CA2240495C - .alpha.,.beta.,.beta.-trifluorostyrene-based and substituted .alpha.,.beta.,.beta.-trifluorostyrene-based composite membranes - Google Patents
.alpha.,.beta.,.beta.-trifluorostyrene-based and substituted .alpha.,.beta.,.beta.-trifluorostyrene-based composite membranes Download PDFInfo
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- CA2240495C CA2240495C CA002240495A CA2240495A CA2240495C CA 2240495 C CA2240495 C CA 2240495C CA 002240495 A CA002240495 A CA 002240495A CA 2240495 A CA2240495 A CA 2240495A CA 2240495 C CA2240495 C CA 2240495C
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- composite membrane
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- perfluoroalkyls
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- 239000012528 membrane Substances 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 26
- -1 PO2H2 Inorganic materials 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 20
- 239000003014 ion exchange membrane Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
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- 229910006095 SO2F Inorganic materials 0.000 claims 6
- 229910006069 SO3H Inorganic materials 0.000 claims 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 6
- 229910004727 OSO3H Inorganic materials 0.000 claims 5
- 229910018828 PO3H2 Inorganic materials 0.000 claims 5
- 239000000758 substrate Substances 0.000 abstract description 45
- 239000000203 mixture Substances 0.000 abstract description 29
- 238000005342 ion exchange Methods 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Chemical class 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 4
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- 229920001903 high density polyethylene Polymers 0.000 description 4
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- 238000011068 loading method Methods 0.000 description 4
- 230000005588 protonation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
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- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WCVOGSZTONGSQY-UHFFFAOYSA-N 2,4,6-trichloroanisole Chemical compound COC1=C(Cl)C=C(Cl)C=C1Cl WCVOGSZTONGSQY-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Classifications
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- B01D71/32—Polyalkenyl halides containing fluorine atoms
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- H01M50/491—Porosity
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A composite membrane is provided in which a porous substrate is impregnated with a polymeric composition comprising various combinations of .alpha.,.beta.,.beta.-trifluorostyrene, substituted .alpha.,.beta.,.beta.-trifluorostyrene and ethylene-based monomeric units. Where the polymeric composition includes ion-exchange moieties, the resultant composite membranes are useful in electrochemical applications, particularly as membrane electrolytes in electrochemical fuel cells.
Description
a, 8, 8-TRIFhUOROSTYRENE-BASED AND SUBSTITUED
a, !3, ~i-TRIFLUOROSTYRENE-BASED COMPOSITE MEI~RANES
Cross-Reference to Related Patents This application corresponds with U.S. Patent No.
5,834,523, issued November 10, 1998, which is a continuation-in-part of U.S. Patent Application Serial No. 08/442,206 filed May 16, 1995, now U.S. Patent No.
5,498,639, issued March 12, 1996, which is a continuation of U.S. Patent Application Serial No. 08/124,9;4 filed September 21, 199:3, now U.S. Patent No. 5,422,9:11 issued June 6, 1995, entitled " Trifluorostyrene and Substituted Trifluorostyrene Copolymeric Compositions and I:on-exchange Membranes Farmed Therefrom " . The °206 and '924 applications describe polymeric compositions derived from copolymers of a, i3, i3-trifluorostyrene with a variety of IS substituted a, f~, i3-trif luorostyrenes . These compositions are suitable for use as membranes, particularly as ion-exchange membranes. This application is also related to U.S. Patent Application Serial No.
08/480,098 filed June 6, 1995, now U.S. Patent 5,602,185, issued February 11, 1997, entitled "Substituted Trifluorostyrene Compositions" . The latter application describes copolymers of a, i3, f~-trifluorostyrene and substituted a, i3, i3-trifluorostyrenes, including sulfonyl fluoride substituted a, f3, i3-trifluorostyrene monomeric units that are conveniently hydrolyzed t:o produce polymeric compositions with ion-exchange maieties.
Field Of The Invention This invention relates generally to composite membranes comprising a porous substrate and a polymeric composition comprising various combinations of a, i3, f3
a, !3, ~i-TRIFLUOROSTYRENE-BASED COMPOSITE MEI~RANES
Cross-Reference to Related Patents This application corresponds with U.S. Patent No.
5,834,523, issued November 10, 1998, which is a continuation-in-part of U.S. Patent Application Serial No. 08/442,206 filed May 16, 1995, now U.S. Patent No.
5,498,639, issued March 12, 1996, which is a continuation of U.S. Patent Application Serial No. 08/124,9;4 filed September 21, 199:3, now U.S. Patent No. 5,422,9:11 issued June 6, 1995, entitled " Trifluorostyrene and Substituted Trifluorostyrene Copolymeric Compositions and I:on-exchange Membranes Farmed Therefrom " . The °206 and '924 applications describe polymeric compositions derived from copolymers of a, i3, i3-trifluorostyrene with a variety of IS substituted a, f~, i3-trif luorostyrenes . These compositions are suitable for use as membranes, particularly as ion-exchange membranes. This application is also related to U.S. Patent Application Serial No.
08/480,098 filed June 6, 1995, now U.S. Patent 5,602,185, issued February 11, 1997, entitled "Substituted Trifluorostyrene Compositions" . The latter application describes copolymers of a, i3, f~-trifluorostyrene and substituted a, i3, i3-trifluorostyrenes, including sulfonyl fluoride substituted a, f3, i3-trifluorostyrene monomeric units that are conveniently hydrolyzed t:o produce polymeric compositions with ion-exchange maieties.
Field Of The Invention This invention relates generally to composite membranes comprising a porous substrate and a polymeric composition comprising various combinations of a, i3, f3
-2-trifluorostyrene, substituted a, f3, i3-trifluorostyrene and ethylene-based monomeric units. Where the polymeric composition includes ion-,exchange moieties, thf=_ resultant composite membranes are useful in electrochemical applications, particularly as membrane electrolytes in electrochemical fuel cells.
8ackqround Of The Invention Dense Films can be obtained from solutions of poly-a, i3, i3-trifluorostyrene. However, the brittleness of these films greatly limits their application. Films obtained from some sulfonated poly- a, f~, f~-t:rifluorostyrene r_an be used as ion-exchange membranes.
However, such films often have unfavourable mechanical properties when wet, and are known to be very brittle in t:he dry state (see, for example, Russian Chemical Reviews, Vo1.59, p. 583 (1998)). Such films are of little practical use in fuel cells due to their poor physical properties. Some improvements in mechanical properties have
8ackqround Of The Invention Dense Films can be obtained from solutions of poly-a, i3, i3-trifluorostyrene. However, the brittleness of these films greatly limits their application. Films obtained from some sulfonated poly- a, f~, f~-t:rifluorostyrene r_an be used as ion-exchange membranes.
However, such films often have unfavourable mechanical properties when wet, and are known to be very brittle in t:he dry state (see, for example, Russian Chemical Reviews, Vo1.59, p. 583 (1998)). Such films are of little practical use in fuel cells due to their poor physical properties. Some improvements in mechanical properties have
- 3 -been achieved by blending suifonated poly-a,i3,i3-trifluorostyrene with polyvinylidene fluoride and triethyl phosphate plasticizes, but these films . remained unsatisfactory for application in electrochemical cells (see Fuel Cell Handbook, A.J.
Appleby, published by Van Nostrand Reinhold, p. 286 (1989) ) .
U.S. Patent No. 5,422,41.1 and the related patent applications mentioned above describe various polymeric compositions incorporating substituted a, i3, f3-trifluorostyrenes and some cases further incorporating substituted ethylenes.
Typically these compositions, as membranes, possess favorable mechanical properties compared to poly-I5 a, !3, i3-trif luorostyrene and sulfonated poly-a, f3, i~-trifluorostyrene, although some of the membranes have a tendency to become brittle in the fully dehydrated state, depending, for example, on the equivalent weight. This effect is most apparent at equivalent weights below approximately 380 g/mol.
Ion-exchange membranes derived from these polymeric compositions are suitable for many applications, including use in electrochemical applications, such as fuel cells.
For ease of handling, for example, in the preparation of membrane electrode assemblies for use in electrochemical fuel cells, the mechanical strength of the membrane in the dry state is important. In electrochemical applications, such as electrolytic cells and fuel cells, the dimensional stability (changes in the dimensions of the membrane due to changes in the degree of hydration) of the membrane during operation is also ' . important. However, to improve performance, it is
Appleby, published by Van Nostrand Reinhold, p. 286 (1989) ) .
U.S. Patent No. 5,422,41.1 and the related patent applications mentioned above describe various polymeric compositions incorporating substituted a, i3, f3-trifluorostyrenes and some cases further incorporating substituted ethylenes.
Typically these compositions, as membranes, possess favorable mechanical properties compared to poly-I5 a, !3, i3-trif luorostyrene and sulfonated poly-a, f3, i~-trifluorostyrene, although some of the membranes have a tendency to become brittle in the fully dehydrated state, depending, for example, on the equivalent weight. This effect is most apparent at equivalent weights below approximately 380 g/mol.
Ion-exchange membranes derived from these polymeric compositions are suitable for many applications, including use in electrochemical applications, such as fuel cells.
For ease of handling, for example, in the preparation of membrane electrode assemblies for use in electrochemical fuel cells, the mechanical strength of the membrane in the dry state is important. In electrochemical applications, such as electrolytic cells and fuel cells, the dimensional stability (changes in the dimensions of the membrane due to changes in the degree of hydration) of the membrane during operation is also ' . important. However, to improve performance, it is
- 4 -generally desirable to reduce membrane thickness and to decrease the equivalent weight (thereby increasing the water content) of the membrane electrolyte, both of which tend to decrease both ' the mechanical strength in the dry state and the dimensional stability in the wet state. One way to improve mechanical strength and dimensional stability in ionomeric membranes is through use of a substrate or support material, to give a composite membrane. The substrate is selected so that it imparts mechanical strength and dimensional stability to the membrane. The substrate material can be combined with the membrane polymeric material to form a composite membrane in a variety of ways. For example, if possible, an unsupported membrane can be preformed and then laminated to the porous substrate. Alternatively, a solution of the polymer can be impregnated into the porous substrate material, and the composite membrane subsequently dried. The formation of composite membranes via impregnation provides a more intimate contact between the two components, thus giving advantages over standard lamination approaches.
Composite ion-exchange membranes prepared by impregnating commercially available porous polytetrafluoroethylene film (Gore-tex~) with Nafion~, a perfluorosulfonate ionomer, have been described in Journal of the Electrochemical Society, Vol. 132, pp. 5I4-515 (1985). The major goal in the study was to develop a composite membrane with the desirable chemical and mechanical features of Nafion~, but which could be produced at low cost. Indeed, based on the polymer loadings necessary to produce these composite membranes, ' CA 02240495 1998-06-16 ,_ ..
they are a low cost alternative to the costly perfluorosulfonic acid membranes. As indicated above, however, these perfluorosulfonate ionomers are known to form membranes suitable for use in electrochemical applications without the use of a substrate.
