JP4161616B2 (ja) * | 2002-05-30 | 2008-10-08 | ダイキン工業株式会社 | 成形体及び固体高分子電解質型燃料電池 |
| US7273537B2 (en) * | 2002-09-12 | 2007-09-25 | Teck Cominco Metals, Ltd. | Method of production of metal particles through electrolysis |
| US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
| US7071271B2 (en) | 2003-10-30 | 2006-07-04 | 3M Innovative Properties Company | Aqueous emulsion polymerization of functionalized fluoromonomers |
| US7179847B2 (en) * | 2003-11-13 | 2007-02-20 | 3M Innovative Properties Company | Polymer electrolytes crosslinked by e-beam |
| US7074841B2 (en) * | 2003-11-13 | 2006-07-11 | Yandrasits Michael A | Polymer electrolyte membranes crosslinked by nitrile trimerization |
| US7259208B2 (en) * | 2003-11-13 | 2007-08-21 | 3M Innovative Properties Company | Reinforced polymer electrolyte membrane |
| US7265162B2 (en) * | 2003-11-13 | 2007-09-04 | 3M Innovative Properties Company | Bromine, chlorine or iodine functional polymer electrolytes crosslinked by e-beam |
| US7060756B2 (en) * | 2003-11-24 | 2006-06-13 | 3M Innovative Properties Company | Polymer electrolyte with aromatic sulfone crosslinking |
| US7112614B2 (en) * | 2003-12-08 | 2006-09-26 | 3M Innovative Properties Company | Crosslinked polymer |
| US7060738B2 (en) | 2003-12-11 | 2006-06-13 | 3M Innovative Properties Company | Polymer electrolytes crosslinked by ultraviolet radiation |
| US7173067B2 (en) * | 2003-12-17 | 2007-02-06 | 3M Innovative Properties Company | Polymer electrolyte membranes crosslinked by direct fluorination |
-
2003
- 2003-12-11 US US10/733,211 patent/US7060738B2/en not_active Expired - Fee Related
-
2004
- 2004-11-22 WO PCT/US2004/039173 patent/WO2005061593A1/en active Application Filing
- 2004-11-22 JP JP2006543845A patent/JP2007517088A/ja not_active Withdrawn
- 2004-11-22 CA CA002549085A patent/CA2549085A1/en not_active Abandoned
- 2004-11-22 KR KR1020067013813A patent/KR20060130095A/ko not_active Application Discontinuation
- 2004-11-22 EP EP04811828A patent/EP1692215A1/en not_active Withdrawn
- 2004-11-22 CN CN2004800368677A patent/CN1890300B/zh not_active Expired - Fee Related
- 2004-12-07 TW TW093137819A patent/TW200535173A/zh unknown
-
2012
- 2012-04-06 JP JP2012087545A patent/JP2012144740A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101252195B (zh) * | 2007-02-21 | 2012-05-30 | 独立行政法人日本原子力研究开发机构 | 包含烷基接枝链的聚合物电解质薄膜及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US7060738B2 (en) | 2006-06-13 |
| KR20060130095A (ko) | 2006-12-18 |
| US20050131097A1 (en) | 2005-06-16 |
| EP1692215A1 (en) | 2006-08-23 |
| CA2549085A1 (en) | 2005-07-07 |
| WO2005061593A1 (en) | 2005-07-07 |
| TW200535173A (en) | 2005-11-01 |
| JP2012144740A (ja) | 2012-08-02 |
| CN1890300B (zh) | 2010-05-26 |
| JP2007517088A (ja) | 2007-06-28 |
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