It has been discovered that polymers which have a tendency to become brittle in the dehydrated state can be rendered mechanically stable, even in the fully dehydrated state, by impregnation into suitable substrates.
Furthermore, it has been discovered that even polymers which are poor film formers, or polymers which form films with mechanical properties and dimensional stability which would preclude their use in electrochemical and other applications, can be made into composite membranes through incorporation into a suitable substrate. The resulting composite membranes have the-desired physical properties for use in a wide range of applications.
Summary Of The Invention A composite membrane comprises a flexible porous polymeric sheet material impregnated with a polymer comprising fragments of formula (I):
-E CF=-CTS-~CF2-CF- n --f CFZ-Ct~z C~--EEC--~CFiZ-CH-)"' P Q ~ s 2 5 \ ~ \\~ ~ ~~I w,~ . ( I ) x M Ax Z
wherein m, n, p, q, r, and s are zero or an integer greater than zero, and at least one of m, n, p and q is an integer greater than zero, whereby the polymer comprises at least one type of substituted AMENDED St~~ET
,.. . .., ., ., - , or unsubstituted cx, f3, f3-trifluorostyrene monomeric unit. The thickness of the flexible polymeric sheet material into which the polymer of formula (I) is impregnated is preferably 10-200 ~.m.
In the above formula:
X is selected from the group consisting of S02F, S03H, P02H2, P03Hz, CHaP03Hz, COON, OS03H, OP02H2, OP03H~, OArS03H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3~ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
A1 and A2 are selected from the group consisting of halogens, CxHYFz (where x is an integer greater than zero and y+z = 2x+1), CF=CF2, CN, NOZ and OH, O-R (where R is selected from the group consisting of alkyls and perfluoroalkyls and aryls), and when m is an integer greater than zero, the group from which A1 and Aa are selected further consists of SOZF, S03H, POzH2, P03H2, CHaP03H2, COOH, OS03H, OP02H2, OP03Ha, OArS03H where Ar is an aryl, NR3~ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
Z is hydrogen or a non-hydrogen substituent whereby, when s is an integer greater than zero, the polymer further comprises styrene or substituted styrene monomeric units;
E is selected from the group consisting of CHa-CHZ, CHz-CHF, CFH-CFH, CFa-CHa, CFa-CHF, CFa-CFa whereby, when r is an integer greater than zero, the polymer further comprises ethylene, partially fluorinated ethylene or tetrafluoroethylene -. hAA~ND~D W~t~' monomeric units.
In some embodiments of the above composite membrane, at least p is an integer greater than zero, whereby the polymer comprises at least one type of "A"-substituted a,f3,i3-trifluorostyrene monomeric unit.
In other embodiments of the above composite membrane, at least m is an integer greater than zero, whereby the polymer comprises at least one type of "X"-substituted a,f3,f3-trifluorostyrene monomeric unit. In preferred embodiments, at least one of n, p and q is also an integer greater than zero, whereby the polymer comprises more than one type of a,f3,f3-trifluorostyrene-based monomeric unit.
In other preferred embodiments, at least one of p and q, as well as m, is an integer greater than zero, whereby the polymer comprises more than one type of substituted cx, f3, f3-trifluorostyrene monomeric unit.
A preferred X-substituent is SOaF, whereby the polymer comprises a,f3,f3-trifluorostyrene sulfonyl fluoride monomeric units. Again, at least one of n, p and q may also be an integer greater than zero.
In particularly preferred embodiments, both n and p are integers greater than zero, and AL is selected from the group consisting of fluorine, CF3 and para-phenoxy.
Another preferred X-substituent is S03H.
Again, n may also be an integer greater than zero, and at least one of p and q may also be an integer greater than zero. In particularly preferred embodiments, both n and p are integers greater than zero, and A1 is selected from the group consisting of fluorine, CF3 and para-phenoxy.
r l~~v~~'~U~ii 3ri~~~
CA 02240495 1998-06-16 ,_ __ _ g _ In still further embodiments of the above composite membrane both m and p are integers greater than zero, and A1 is selected from the group consisting of S02F, S03H, POzHz, P03H2, CH~PO,Hz, COOH, OS03H, OP02Ha, OP03H2, OArS03H where Ar is an aryl, NR3~ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH~NR,+
(where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls). In these embodiments the polymer comprises more than one type of ion-exchange moiety.
In the composite membranes described above, preferred flexible polymeric sheet materials include those comprising polytetrafluorethylene, a polyolefin or a partially fluorinated polyolefin.
Flexible polyermic sheet materials comprising a polymer selected from the group consisting of polyethylene, polypropylene, polyvinylidene fluoride, poly(ethylene-co-tetrafluoroethylene) and poly(tetrafluoroethylene-co-hexafluoropropylene) are particularly preferred for certain applicatiori.s.
Expanded polytetrafluoroethylene is another example of a preferred substrate.
For certain applications, such as fuel cell applications, the composite membrane is preferably substantially gas impermeable.
In the aspects and embodiments described above, the polymeric compositions can consist essentially of the described monomeric units.
In the aspects and embodiments described above, the A1, A2, A3 substituents may be further elaborated by known means such as, for example, by hydrolysis of the CN group to form COOH or by reduction with common reducing agents (such as, for example, Raney AN1END~D S~i~.GT
" ..
' o -, , , , , . , , , , , ., ,, , , " " , ."
nickel) to form a primary amine, thereby transforming the A1, Aa and A3 substituents into ion-exchange moieties. The resulting polymeric composition may thus comprise one or more type of ion-exchange moiety, and may also comprise both cation-exchange and anion-exchange moieties.
The term "monomeric unit" as used herein indicates that the polymeric composition contains the described fragment or unit, and is obtained by a polymerization reaction involving the corresponding unsaturated monomer.
The substituents on the aromatic rings (including, for example, A1, A2, A3, X, B and D) may each be located in the ortho, meta or para positions, as indicated in the formulas wherein the chemical bond drawn for the substituents intersects the aromatic ring. In preferred aspects of the described embodiments, the substituents are in the meta or para positions.
As used herein, the term "aryl" refers to a substituted or unsubstituted phenyl group. The formula CXH~,FZ (where x is an integer greater than zero and y+z = 2x+1) is used to indicate alkyl, perfluoroalkyl or partially fluorinated alkyl groups.
In accordance with convention in the art, the above chemical formulas for polymeric compositions containing more than two monomeric units (where at least three of m, n, p and q are greater than zero) are intended to indicate that the monomeric units are present in the polymeric composition, but are not limited to the particular order in which the monomeric units are set forth in each general formula. For example, random linear copolymers, A~i~~iDED 5~~~'f . , , , ;
. . , , , . , " . .., ,, :, alternating copolymers and linear block copolymers, formed from the indicated monomeric units, are contemplated.
ARAEPiDED SHEFt y _ , - , ,., , , , , ; ., , - , , , _. _, ~:., "
Brief Descri-ption Of The Drawings FIG. 1 is a plot of cell voltage as a function of current density (expressed in milliamperes per square centimeter) in an electrochemical fuel cell employing a composite membrane of porous polyethylene impregnated with a sulfonated copolymer of a,f3,13-trifluorostyrene and m-trifluoromethyl-a,i3,f~-trifluorostyrene, as the proton exchange membrane.
FIG. 2 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane, prepared by impregnation of porous polyethylene with sulfonated poly-a, i3, f3-trifluorostyrene, as the proton exchange membrane.
FIG. 3 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane, prepared by impregnation of porous polyethylene with a copolymer of a, f3, i3-trifluorostyrene, m-trifluoromethyl-a, f3, f~-trifluorostyrene and p-sulfonyl fluoride-a,f3,f3-trifluorostyrene, and subsequent hydrolysis, as the proton exchange membrane.
a~~rin~.o s~~FT
' . . , ~ - . . :.' . : , ; ; ; , ,.,.; ~ ...
. . , , ., . , , ., FIG. 4 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane of expanded polytetrafluoroethylene impregnated with a sulfonated copolymer of a, fS, f3-trifluorostyrene and m-trifluoromethyl-a,f3,i3-trifluorostyrene, as the proton exchange membrane.
FIG. 5 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane of expanded polytetrafluoroethylene impregnated with a low equivalent weight sulfonated copolymer of a,i3,i3-trifluorostyrene and m-trifluoromethyl-a, i3, f3-tri-fluorostyrene, as the proton exchange membrane.
Detailed Description Of The Preferred Embodiments Methods for preparing the polymeric compositions described herein are described in the related applications or will be apparent to those skilled in the art.
The preferred substrate material is dependent on the application in which the composite membrane is to be used. The substrate material preferably has good mechanical properties, is chemically and thermally stable in the environment in which the composite membrane is to be used, is tolerant of the solvent used for impregnation, and in most applications is preferably flexible. Preferred substrates for electrochemical applications are porous polymeric materials. Preferred polymeric materials are, for example, ~~riE'~1~'~J S!-~~~?' hydrocarbons such as porous polyolefins, especially polyethylene and pclypropylene. In some applications, a perfluorinated polymeric substrate may be preferred, for example, a preferred substrate material, when the composite membrane is to be used in an electrochemical fuel cell, is porous polytetrafluoroethylene, also known as expanded polytetrafluoraethylene. Porous polyolefins and polytetrafluoroethylenes typically have excellent mechanical strength, flexibility and do not swell in water. Polytetrafluoroethylene offers additional advantages in that it is also chemically inert, and porous polytetrafluoroethylene films with different characteristics are commercially available from various sources. It may be possible to obtain or prepare other suitable porous polymeric substrates from, such as, for example, polyvinylidene fluoride or polysulfones. Copolymeric substrates such as, for example, poly(ethylene-co-tetrafluoroethylene) and poly(tetrafluoroethylene-co-hexafluoropropylene), may also be used.
The degree of porosity, pore size and thickness of the substrate used in the composite membrane can be selected to suit the application.
For use of the composite membrane as an electrolyte in an electrochemical fuel cell, the substrate thickness is preferably 10-200 ~Cm, and more preferably 25-50 /cm, the preferable average pore diameter is 0.1-1.0 ~.m, and the preferable porosity is 50-98%, more preferably 75-90%.
- Depending on the application the resultant composite membrane.may be gas permeable or gas impermeable. The loading of the polymeric composition on the substrate can be varied in order to control the porosity of the resultant composite membrane. For fuel cell applications, the composite membrane is preferably substantially gas impermeable, thus the degree of impregnation and . loading is such that the porosity of the composite membrane is reduced essentially to zero.
In a method for preparing composite membranes, the polymeric composition is dissolved in a to solvent, typically an organic solvent, to form a solution. The solvent used will depend, for example, on both the nature of the polymeric composition and the substrate. For impregnation of porous polyolefins with the type of polymeric compositions described herein, suitable solvents include N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and N,N-dimethylacetamide. When polytetrafluoroethylene is the substrate, an alcohol or mixture of alcohols (chosen, for example, from methanol, ethanol and propan-2-ol) is often the preferred solvent. The concentration of the solution will depend on the loading desired, and whether the composite membrane is to be porous or not. For example, if the composite membrane is to be gas permeable a lower concentration is .
generally preferred.
The porous substrate is then impregnated, for example, by constraining the substrate in a frame and dipping or soaking it in the solution. The contact time is dependent on the viscosity and°
percentage solids of the solution. Other techniques known in the art, such as ultrasonication, may be used to facilitate impregnation. Also, multiple impregnations, possibly with different polymeric compositions, may ' be desirable for some applications. The substrate is then removed from the solution and the composite membrane dried preferably in a humidity controlled atmosphere (generally at less than or equal to 2%
relative humidity) at above ambient temperatures.
If the composite membrane includes proton exchange moieties and is to be used in, for example, a proton-exchange membrane fuel cell, it is removed from the frame, treated with 1 M
hydrochloric acid and washed with deionized water prior to use.
The means by which the process described above could be modified for impregnation of non-membrane substrates, and also for a continuous composite membrane manufacturing process will be apparent to those skilled in the art.
In the preparation of composite ion-exchange membranes, the ion-exchange moieties can be:
(l) present in the polymeric composition prior to its impregnation into the substrate; or (ii) introduced post-impregnation through further reaction of the polymeric composition on the substrate; or (iii.) introduced via conversion of precursor groups, present in the polymeric composition, after impregnation.
If the ion-exchange moieties are to be introduced via a post-impregnation conversion or reaction, the substrate needs to selected such that it can withstand the post-impregnation treatment step. For example, in post-impregnation introduction of ion-exchange moieties, the ion-exchange moieties may be introduced into polymeric compositions containing unsubstituted a,b,B-tri-fluorostyrene units (so called "base polymers") via aromatic substitution of at least a portion of those units, after preparation of a composite membrane. For example, pendant unsubstituted phenyl rings in the composite membrane can be conveniently sulfonated (see U.S. Patent 5,422,411) to produce a composite ration-exchange membrane.
Similarly, such pendant unsubstituted phenyl rings may be phosphorylated, carboxylated, quaternary-aminoalkylated or chloromethylated, and further modified to include -CH2PO,H2, -CHsNR,' where R is an alkyl, or -CH2NAr3' (where Ar is a substituted or unsubstituted phenyl group) and other substituents, to provide ration-exchange or anion-exchange composite membranes. Further still, the pendent phenyl moiety may contain a hydroxyl group which can be elaborated by known methods to generate -OSO,H, -OPOZHz and -OPO,HZ ration-exchange sites on the composite membrane.
The approach in which the ion-exchange functionality is introduced post-impregnation via conversion of a precursor using simple post-impregnation procedure, such as hydrolysis, can be advantageous. For example, composite membranes comprising polymers containing sulfonyl fluoride moieties (-SO=F) can be hydrolyzed to generate -SO,H
ration-exchange sites. In a typical hydrolysis reaction, the sulfonyl fluoride is converted to the free sulfonic acid functionality by treatment of the composite membrane with concentrated aqueous alkali metal hydroxide at elevated temperatures.
This and other procedures for the hydrolysis of -SOzF to -SO,H are well-known to those skilled in the art. The latter approach to the introduction of -SO,H moieties offers advantages over sulfonation of a base polymer in the composite membrane. For example, it permits greater control over the ion-s exchange capacity of the resultant composite membrane.
Membranes including sulfonyl fluoride substituted a,i3,f~-trifluorostyrene monomeric units are described in a related application.
Unsupported membranes containing a significant proportion of sulfonyl fluoride substituted cr, f3, 13-trifluorostyrene monomeric units can be very fragile. The mechanical properties of these precursor ion-exchange membranes can be significantly enhanced through incorporation into a porous substrate.
It may be advantageous to introduce ion-exchange moieties after preparation of the composite membranes, as described in (ii) and (iii) above. For example, in electrochemical applications where the preferred substrates are typically hydrophobic, the preparation of a composite membrane by first impregnating the substrate with a solution of a non-ionic polymer which is also essentially hydrophobic may lead to more facile and improved impregnation.
The following examples are for purposes of illustration and are not intended to limit the invention. Examples 1-3 describe the preparation of composite ion-exchange membranes in which porous, high density polyethylene is used as the substrate. Examples 4 and 5 describe the preparation of composite ion-exchange membranes in which expanded polytetrafluoroethylene is used as .. .~h, ; :--;;~ r ~°.:_~.*~..~
.. _, _ ' , ~,.~ , , ; , , , > >
_ , . . , , ., , ., the porous substrate. In Examples 1, 2, 4 and 5 the ion-exchange moieties were present in the polymeric composition prior to its impregnation into the substrate. In Example 3 the ion-exchange moiety was generated by hydrolysis of sulfonyl fluoride moieties after preparation of the composite membrane. Example 6 sets forth the procedure used to test the composite ion-exchange membranes, prepared as described in Examples 1-5, as membrane electrolytes in an electrochemical fuel cell.
Example 1 Porous polyethylene impregnated with a sulfonated copolymer of a,i3,i3-tra.fluorostyrene and m tri f luoromethyl -cx, i3, f3- tri f luoro s tyrene (Composite Membrane A) The substrate,.a 22.9 cm x 22.9 cm piece of high density polyethylene (obtained from 3M, product ID #43-9100-6770-l, 81% porosity, approximately 50 micrometer) was clamped in a frame and immersed in a N,N-dimethylformamide solution (7o w/w) of a sulfonated copolymer of a,i3,f3-trifluorostyrene and m-trifluoromethyl-a,i3,i3-trifluorostyrene (equivalent weight 384 g/mol) in a glass container. The container was covered to exclude moisture and particulate contaminants. After 1 hour excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2°s relative humidity, at 50°C. After approximately 3 hours the dry composite membrane, now opaque, was a mechanically strong flexible film.
On immersion in 1 M hydrochloric acid (to ~,~ W ~~: ~, s . i~..~~~u .. ~ ._ ..
,~~.. , , .; , ., . , , .. , , . . , . , . , , ;
, . . . . , , , ., ensure protonation of all the sulfonic acid moieties), and subsequent washing with deionized water, the composite membrane once again became transparent. The wet composite membrane (50-60 micrometer thick) was also strong and flexible.
Example 2 Porous polyethylene impregnated with sulfonated poly-a, i3, f3-trifluorostyrene (Composite Membrane B) The substrate, a 25.4 cm x 25.4 cm piece of high density polyethylene (from 3M, product ID #43-9100-6770-1, 81% porosity, 50 micrometer) was clamped in a frame and immersed in a N,N-dimethylformamide solution (7o w/w) of a sulfonated polymer of a,f3,f3-trifluorostyrene (equivalent weight 430 g/mol) in a glass container. The container was covered to exclude moisture and particulate contaminants. After 2 hours excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2%
relative humidity, at 50°C. After approximately 3 hours the dry composite membrane, now opaque, was a mechanically strong flexible film, in contrast to the analogous unsupported membrane which would be extremely fragile in the dry state. On immersion in 1 M hydrochloric acid (to ensure protonation of all the sulfonic acid moieties), and subsequent washing with deionized water, the composite membrane once again became transparent. The wet composite membrane (approximately 100 micrometer thick)was also strong and flexible.
At~~r~~~~ sr~~~r ., , 1 . . ~ . . 7 n ~ , o , .. , n ~ ' -> > . , . o n . , , ~ y . 7 7 Examr~le 3 Porous polyethylene impregnated with a copolymer of a, i3, f~-trifluorostyrene, m-trifluoromethyl-a,f3,f3-trifluorostyrene and p-sulfonyl fluoride-cx,i3, f3-trifluorostyrene, and subsequent hydrolysis (Composite Membrane C) The substrate, a 25.4 cm x 25.4 cm piece of high density polyethylene (from 3M, product ID #43 9100-6770-I, 81% porosity, approximately 50 micrometer) was clamped in a frame and immersed in a N,N-dimethylformamide solution (5% w/w) of a copolymer of a, f~, f3-trifluorostyrene, m-trifluoromethyl-a, f3, i3-trifluorostyrene and p-sulfonyl fluoride-a, f3, f3-trifluorostyrene (equivalent weight 480 g/mol after hydrolysis) in a glass container. The container was covered to exclude moisture and particulate contaminants. After 2 hours excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2% relative humidity, at 50°C. After approximately 3 hours the dry composite membrane was a mechanically strong flexible film.
The sulfonyl fluoride moieties were hydrolyzed by treatment of the composite membrane with potassium hydroxide solution (approximately 6% w/w, in 5:1 w/w water:l-methoxy-2-propanol) at 60°C (see U.S. Patent No. 5,310,765). The composite membrane was then immersed in 1 M hydrochloric acid to ensure protonation of all the sulfonic acid moieties in the composite membrane, and subsequently washed with deionized water. The wet, hydrolyzed composite membrane (50-70 micrometer thick) was also AA~9ShiD~D S'~i~ET
.,, . , ._ , ' ' _., ., .., strong and flexible.
Example 4 Expanded polytetrafluoroethylene impregnated with a sulfonated copolymer of a,i3,i3-trifluorostyrene and m-trifluoromethyl-a,i3,i3-trifluorostyrene (Composite Membrane D) The substrate, an 20.3 cm x 20.3 cm piece of expanded polytetrafluoroethylene (Tetratex° obtained from Tetratec Corporation, 80-90% porosity, approximately 38 micrometer, 0.45 micrometer pore size) was clamped in a frame and immersed in a methanol/propan-2-of (3:1) solution (approximately
Composite ion-exchange membranes prepared by impregnating commercially available porous polytetrafluoroethylene film (Gore-tex~) with Nafion~, a perfluorosulfonate ionomer, have been described in Journal of the Electrochemical Society, Vol. 132, pp. 5I4-515 (1985). The major goal in the study was to develop a composite membrane with the desirable chemical and mechanical features of Nafion~, but which could be produced at low cost. Indeed, based on the polymer loadings necessary to produce these composite membranes, ' CA 02240495 1998-06-16 ,_ ..
they are a low cost alternative to the costly perfluorosulfonic acid membranes. As indicated above, however, these perfluorosulfonate ionomers are known to form membranes suitable for use in electrochemical applications without the use of a substrate.
It has been discovered that polymers which have a tendency to become brittle in the dehydrated state can be rendered mechanically stable, even in the fully dehydrated state, by impregnation into suitable substrates.
Furthermore, it has been discovered that even polymers which are poor film formers, or polymers which form films with mechanical properties and dimensional stability which would preclude their use in electrochemical and other applications, can be made into composite membranes through incorporation into a suitable substrate. The resulting composite membranes have the-desired physical properties for use in a wide range of applications.
Summary Of The Invention A composite membrane comprises a flexible porous polymeric sheet material impregnated with a polymer comprising fragments of formula (I):
-E CF=-CTS-~CF2-CF- n --f CFZ-Ct~z C~--EEC--~CFiZ-CH-)"' P Q ~ s 2 5 \ ~ \\~ ~ ~~I w,~ . ( I ) x M Ax Z
wherein m, n, p, q, r, and s are zero or an integer greater than zero, and at least one of m, n, p and q is an integer greater than zero, whereby the polymer comprises at least one type of substituted AMENDED St~~ET
,.. . .., ., ., - , or unsubstituted cx, f3, f3-trifluorostyrene monomeric unit. The thickness of the flexible polymeric sheet material into which the polymer of formula (I) is impregnated is preferably 10-200 ~.m.
In the above formula:
X is selected from the group consisting of S02F, S03H, P02H2, P03Hz, CHaP03Hz, COON, OS03H, OP02H2, OP03H~, OArS03H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3~ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
A1 and A2 are selected from the group consisting of halogens, CxHYFz (where x is an integer greater than zero and y+z = 2x+1), CF=CF2, CN, NOZ and OH, O-R (where R is selected from the group consisting of alkyls and perfluoroalkyls and aryls), and when m is an integer greater than zero, the group from which A1 and Aa are selected further consists of SOZF, S03H, POzH2, P03H2, CHaP03H2, COOH, OS03H, OP02H2, OP03Ha, OArS03H where Ar is an aryl, NR3~ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
Z is hydrogen or a non-hydrogen substituent whereby, when s is an integer greater than zero, the polymer further comprises styrene or substituted styrene monomeric units;
E is selected from the group consisting of CHa-CHZ, CHz-CHF, CFH-CFH, CFa-CHa, CFa-CHF, CFa-CFa whereby, when r is an integer greater than zero, the polymer further comprises ethylene, partially fluorinated ethylene or tetrafluoroethylene -. hAA~ND~D W~t~' monomeric units.
In some embodiments of the above composite membrane, at least p is an integer greater than zero, whereby the polymer comprises at least one type of "A"-substituted a,f3,i3-trifluorostyrene monomeric unit.
In other embodiments of the above composite membrane, at least m is an integer greater than zero, whereby the polymer comprises at least one type of "X"-substituted a,f3,f3-trifluorostyrene monomeric unit. In preferred embodiments, at least one of n, p and q is also an integer greater than zero, whereby the polymer comprises more than one type of a,f3,f3-trifluorostyrene-based monomeric unit.
In other preferred embodiments, at least one of p and q, as well as m, is an integer greater than zero, whereby the polymer comprises more than one type of substituted cx, f3, f3-trifluorostyrene monomeric unit.
A preferred X-substituent is SOaF, whereby the polymer comprises a,f3,f3-trifluorostyrene sulfonyl fluoride monomeric units. Again, at least one of n, p and q may also be an integer greater than zero.
In particularly preferred embodiments, both n and p are integers greater than zero, and AL is selected from the group consisting of fluorine, CF3 and para-phenoxy.
Another preferred X-substituent is S03H.
Again, n may also be an integer greater than zero, and at least one of p and q may also be an integer greater than zero. In particularly preferred embodiments, both n and p are integers greater than zero, and A1 is selected from the group consisting of fluorine, CF3 and para-phenoxy.
r l~~v~~'~U~ii 3ri~~~
CA 02240495 1998-06-16 ,_ __ _ g _ In still further embodiments of the above composite membrane both m and p are integers greater than zero, and A1 is selected from the group consisting of S02F, S03H, POzHz, P03H2, CH~PO,Hz, COOH, OS03H, OP02Ha, OP03H2, OArS03H where Ar is an aryl, NR3~ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH~NR,+
(where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls). In these embodiments the polymer comprises more than one type of ion-exchange moiety.
In the composite membranes described above, preferred flexible polymeric sheet materials include those comprising polytetrafluorethylene, a polyolefin or a partially fluorinated polyolefin.
Flexible polyermic sheet materials comprising a polymer selected from the group consisting of polyethylene, polypropylene, polyvinylidene fluoride, poly(ethylene-co-tetrafluoroethylene) and poly(tetrafluoroethylene-co-hexafluoropropylene) are particularly preferred for certain applicatiori.s.
Expanded polytetrafluoroethylene is another example of a preferred substrate.
For certain applications, such as fuel cell applications, the composite membrane is preferably substantially gas impermeable.
In the aspects and embodiments described above, the polymeric compositions can consist essentially of the described monomeric units.
In the aspects and embodiments described above, the A1, A2, A3 substituents may be further elaborated by known means such as, for example, by hydrolysis of the CN group to form COOH or by reduction with common reducing agents (such as, for example, Raney AN1END~D S~i~.GT
" ..
' o -, , , , , . , , , , , ., ,, , , " " , ."
nickel) to form a primary amine, thereby transforming the A1, Aa and A3 substituents into ion-exchange moieties. The resulting polymeric composition may thus comprise one or more type of ion-exchange moiety, and may also comprise both cation-exchange and anion-exchange moieties.
The term "monomeric unit" as used herein indicates that the polymeric composition contains the described fragment or unit, and is obtained by a polymerization reaction involving the corresponding unsaturated monomer.
The substituents on the aromatic rings (including, for example, A1, A2, A3, X, B and D) may each be located in the ortho, meta or para positions, as indicated in the formulas wherein the chemical bond drawn for the substituents intersects the aromatic ring. In preferred aspects of the described embodiments, the substituents are in the meta or para positions.
As used herein, the term "aryl" refers to a substituted or unsubstituted phenyl group. The formula CXH~,FZ (where x is an integer greater than zero and y+z = 2x+1) is used to indicate alkyl, perfluoroalkyl or partially fluorinated alkyl groups.
In accordance with convention in the art, the above chemical formulas for polymeric compositions containing more than two monomeric units (where at least three of m, n, p and q are greater than zero) are intended to indicate that the monomeric units are present in the polymeric composition, but are not limited to the particular order in which the monomeric units are set forth in each general formula. For example, random linear copolymers, A~i~~iDED 5~~~'f . , , , ;
. . , , , . , " . .., ,, :, alternating copolymers and linear block copolymers, formed from the indicated monomeric units, are contemplated.
ARAEPiDED SHEFt y _ , - , ,., , , , , ; ., , - , , , _. _, ~:., "
Brief Descri-ption Of The Drawings FIG. 1 is a plot of cell voltage as a function of current density (expressed in milliamperes per square centimeter) in an electrochemical fuel cell employing a composite membrane of porous polyethylene impregnated with a sulfonated copolymer of a,f3,13-trifluorostyrene and m-trifluoromethyl-a,i3,f~-trifluorostyrene, as the proton exchange membrane.
FIG. 2 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane, prepared by impregnation of porous polyethylene with sulfonated poly-a, i3, f3-trifluorostyrene, as the proton exchange membrane.
FIG. 3 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane, prepared by impregnation of porous polyethylene with a copolymer of a, f3, i3-trifluorostyrene, m-trifluoromethyl-a, f3, f~-trifluorostyrene and p-sulfonyl fluoride-a,f3,f3-trifluorostyrene, and subsequent hydrolysis, as the proton exchange membrane.
a~~rin~.o s~~FT
' . . , ~ - . . :.' . : , ; ; ; , ,.,.; ~ ...
. . , , ., . , , ., FIG. 4 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane of expanded polytetrafluoroethylene impregnated with a sulfonated copolymer of a, fS, f3-trifluorostyrene and m-trifluoromethyl-a,f3,i3-trifluorostyrene, as the proton exchange membrane.
FIG. 5 is a plot of cell voltage as a function of current density in an electrochemical fuel cell employing a composite membrane of expanded polytetrafluoroethylene impregnated with a low equivalent weight sulfonated copolymer of a,i3,i3-trifluorostyrene and m-trifluoromethyl-a, i3, f3-tri-fluorostyrene, as the proton exchange membrane.
Detailed Description Of The Preferred Embodiments Methods for preparing the polymeric compositions described herein are described in the related applications or will be apparent to those skilled in the art.
The preferred substrate material is dependent on the application in which the composite membrane is to be used. The substrate material preferably has good mechanical properties, is chemically and thermally stable in the environment in which the composite membrane is to be used, is tolerant of the solvent used for impregnation, and in most applications is preferably flexible. Preferred substrates for electrochemical applications are porous polymeric materials. Preferred polymeric materials are, for example, ~~riE'~1~'~J S!-~~~?' hydrocarbons such as porous polyolefins, especially polyethylene and pclypropylene. In some applications, a perfluorinated polymeric substrate may be preferred, for example, a preferred substrate material, when the composite membrane is to be used in an electrochemical fuel cell, is porous polytetrafluoroethylene, also known as expanded polytetrafluoraethylene. Porous polyolefins and polytetrafluoroethylenes typically have excellent mechanical strength, flexibility and do not swell in water. Polytetrafluoroethylene offers additional advantages in that it is also chemically inert, and porous polytetrafluoroethylene films with different characteristics are commercially available from various sources. It may be possible to obtain or prepare other suitable porous polymeric substrates from, such as, for example, polyvinylidene fluoride or polysulfones. Copolymeric substrates such as, for example, poly(ethylene-co-tetrafluoroethylene) and poly(tetrafluoroethylene-co-hexafluoropropylene), may also be used.
The degree of porosity, pore size and thickness of the substrate used in the composite membrane can be selected to suit the application.
For use of the composite membrane as an electrolyte in an electrochemical fuel cell, the substrate thickness is preferably 10-200 ~Cm, and more preferably 25-50 /cm, the preferable average pore diameter is 0.1-1.0 ~.m, and the preferable porosity is 50-98%, more preferably 75-90%.
- Depending on the application the resultant composite membrane.may be gas permeable or gas impermeable. The loading of the polymeric composition on the substrate can be varied in order to control the porosity of the resultant composite membrane. For fuel cell applications, the composite membrane is preferably substantially gas impermeable, thus the degree of impregnation and . loading is such that the porosity of the composite membrane is reduced essentially to zero.
In a method for preparing composite membranes, the polymeric composition is dissolved in a to solvent, typically an organic solvent, to form a solution. The solvent used will depend, for example, on both the nature of the polymeric composition and the substrate. For impregnation of porous polyolefins with the type of polymeric compositions described herein, suitable solvents include N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and N,N-dimethylacetamide. When polytetrafluoroethylene is the substrate, an alcohol or mixture of alcohols (chosen, for example, from methanol, ethanol and propan-2-ol) is often the preferred solvent. The concentration of the solution will depend on the loading desired, and whether the composite membrane is to be porous or not. For example, if the composite membrane is to be gas permeable a lower concentration is .
generally preferred.
The porous substrate is then impregnated, for example, by constraining the substrate in a frame and dipping or soaking it in the solution. The contact time is dependent on the viscosity and°
percentage solids of the solution. Other techniques known in the art, such as ultrasonication, may be used to facilitate impregnation. Also, multiple impregnations, possibly with different polymeric compositions, may ' be desirable for some applications. The substrate is then removed from the solution and the composite membrane dried preferably in a humidity controlled atmosphere (generally at less than or equal to 2%
relative humidity) at above ambient temperatures.
If the composite membrane includes proton exchange moieties and is to be used in, for example, a proton-exchange membrane fuel cell, it is removed from the frame, treated with 1 M
hydrochloric acid and washed with deionized water prior to use.
The means by which the process described above could be modified for impregnation of non-membrane substrates, and also for a continuous composite membrane manufacturing process will be apparent to those skilled in the art.
In the preparation of composite ion-exchange membranes, the ion-exchange moieties can be:
(l) present in the polymeric composition prior to its impregnation into the substrate; or (ii) introduced post-impregnation through further reaction of the polymeric composition on the substrate; or (iii.) introduced via conversion of precursor groups, present in the polymeric composition, after impregnation.
If the ion-exchange moieties are to be introduced via a post-impregnation conversion or reaction, the substrate needs to selected such that it can withstand the post-impregnation treatment step. For example, in post-impregnation introduction of ion-exchange moieties, the ion-exchange moieties may be introduced into polymeric compositions containing unsubstituted a,b,B-tri-fluorostyrene units (so called "base polymers") via aromatic substitution of at least a portion of those units, after preparation of a composite membrane. For example, pendant unsubstituted phenyl rings in the composite membrane can be conveniently sulfonated (see U.S. Patent 5,422,411) to produce a composite ration-exchange membrane.
Similarly, such pendant unsubstituted phenyl rings may be phosphorylated, carboxylated, quaternary-aminoalkylated or chloromethylated, and further modified to include -CH2PO,H2, -CHsNR,' where R is an alkyl, or -CH2NAr3' (where Ar is a substituted or unsubstituted phenyl group) and other substituents, to provide ration-exchange or anion-exchange composite membranes. Further still, the pendent phenyl moiety may contain a hydroxyl group which can be elaborated by known methods to generate -OSO,H, -OPOZHz and -OPO,HZ ration-exchange sites on the composite membrane.
The approach in which the ion-exchange functionality is introduced post-impregnation via conversion of a precursor using simple post-impregnation procedure, such as hydrolysis, can be advantageous. For example, composite membranes comprising polymers containing sulfonyl fluoride moieties (-SO=F) can be hydrolyzed to generate -SO,H
ration-exchange sites. In a typical hydrolysis reaction, the sulfonyl fluoride is converted to the free sulfonic acid functionality by treatment of the composite membrane with concentrated aqueous alkali metal hydroxide at elevated temperatures.
This and other procedures for the hydrolysis of -SOzF to -SO,H are well-known to those skilled in the art. The latter approach to the introduction of -SO,H moieties offers advantages over sulfonation of a base polymer in the composite membrane. For example, it permits greater control over the ion-s exchange capacity of the resultant composite membrane.
Membranes including sulfonyl fluoride substituted a,i3,f~-trifluorostyrene monomeric units are described in a related application.
Unsupported membranes containing a significant proportion of sulfonyl fluoride substituted cr, f3, 13-trifluorostyrene monomeric units can be very fragile. The mechanical properties of these precursor ion-exchange membranes can be significantly enhanced through incorporation into a porous substrate.
It may be advantageous to introduce ion-exchange moieties after preparation of the composite membranes, as described in (ii) and (iii) above. For example, in electrochemical applications where the preferred substrates are typically hydrophobic, the preparation of a composite membrane by first impregnating the substrate with a solution of a non-ionic polymer which is also essentially hydrophobic may lead to more facile and improved impregnation.
The following examples are for purposes of illustration and are not intended to limit the invention. Examples 1-3 describe the preparation of composite ion-exchange membranes in which porous, high density polyethylene is used as the substrate. Examples 4 and 5 describe the preparation of composite ion-exchange membranes in which expanded polytetrafluoroethylene is used as .. .~h, ; :--;;~ r ~°.:_~.*~..~
.. _, _ ' , ~,.~ , , ; , , , > >
_ , . . , , ., , ., the porous substrate. In Examples 1, 2, 4 and 5 the ion-exchange moieties were present in the polymeric composition prior to its impregnation into the substrate. In Example 3 the ion-exchange moiety was generated by hydrolysis of sulfonyl fluoride moieties after preparation of the composite membrane. Example 6 sets forth the procedure used to test the composite ion-exchange membranes, prepared as described in Examples 1-5, as membrane electrolytes in an electrochemical fuel cell.
Example 1 Porous polyethylene impregnated with a sulfonated copolymer of a,i3,i3-tra.fluorostyrene and m tri f luoromethyl -cx, i3, f3- tri f luoro s tyrene (Composite Membrane A) The substrate,.a 22.9 cm x 22.9 cm piece of high density polyethylene (obtained from 3M, product ID #43-9100-6770-l, 81% porosity, approximately 50 micrometer) was clamped in a frame and immersed in a N,N-dimethylformamide solution (7o w/w) of a sulfonated copolymer of a,i3,f3-trifluorostyrene and m-trifluoromethyl-a,i3,i3-trifluorostyrene (equivalent weight 384 g/mol) in a glass container. The container was covered to exclude moisture and particulate contaminants. After 1 hour excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2°s relative humidity, at 50°C. After approximately 3 hours the dry composite membrane, now opaque, was a mechanically strong flexible film.
On immersion in 1 M hydrochloric acid (to ~,~ W ~~: ~, s . i~..~~~u .. ~ ._ ..
,~~.. , , .; , ., . , , .. , , . . , . , . , , ;
, . . . . , , , ., ensure protonation of all the sulfonic acid moieties), and subsequent washing with deionized water, the composite membrane once again became transparent. The wet composite membrane (50-60 micrometer thick) was also strong and flexible.
Example 2 Porous polyethylene impregnated with sulfonated poly-a, i3, f3-trifluorostyrene (Composite Membrane B) The substrate, a 25.4 cm x 25.4 cm piece of high density polyethylene (from 3M, product ID #43-9100-6770-1, 81% porosity, 50 micrometer) was clamped in a frame and immersed in a N,N-dimethylformamide solution (7o w/w) of a sulfonated polymer of a,f3,f3-trifluorostyrene (equivalent weight 430 g/mol) in a glass container. The container was covered to exclude moisture and particulate contaminants. After 2 hours excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2%
relative humidity, at 50°C. After approximately 3 hours the dry composite membrane, now opaque, was a mechanically strong flexible film, in contrast to the analogous unsupported membrane which would be extremely fragile in the dry state. On immersion in 1 M hydrochloric acid (to ensure protonation of all the sulfonic acid moieties), and subsequent washing with deionized water, the composite membrane once again became transparent. The wet composite membrane (approximately 100 micrometer thick)was also strong and flexible.
At~~r~~~~ sr~~~r ., , 1 . . ~ . . 7 n ~ , o , .. , n ~ ' -> > . , . o n . , , ~ y . 7 7 Examr~le 3 Porous polyethylene impregnated with a copolymer of a, i3, f~-trifluorostyrene, m-trifluoromethyl-a,f3,f3-trifluorostyrene and p-sulfonyl fluoride-cx,i3, f3-trifluorostyrene, and subsequent hydrolysis (Composite Membrane C) The substrate, a 25.4 cm x 25.4 cm piece of high density polyethylene (from 3M, product ID #43 9100-6770-I, 81% porosity, approximately 50 micrometer) was clamped in a frame and immersed in a N,N-dimethylformamide solution (5% w/w) of a copolymer of a, f~, f3-trifluorostyrene, m-trifluoromethyl-a, f3, i3-trifluorostyrene and p-sulfonyl fluoride-a, f3, f3-trifluorostyrene (equivalent weight 480 g/mol after hydrolysis) in a glass container. The container was covered to exclude moisture and particulate contaminants. After 2 hours excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2% relative humidity, at 50°C. After approximately 3 hours the dry composite membrane was a mechanically strong flexible film.
The sulfonyl fluoride moieties were hydrolyzed by treatment of the composite membrane with potassium hydroxide solution (approximately 6% w/w, in 5:1 w/w water:l-methoxy-2-propanol) at 60°C (see U.S. Patent No. 5,310,765). The composite membrane was then immersed in 1 M hydrochloric acid to ensure protonation of all the sulfonic acid moieties in the composite membrane, and subsequently washed with deionized water. The wet, hydrolyzed composite membrane (50-70 micrometer thick) was also AA~9ShiD~D S'~i~ET
.,, . , ._ , ' ' _., ., .., strong and flexible.
Example 4 Expanded polytetrafluoroethylene impregnated with a sulfonated copolymer of a,i3,i3-trifluorostyrene and m-trifluoromethyl-a,i3,i3-trifluorostyrene (Composite Membrane D) The substrate, an 20.3 cm x 20.3 cm piece of expanded polytetrafluoroethylene (Tetratex° obtained from Tetratec Corporation, 80-90% porosity, approximately 38 micrometer, 0.45 micrometer pore size) was clamped in a frame and immersed in a methanol/propan-2-of (3:1) solution (approximately
5% w/v) of a sulfonated copolymer of a, f3, f3-tri-fluorostyrene and m-trifluoromethyl-a, f3, f3-tri-fluorostyrene (equivalent weight 412 g/mol) in a glass container. The container was covered to exclude moisture and particulate contaminants.
After 18 hours excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2% relative humidity, at 50°C. After approximately 1.5 hours the dry composite membrane, now opaque, was a mechanically strong flexible film. On immersion in 1 M hydrochloric acid (to ensure protonation of all the sulfonic acid moieties), and subsequent washing with deionized water, the composite membrane once again became transparent. The wet composite membrane (50-60 micrometer thick) was also strong and flexible.
ANIEPiDCD S1-ltE~
Ex-ample 5 Expanded polytetrafluoroethylene impregnated v~rith a sulfonated copolymer of a, i~, i3-trifluorostyrene and m-trifluoromethyl- a, f3, i3-trifluorostyrene (Composite Membrane E) The composite membrane was prepared as des>cribed in Example 4, using a sulfonated copolymer of a, f~, i3--trifluorostyrene and m-trifluoromethyl- a, f3, f3-trifluorostyrene with a lower equivalent weight (362 g/mol) and impregnating the substrate for 30 minutes. The resulting dry composite membrane was a mechanically strong flexible film, in contrast to the analogous unsupported membrane which, at~ t.his low equivalent weight, is extremely fragile and readily reduced to a powder on handling.
The wet composite membrane (25-40 micrometer thick) was also strong and flexible, again in contrast to the unsupported membrane which is fragile and dimensionally unstable, and is therefore of limited use in electrochemical fuel cells.
Exa~le__ 6 Each of the composite membranes prepared as described above was bonded to two catalyzed carbon fiber paper electrodes at room temperature under 3,402 kilograms of pressure. Each membrane electrode assembly was tested in a Ballard Mark IV single cell fuel cell (see U.S. Patent No's. 4,988,583; 5,108,849; 5,170,124;
5, 176, 966 and 5, 200, 278) . The fol.lowir~c~ operating conditions applied to the fuel cell in which the membranes were tested:
Temperature: 70°C
Reactant inlet pressure:
165 kiloNewtons/meter squared for both ai.r and hydrogen Reactant stoi.chiometries:
2.0 air and 1.15 hydrogen.
The membrane electrode assemblies incorporating the composite membranes were tested for 200-14~~0 hours, depending on availability of testing equipment.
FIGS. 1-5 are polarization plots of voltage as a function of current density for composite membranes A-~, respectively, employed in membrane electrode assemblies :i.n the electrochemical Fuel cell. The data is comparable to data reported for unsupported membrane: in related ~J. S. Fatent No. 5, 422, 411 .
After 18 hours excess polymer solution was removed and the transparent, wetted substrate was placed to dry in a chamber at approximately 2% relative humidity, at 50°C. After approximately 1.5 hours the dry composite membrane, now opaque, was a mechanically strong flexible film. On immersion in 1 M hydrochloric acid (to ensure protonation of all the sulfonic acid moieties), and subsequent washing with deionized water, the composite membrane once again became transparent. The wet composite membrane (50-60 micrometer thick) was also strong and flexible.
ANIEPiDCD S1-ltE~
Ex-ample 5 Expanded polytetrafluoroethylene impregnated v~rith a sulfonated copolymer of a, i~, i3-trifluorostyrene and m-trifluoromethyl- a, f3, i3-trifluorostyrene (Composite Membrane E) The composite membrane was prepared as des>cribed in Example 4, using a sulfonated copolymer of a, f~, i3--trifluorostyrene and m-trifluoromethyl- a, f3, f3-trifluorostyrene with a lower equivalent weight (362 g/mol) and impregnating the substrate for 30 minutes. The resulting dry composite membrane was a mechanically strong flexible film, in contrast to the analogous unsupported membrane which, at~ t.his low equivalent weight, is extremely fragile and readily reduced to a powder on handling.
The wet composite membrane (25-40 micrometer thick) was also strong and flexible, again in contrast to the unsupported membrane which is fragile and dimensionally unstable, and is therefore of limited use in electrochemical fuel cells.
Exa~le__ 6 Each of the composite membranes prepared as described above was bonded to two catalyzed carbon fiber paper electrodes at room temperature under 3,402 kilograms of pressure. Each membrane electrode assembly was tested in a Ballard Mark IV single cell fuel cell (see U.S. Patent No's. 4,988,583; 5,108,849; 5,170,124;
5, 176, 966 and 5, 200, 278) . The fol.lowir~c~ operating conditions applied to the fuel cell in which the membranes were tested:
Temperature: 70°C
Reactant inlet pressure:
165 kiloNewtons/meter squared for both ai.r and hydrogen Reactant stoi.chiometries:
2.0 air and 1.15 hydrogen.
The membrane electrode assemblies incorporating the composite membranes were tested for 200-14~~0 hours, depending on availability of testing equipment.
FIGS. 1-5 are polarization plots of voltage as a function of current density for composite membranes A-~, respectively, employed in membrane electrode assemblies :i.n the electrochemical Fuel cell. The data is comparable to data reported for unsupported membrane: in related ~J. S. Fatent No. 5, 422, 411 .
Claims (21)
1. A composite membrane comprising a flexible porous polymeric sheet material having a thickness of 10-200 µm impregnated with a polymer comprising fragments of formula (I):
wherein m, n, p, q, r, and s are zero or an integer greater than zero, and at least one of m, n, p and q is an integer greater than zero;
X is selected from the group consisting of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
A1 and A2 are selected from the group consisting of halogens, C x H y F z (where x is an integer greater than zero and y+z = 2x+1), CF=CF2, CN, NO2 and OH, O-R (where R is selected from the group consisting of alkyls and perfluoroalkyls and aryls), and when m is an integer greater than zero, the group from which A1 and A2 are selected further consists of SO2F, SO3H, PO2H2 , PO3H2 , CH2PO3H2 , COOH, OSO3H, OPO2H2 , OPO3H2 , OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
Z is selected from the group consisting of hydrogen and a non-hydrogen substituent; and E is selected from the group consisting of CH2-CH2, CH2-CHF, CFH-CFH, CF2-CH2, CF2-CHF, CF2-CF2 .
wherein m, n, p, q, r, and s are zero or an integer greater than zero, and at least one of m, n, p and q is an integer greater than zero;
X is selected from the group consisting of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
A1 and A2 are selected from the group consisting of halogens, C x H y F z (where x is an integer greater than zero and y+z = 2x+1), CF=CF2, CN, NO2 and OH, O-R (where R is selected from the group consisting of alkyls and perfluoroalkyls and aryls), and when m is an integer greater than zero, the group from which A1 and A2 are selected further consists of SO2F, SO3H, PO2H2 , PO3H2 , CH2PO3H2 , COOH, OSO3H, OPO2H2 , OPO3H2 , OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
Z is selected from the group consisting of hydrogen and a non-hydrogen substituent; and E is selected from the group consisting of CH2-CH2, CH2-CHF, CFH-CFH, CF2-CH2, CF2-CHF, CF2-CF2 .
2. The composite membrane of claim 1 wherein p is an integer greater than zero.
3. The composite membrane of claim 1 wherein m is an integer greater than zero.
4. The composite membrane of claim 3 wherein at least one of n, p and q is an integer greater than zero.
5. The composite membrane of claim 3 wherein at least one of p and q is an integer greater than zero.
6. The composite membrane of claim 3 wherein X is SO2F.
7. The composite membrane of claim 6 wherein at least one of n, p and q is an integer greater than zero.
8. The composite membrane of claim 6 wherein n and p are integers greater than zero, and A1 is selected from the group consisting of fluorine, CF3 and para-phenoxy.
9. The composite membrane of claim 3 wherein X is SO3H and n is an integer greater than zero.
10. The composite membrane of claim 9 wherein at least one of p and q is an integer greater than zero.
11. The composite membrane of claim 10 wherein p is an integer greater than zero, and A1 is selected from the group consisting of fluorine, CF3 and para-phenoxy.
12. The composite membrane of claim 3 wherein p is an integer greater than zero, and A1 is selected from the group consisting of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls).
13. The composite membrane of claim 1 wherein said porous polymeric sheet material comprises polytetrafluorethylene.
14. The composite membrane of claim 1 wherein said porous polymeric sheet material comprises a polyolefin.
7.5. The composite membrane of claim 1 wherein said porous polymeric sheet material comprises a partially fluorinated polyolefin.
16. The composite membrane of claim 1 wherein said porous polymeric sheet material comprises a polymer selected from the group consisting of polyethylene, polypropylene, polyvinylidene fluoride, poly(ethylene-co-tetrafluoroethylene) and poly(tetrafluoroethylene-co-hexafluoropropylene).
17. The composite membrane as in any of claims 1-13, wherein said flexible porous polymeric sheet material is expanded polytetrafluoroethylene.
18. The composite membrane as in any of claims 1-16 wherein said composite membrane is substantially gas impermeable.
19. A composite membrane comprising a flexible porous polymeric sheet material having a thickness of 10-200 µm impregnated with a polymer consisting essentially of fragments of formula (I):
wherein m, n, p, q, r, and s are zero or an integer greater than zero, and at least one of m, n, p and q is an integer greater than zero;
X is selected from the group consisting of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
A1 and A2 are selected from the group consisting of halogens, C x H y F z (where x is an integer greater than zero and y+z = 2x+1), CF=CF2, CN, NO2 and OH, O-R (where R is selected from the group consisting of alkyls and perfluoroalkyls and aryls), and when m is an integer greater than zero, the group from which A1 and A2 are selected further consists of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
Z is selected from the group consisting of hydrogen and a non-hydrogen substituent; and E is selected from the group consisting of CH2-CH2, CH2-CHF, CFH-CFH, CF2-CH2, CF2-CHF, CF2-CF2.
wherein m, n, p, q, r, and s are zero or an integer greater than zero, and at least one of m, n, p and q is an integer greater than zero;
X is selected from the group consisting of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
A1 and A2 are selected from the group consisting of halogens, C x H y F z (where x is an integer greater than zero and y+z = 2x+1), CF=CF2, CN, NO2 and OH, O-R (where R is selected from the group consisting of alkyls and perfluoroalkyls and aryls), and when m is an integer greater than zero, the group from which A1 and A2 are selected further consists of SO2F, SO3H, PO2H2, PO3H2, CH2PO3H2, COOH, OSO3H, OPO2H2, OPO3H2, OArSO3H where Ar is an aryl, NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls) and CH2NR3+ (where R is selected from the group consisting of alkyls, perfluoroalkyls and aryls);
Z is selected from the group consisting of hydrogen and a non-hydrogen substituent; and E is selected from the group consisting of CH2-CH2, CH2-CHF, CFH-CFH, CF2-CH2, CF2-CHF, CF2-CF2.
20. A membrane electrode assembly comprising a composite membrane of claim 1, wherein said composite membrane is a substantially gas impermeable ion-exchange membrane.
21. An electrochemical fuel cell comprising a composite membrane of claim 1, wherein said composite membrane is a substantially gas impermeable ion-exchange membrane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/583,638 | 1996-01-05 | ||
| US08/583,638 US5834523A (en) | 1993-09-21 | 1996-01-05 | Substituted α,β,β-trifluorostyrene-based composite membranes |
| PCT/CA1997/000003 WO1997025369A1 (en) | 1996-01-05 | 1997-01-03 | α,β,β-TRIFLUOROSTYRENE-BASED AND SUBSTITUTED α,β,β-TRIFLUOROSTYRENE-BASED COMPOSITE MEMBRANES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2240495A1 CA2240495A1 (en) | 1997-07-17 |
| CA2240495C true CA2240495C (en) | 2003-04-01 |
Family
ID=24333969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002240495A Expired - Fee Related CA2240495C (en) | 1996-01-05 | 1997-01-03 | .alpha.,.beta.,.beta.-trifluorostyrene-based and substituted .alpha.,.beta.,.beta.-trifluorostyrene-based composite membranes |
Country Status (8)
| Country | Link |
|---|---|
| US (5) | US5834523A (en) |
| EP (1) | EP0882088B1 (en) |
| JP (1) | JP2000502625A (en) |
| AT (1) | ATE194366T1 (en) |
| AU (1) | AU704923B2 (en) |
| CA (1) | CA2240495C (en) |
| DE (1) | DE69702442T2 (en) |
| WO (1) | WO1997025369A1 (en) |
Families Citing this family (94)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834523A (en) * | 1993-09-21 | 1998-11-10 | Ballard Power Systems, Inc. | Substituted α,β,β-trifluorostyrene-based composite membranes |
| JPH1092444A (en) | 1996-09-13 | 1998-04-10 | Japan Gore Tex Inc | Solid high molecular electrolyte complex for electrochemical reaction device and electrochemical reaction device using it |
| US6444343B1 (en) * | 1996-11-18 | 2002-09-03 | University Of Southern California | Polymer electrolyte membranes for use in fuel cells |
| GB9708365D0 (en) * | 1997-04-25 | 1997-06-18 | Johnson Matthey Plc | Proton conducting membranes |
| US6605679B1 (en) * | 1997-07-23 | 2003-08-12 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
| US6635384B2 (en) | 1998-03-06 | 2003-10-21 | Gore Enterprise Holdings, Inc. | Solid electrolyte composite for electrochemical reaction apparatus |
| US6136412A (en) * | 1997-10-10 | 2000-10-24 | 3M Innovative Properties Company | Microtextured catalyst transfer substrate |
| US6042959A (en) * | 1997-10-10 | 2000-03-28 | 3M Innovative Properties Company | Membrane electrode assembly and method of its manufacture |
| US5879828A (en) * | 1997-10-10 | 1999-03-09 | Minnesota Mining And Manufacturing Company | Membrane electrode assembly |
| US5879827A (en) * | 1997-10-10 | 1999-03-09 | Minnesota Mining And Manufacturing Company | Catalyst for membrane electrode assembly and method of making |
| US6723758B2 (en) | 1997-11-12 | 2004-04-20 | Ballard Power Systems Inc. | Graft polymeric membranes and ion-exchange membranes formed therefrom |
| US6359019B1 (en) * | 1997-11-12 | 2002-03-19 | Ballard Power Systems Inc. | Graft polymeric membranes and ion-exchange membranes formed therefrom |
| JP5073883B2 (en) | 1998-01-30 | 2012-11-14 | ハイドロ−ケベック | Crosslinkable bisulfonyl derivatives and their use for the production of ion exchange membranes |
| US6495209B1 (en) | 1998-02-20 | 2002-12-17 | Lynntech, Inc. | Process of making a composite membrane |
| US6458257B1 (en) | 1999-02-09 | 2002-10-01 | Lynntech International Ltd | Microorganism control of point-of-use potable water sources |
| WO2000063995A1 (en) * | 1999-04-20 | 2000-10-26 | Lynntech, Inc. | Process of making a composite membrane |
| US6277512B1 (en) | 1999-06-18 | 2001-08-21 | 3M Innovative Properties Company | Polymer electrolyte membranes from mixed dispersions |
| GB9914499D0 (en) | 1999-06-22 | 1999-08-25 | Johnson Matthey Plc | Non-woven fibre webs |
| US6497977B1 (en) | 1999-11-30 | 2002-12-24 | Ballard Power Systems Inc. | Method of making stripped porous polymer films |
| US6646075B2 (en) | 1999-12-23 | 2003-11-11 | 3M Innovative Properties Company | High molecular weight perfluorocyclobutane polymers and method of making |
| US6479182B1 (en) | 2000-09-28 | 2002-11-12 | Graftech Inc. | Fuel cell electrode assembly with selective catalyst loading |
| US6589682B1 (en) * | 2000-01-27 | 2003-07-08 | Karen Fleckner | Fuel cells incorporating nanotubes in fuel feed |
| JP4042285B2 (en) | 2000-02-23 | 2008-02-06 | トヨタ自動車株式会社 | Solid polymer electrolyte membrane and method for producing the same |
| GB0006429D0 (en) * | 2000-03-17 | 2000-05-03 | Johnson Matthey Plc | Electrochemical cell |
| US20040028977A1 (en) * | 2000-05-30 | 2004-02-12 | Peter Pickup | Fuel cell incorporating a modified ion exchange membrane |
| US6268532B1 (en) | 2000-06-05 | 2001-07-31 | 3M Innovative Properties Company | Sulfonated perfluorovinyl functional monomers |
| US6559237B1 (en) | 2000-06-05 | 2003-05-06 | 3M Innovative Properties Company | Sulfonated perfluorocyclobutane ion-conducting membranes |
| KR100370399B1 (en) | 2000-06-30 | 2003-01-29 | 삼성전자 주식회사 | Partially fluorinated copolymer based on trifluorostyrene and substituted vinyl compound and ion conductive polymer layer formed therefrom |
| GB2364355B (en) | 2000-07-01 | 2004-08-04 | Trw Ltd | Electro-hydraulic braking systems |
| GB0016752D0 (en) | 2000-07-08 | 2000-08-30 | Johnson Matthey Plc | Electrochemical structure |
| US7014947B2 (en) * | 2000-09-27 | 2006-03-21 | Proton Energy Systems, Inc. | Integral membrane support and frame structure |
| US6605379B1 (en) | 2000-11-03 | 2003-08-12 | Grafttech Inc. | Hydrophobic fuel cell electrode |
| US6521369B1 (en) | 2000-11-16 | 2003-02-18 | Graftech Inc. | Flooding-reducing fuel cell electrode |
| US6517964B2 (en) * | 2000-11-30 | 2003-02-11 | Graftech Inc. | Catalyst support material for fuel cell |
| US6823584B2 (en) * | 2001-05-03 | 2004-11-30 | Ballard Power Systems Inc. | Process for manufacturing a membrane electrode assembly |
| US6689501B2 (en) * | 2001-05-25 | 2004-02-10 | Ballard Power Systems Inc. | Composite ion exchange membrane for use in a fuel cell |
| US20020180094A1 (en) * | 2001-06-01 | 2002-12-05 | Gough Jeffrey John | Hydrophobic fuel cell component |
| JP2003017090A (en) * | 2001-07-03 | 2003-01-17 | Sumitomo Chem Co Ltd | Polymer electrolyte membrane and fuel cell using it |
| CA2392241A1 (en) * | 2001-07-03 | 2003-01-03 | Sumitomo Chemical Co., Ltd. | Polymer electrolyte membrane and fuel cell |
| JP4102299B2 (en) * | 2001-07-05 | 2008-06-18 | ダブリュ．エル．ゴア アンド アソシエイツ，インコーポレイティド | Ionomer used in fuel cell and method for producing the same |
| TW589760B (en) * | 2001-08-09 | 2004-06-01 | Sumitomo Chemical Co | Polymer electrolyte composition and fuel cell |
| EP1448628A2 (en) * | 2001-11-16 | 2004-08-25 | E.I. Du Pont De Nemours And Company | Copolymers of olefins and vinyl- and allylsilanes |
| US6653515B2 (en) | 2001-12-14 | 2003-11-25 | Ballard Power Systems Inc. | Synthesis of α, β, β-trifluorostyrene via in-situ formation of trifluorovinyl metal halide |
| DE10163518A1 (en) * | 2001-12-21 | 2003-07-10 | Fraunhofer Ges Forschung | Proton-conductive membranes / layers and process for their preparation |
| US7651797B2 (en) * | 2002-01-14 | 2010-01-26 | The Board Of Trustees Of The University Of Illinois | Electrochemical cells comprising laminar flow induced dynamic conducting interfaces, electronic devices comprising such cells, and methods employing same |
| CA2473907A1 (en) * | 2002-01-23 | 2003-07-31 | Polyfuel, Inc. | Acid-base proton conducting polymer blend membrane |
| GB0210194D0 (en) | 2002-05-03 | 2002-06-12 | Johnson Matthey Plc | Composite membrane |
| CA2485971A1 (en) | 2002-05-13 | 2004-05-21 | Polyfuel, Inc. | Ion conductive block copolymers |
| US7354679B2 (en) | 2002-05-13 | 2008-04-08 | Polyfuel, Inc. | Ion conductive random copolymers |
| WO2003095509A1 (en) | 2002-05-13 | 2003-11-20 | Polyfuel, Inc. | Sulfonated copolymer |
| US7297429B2 (en) | 2002-07-05 | 2007-11-20 | Gore Enterprise Holdings, Inc. | Ionomer for use in fuel cells and method of making same |
| FR2843398B1 (en) * | 2002-08-09 | 2007-04-27 | Commissariat Energie Atomique | FLUORINATED POLYMERS, MEMBRANES PREPARED THEREFROM, AND FUEL CELL DEVICE COMPRISING THESE MEMBRANES |
| US20040036394A1 (en) * | 2002-08-21 | 2004-02-26 | 3M Innovative Properties Company | Process for preparing multi-layer proton exchange membranes and membrane electrode assemblies |
| JP3891484B2 (en) * | 2002-09-05 | 2007-03-14 | 株式会社ノリタケカンパニーリミテド | Electrolyte membrane and fuel cell comprising the membrane |
| DE10246461A1 (en) * | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Polymer electrolyte membrane containing a polyazole blend for use, e.g. in fuel cells, obtained by processing a mixture of polyphosphoric acid, polyazole and non-polyazole polymer to form a self-supporting membrane |
| DE10246373A1 (en) | 2002-10-04 | 2004-04-15 | Celanese Ventures Gmbh | Polymer electrolyte membrane for use, e.g. in fuel cells, manufactured by heating a mixture of sulfonated aromatic polyazole monomers in polyphosphoric acid and then processing to form a self-supporting membrane |
| US20040116546A1 (en) * | 2002-12-13 | 2004-06-17 | Kosek John A. | Direct organic fuel cell proton exchange membrane and method of manufacturing the same |
| US7205064B2 (en) * | 2003-06-27 | 2007-04-17 | The Board Of Trustees Of The University Of Illinois | Emulsions for fuel cells |
| JP2007528907A (en) * | 2003-06-27 | 2007-10-18 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Trifluorostyrene-containing compounds and their use in polymer electrolyte membranes |
| KR20060023174A (en) * | 2003-06-30 | 2006-03-13 | 스미또모 가가꾸 가부시키가이샤 | Polymer electrolyte composite film, method for production thereof and use thereof |
| US7632590B2 (en) * | 2003-07-15 | 2009-12-15 | Hewlett-Packard Development Company, L.P. | System and a method for manufacturing an electrolyte using electrodeposition |
| DE10340927A1 (en) * | 2003-09-04 | 2005-03-31 | Celanese Ventures Gmbh | Proton-conducting polymer membrane comprising polymers having covalently bonded to aromatic groups sulfonic acid groups, membrane-electrode unit and their application in fuel cells |
| DE10340929A1 (en) * | 2003-09-04 | 2005-04-07 | Celanese Ventures Gmbh | Proton-conducting polymer membrane comprising at least one porous carrier material and its application in fuel cells |
| US7338692B2 (en) | 2003-09-12 | 2008-03-04 | 3M Innovative Properties Company | Microporous PVDF films |
| WO2005049204A2 (en) * | 2003-09-29 | 2005-06-02 | E.I. Dupont De Nemours And Company | Trifluorostyrene containing compounds grafted to base polymers |
| WO2005082024A2 (en) * | 2004-02-24 | 2005-09-09 | Ini Power Systems, Inc. | Fuel cell apparatus and method of fabrication |
| KR100647287B1 (en) * | 2004-08-31 | 2006-11-23 | 삼성에스디아이 주식회사 | Polymer electrolyte membrane and fuel cell employing the same |
| US8642228B2 (en) * | 2004-08-31 | 2014-02-04 | Samsung Sdi Co., Ltd. | Polymer electrolyte membrane and fuel cell using the polymer electrolyte membrane |
| JP2008513962A (en) * | 2004-09-15 | 2008-05-01 | アイエヌアイ パワー システムズ インコーポレイテッド | Electrochemical cell |
| CN100487003C (en) * | 2004-12-21 | 2009-05-13 | 比亚迪股份有限公司 | A kind of polymer and proton exchange membrane of containing polymer |
| KR20080015020A (en) * | 2005-06-01 | 2008-02-15 | 폴리퓨얼, 인코포레이티드 | Polymer blend comprising ion-conducting copolymer and non-ionic polymer |
| WO2007041415A2 (en) * | 2005-09-30 | 2007-04-12 | Battelle Memorial Institute | Polymers for use in fuel cell components |
| US7901817B2 (en) * | 2006-02-14 | 2011-03-08 | Ini Power Systems, Inc. | System for flexible in situ control of water in fuel cells |
| TWI305214B (en) * | 2006-05-02 | 2009-01-11 | Univ Yuan Ze | A novel proton exchange composite membrane with low thickness and preparation thereof |
| US8158300B2 (en) | 2006-09-19 | 2012-04-17 | Ini Power Systems, Inc. | Permselective composite membrane for electrochemical cells |
| US8802238B2 (en) * | 2007-03-29 | 2014-08-12 | Akron Polymer Systems, Inc. | Optical compensation films based on fluoropolymers |
| US8889043B2 (en) | 2007-03-29 | 2014-11-18 | Akron Polymer Systems, Inc. | Optical films cast from styrenic fluoropolymer solutions |
| US8435636B2 (en) * | 2007-03-29 | 2013-05-07 | Akron Polymer Systems, Inc. | Optical compensation films of brominated styrenic polymers and related methods |
| US8551667B2 (en) * | 2007-04-17 | 2013-10-08 | Ini Power Systems, Inc. | Hydrogel barrier for fuel cells |
| US20090035644A1 (en) * | 2007-07-31 | 2009-02-05 | Markoski Larry J | Microfluidic Fuel Cell Electrode System |
| US20090042078A1 (en) * | 2007-08-09 | 2009-02-12 | Matsushita Electric Industrial Co., Ltd. | Surface-treated hydrocarbon-based polymer electrolyte membranes for direct oxidation fuel cells |
| KR100986493B1 (en) * | 2008-05-08 | 2010-10-08 | 주식회사 동진쎄미켐 | Polymeric mea for fuel cell |
| US8163429B2 (en) * | 2009-02-05 | 2012-04-24 | Ini Power Systems, Inc. | High efficiency fuel cell system |
| EP2470290B1 (en) | 2009-08-26 | 2019-07-24 | Evoqua Water Technologies Pte. Ltd. | Ion exchange membranes |
| CN101728549B (en) * | 2009-12-10 | 2011-05-04 | 山东东岳神舟新材料有限公司 | High-temperature proton exchange compound film |
| US9856376B2 (en) | 2011-07-05 | 2018-01-02 | Akron Polymer Systems, Inc. | Aromatic polyamide films for solvent resistant flexible substrates |
| EP2744851B1 (en) | 2011-08-19 | 2018-09-19 | Akron Polymer Systems, Inc. | Thermally stable, low birefringent copolyimide films |
| US8871882B2 (en) | 2012-02-14 | 2014-10-28 | Akron Polymer Systems, Inc. | Method for the preparation of styrenic fluoropolymers |
| CN103904344B (en) * | 2014-04-23 | 2016-02-10 | 北京九谷超微科技有限公司 | A kind of proton exchange membrane and preparation method thereof |
| JP6781434B2 (en) * | 2015-07-13 | 2020-11-04 | ダイキン工業株式会社 | Fluorine-containing polymer |
| US10130918B2 (en) * | 2016-09-16 | 2018-11-20 | Pall Corporation | Fluoropolymers and membranes comprising fluoropolymers (III) |
| DE102019104561A1 (en) | 2019-02-22 | 2020-08-27 | Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. | Method for producing a composite layer, electrochemical unit and use of the composite layer |
| CN110010942B (en) * | 2019-03-15 | 2021-01-05 | 浙江吉利汽车研究院有限公司 | Composite proton exchange membrane and preparation method thereof |
| CN113786743B (en) * | 2021-09-28 | 2023-07-18 | 常熟三爱富中昊化工新材料有限公司 | Gas separation membrane, method for the production and use thereof |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2651627A (en) | 1950-02-08 | 1953-09-08 | Gen Electric | Process for polymerizing phenyltrifluoroethylene |
| US3282875A (en) | 1964-07-22 | 1966-11-01 | Du Pont | Fluorocarbon vinyl ether polymers |
| US3341366A (en) * | 1964-08-19 | 1967-09-12 | Gen Electric | Sulfonated polymers of alpha, beta, beta-trifluorostyrene, with applications to structures and cells |
| US3528858A (en) | 1968-12-04 | 1970-09-15 | Gen Electric | Sulfonated aryl-substituted polyphenylene ether ion exchange membranes |
| US3945927A (en) * | 1972-06-05 | 1976-03-23 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Ion-exchange group bearing composite membranes |
| US4012303A (en) * | 1974-12-23 | 1977-03-15 | Hooker Chemicals & Plastics Corporation | Trifluorostyrene sulfonic acid membranes |
| JPS6046123B2 (en) | 1976-08-25 | 1985-10-14 | ダイキン工業株式会社 | Fluorine-containing copolymer and method for producing the same |
| JPS5569298A (en) | 1978-11-17 | 1980-05-24 | Kureha Chem Ind Co Ltd | Electrodeposition method of protein |
| NZ195570A (en) * | 1979-12-28 | 1983-05-31 | Ici Australia Ltd | Cation exchange resin based on perhalogenated fluorine-containing polymer |
| US4330654A (en) | 1980-06-11 | 1982-05-18 | The Dow Chemical Company | Novel polymers having acid functionality |
| ZA824471B (en) * | 1981-06-26 | 1983-04-27 | Ici Australia Ltd | Polymers |
| US4469564A (en) * | 1982-08-11 | 1984-09-04 | At&T Bell Laboratories | Copper electroplating process |
| NO843527L (en) | 1983-09-06 | 1985-03-07 | Chlorine Eng Corp Ltd | PROCEDURE FOR PREPARING A MEMBRANE OF POOD POLYMES |
| US4666991A (en) * | 1984-11-05 | 1987-05-19 | Sagami Chemical Research Center | Fluorine-containing graft copolymer and adhesive and composite membrane made thereof |
| US4650551A (en) * | 1985-05-31 | 1987-03-17 | The Dow Chemical Company | Supported ion exchange membrane films |
| US4865930A (en) * | 1988-10-27 | 1989-09-12 | Hughes Aircraft Company | Method for forming a gas-permeable and ion-permeable membrane |
| US5094895A (en) * | 1989-04-28 | 1992-03-10 | Branca Phillip A | Composite, porous diaphragm |
| JPH0327053A (en) | 1989-06-23 | 1991-02-05 | Daikin Ind Ltd | Electrostatic charge developing carrier |
| JPH03232529A (en) * | 1990-02-09 | 1991-10-16 | Yuasa Kasei Kk | Separating membrane |
| CA2085549A1 (en) * | 1991-12-25 | 1993-06-26 | Noboru Nakano | Fuel cell and electrolyte membrane therefor |
| JPH0629032A (en) * | 1992-07-08 | 1994-02-04 | Sumitomo Electric Ind Ltd | High polymer electrolyte film and its manufacture |
| JP3232529B2 (en) | 1992-09-25 | 2001-11-26 | 日新製鋼株式会社 | Fe-Ni alloy for lead frame and method of manufacturing the same |
| US5602185A (en) | 1993-09-21 | 1997-02-11 | Ballard Power Systems Inc. | Substituted trifluorostyrene compositions |
| US5422411A (en) * | 1993-09-21 | 1995-06-06 | Ballard Power Systems Inc. | Trifluorostyrene and substituted trifluorostyrene copolymeric compositions and ion-exchange membranes formed therefrom |
| US5834523A (en) * | 1993-09-21 | 1998-11-10 | Ballard Power Systems, Inc. | Substituted α,β,β-trifluorostyrene-based composite membranes |
| US5599614A (en) * | 1995-03-15 | 1997-02-04 | W. L. Gore & Associates, Inc. | Integral composite membrane |
| US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
| AU5889296A (en) * | 1995-06-07 | 1996-12-30 | Ballard Power Systems Inc. | Copolymeric compositions of trifluorostyrene, substituted tr ifluorostyrene and substituted ethylene, and ion-exchange me mbranes formed therefrom |
-
1996
- 1996-01-05 US US08/583,638 patent/US5834523A/en not_active Expired - Fee Related
-
1997
- 1997-01-03 DE DE69702442T patent/DE69702442T2/en not_active Expired - Lifetime
- 1997-01-03 WO PCT/CA1997/000003 patent/WO1997025369A1/en active IP Right Grant
- 1997-01-03 AU AU11872/97A patent/AU704923B2/en not_active Ceased
- 1997-01-03 EP EP97900054A patent/EP0882088B1/en not_active Expired - Lifetime
- 1997-01-03 JP JP9524691A patent/JP2000502625A/en active Pending
- 1997-01-03 CA CA002240495A patent/CA2240495C/en not_active Expired - Fee Related
- 1997-01-03 AT AT97900054T patent/ATE194366T1/en not_active IP Right Cessation
-
1998
- 1998-11-05 US US09/186,449 patent/US5985942A/en not_active Expired - Fee Related
-
1999
- 1999-11-15 US US09/441,181 patent/US6258861B1/en not_active Expired - Fee Related
-
2001
- 2001-07-09 US US09/901,269 patent/US6437011B2/en not_active Expired - Fee Related
-
2002
- 2002-06-25 US US10/179,073 patent/US20020161061A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ATE194366T1 (en) | 2000-07-15 |
| AU704923B2 (en) | 1999-05-06 |
| JP2000502625A (en) | 2000-03-07 |
| DE69702442D1 (en) | 2000-08-10 |
| CA2240495A1 (en) | 1997-07-17 |
| US6258861B1 (en) | 2001-07-10 |
| US5834523A (en) | 1998-11-10 |
| AU1187297A (en) | 1997-08-01 |
| US5985942A (en) | 1999-11-16 |
| US20020161061A1 (en) | 2002-10-31 |
| EP0882088A1 (en) | 1998-12-09 |
| US20010056128A1 (en) | 2001-12-27 |
| DE69702442T2 (en) | 2001-02-08 |
| US6437011B2 (en) | 2002-08-20 |
| EP0882088B1 (en) | 2000-07-05 |
| WO1997025369A1 (en) | 1997-07-17 |
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| EEER | Examination request | ||
| MKLA | Lapsed |