TWI312787B - Process for producing a porous polymeric memberane - Google Patents
Process for producing a porous polymeric memberane Download PDFInfo
- Publication number
- TWI312787B TWI312787B TW092117807A TW92117807A TWI312787B TW I312787 B TWI312787 B TW I312787B TW 092117807 A TW092117807 A TW 092117807A TW 92117807 A TW92117807 A TW 92117807A TW I312787 B TWI312787 B TW I312787B
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- Taiwan
- Prior art keywords
- solvent
- solution
- polymer
- film
- zone
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 32
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011877 solvent mixture Substances 0.000 claims abstract description 5
- 238000005266 casting Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 26
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims 2
- 238000007614 solvation Methods 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 229920006373 Solef Polymers 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
- B01D2323/22—Specific non-solvents or non-solvent system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
- Laminated Bodies (AREA)
- Fuel Cell (AREA)
Description
1312787 ， ϊ 玖、發明說明： (—)發明所屬之技術領域 本發明係關於多孔性聚合物膜。本發明特別地關於一 種製造多孔性聚合物膜之方法及此膜在鋰電池中或在燃料 電池中之用途。 (二）先前技術 多年來已知製造具鋰金屬陽極、及其中可添加或插入 鋰離子之材料之陰極之電池。此電池可使用鋰鹽於有機液 體（如碳酸伸丙酯）中之溶液作爲電解質，及如濾紙或聚 丙烯之分隔件。更近來，亦已建議使用固態離子傳導聚合 物作爲電解質。對於二次或可充電鋰電池，使用鋰金屬陽 極並不令人滿意，因爲枝狀物生長引發問題。現在可藉由 使用可在非常低電壓可逆地添加鋰離子之材料（如石墨） ，造成所謂之「鋰離子」、「搖椅」、或「搖擺」鋰充電 電池組，而排除此問題。這些鋰電池係基於在循環之充電 及放電部份時，其不僅含鋰金屬，亦含鋰離子在兩種添加 材料間來回搖擺之原理操作。
Gozdz等人（美國專利5,296,318)已提議一種聚合物 電解質，其包括75至92%氟亞乙烯與8至25%六氟丙烯之 共聚物，摻合鋰鹽與相容性溶劑，如碳酸伸乙酯/碳酸伸丙 酯混合物，而且由在如四氫呋喃之低沸點溶劑中之溶液流 延。GB 2 309 701 B專利（AE A Technology)敘述聚合電解 質組成物之黏附性可藉由將適當單不飽合基接枝至聚合物 鏈上而增強，而且在此情形，聚合物鏈可爲均一聚合物PVdF 1312787 ，或主要包括氟亞乙烯之共聚物或三聚物。亦可藉由首先 製造聚合物材料之多孔性膜，然後將此膜浸於鋰鹽於有機 溶劑之溶液中使電解質溶液組合聚合物膜，而製造固態聚 合物電解質，如EP 0 7 30 3 1 6 A專利（Elf Atochem)所述 。然而，製造多孔性膜之已知方法難以得到實質上大小均 勻之微孔及控制所得膜之多孔性。 燃料電池使用多孔性膜分隔陽極與陰極。此膜一般爲 多層組合件且可包括，例如，多孔性膜及一或更多層擴散 層。需要改良之膜以改良氣體至燃料電池板之均勻輸送。 (三）發明內容 本發明提供一種製造多孔性聚合物膜之方法，此方法 包括： a)製備在溶劑/非溶劑混合物中含戴亞乙烯之含聚合物之 溶液，其係藉由在加入溶劑前將聚合物分散於非溶劑中 t b )使此溶液保持在高溫直到聚合物完全溶劑合化； c )流延此溶液形成薄層；及 d )將此薄層乾燥形成膜。 此聚合物一般主要包括氟亞乙烯。因此，此聚合物可 爲均一聚合物，如聚氟亞乙烯（PVdF)，或例如，氟亞乙烯 與六氟丙烯之共聚物，或三聚物。一般而言，較佳等級之 聚合物爲PVdF均一聚合物Solvay Solef 1015或6020，共 聚物 Solvay Solef 20615 或 20815 或 Atochem 2801，及含 氟亞乙烯、六氟丙烯與氯三氟乙烯之三聚物，如W0 02/11230 -6- 1312787 專利所述。 此聚合物亦可爲其中聚合物鏈主要包括氟亞乙烯之聚 合物，其上接枝單不飽合羧酸、磺酸或磷酸、酯、或醯胺 。接枝於聚合物鏈上之單體應在碳鏈R -中僅具有一個雙鍵 ，及一或更多個羧酸基-COOH、磺酸基-S020H、膦酸基-P〇(〇H)2、酯基-COOR’、或醯胺基-CONH2。通常單體越小， 碳鏈R -上具有少於5個碳原子，則越佳。例如，丙烯酸； 巴豆酸、乙烯基乙酸、甲基丙烯酸（其爲丁烯酸之異構物 );戊烯酸之異構物，如烯丙基乙酸等。亦可使用對應之 醯胺（及經取代醯胺）。在酯中，R’基可爲甲基、乙基或 丁基；例如，可使用如丙烯酸甲酯或丙烯酸丁酯之酯。一 些較佳之接枝單體爲丙烯酸或二甲基丙烯醯胺，但是一定 範圍之其他加入最終基之單體亦爲適當的。 接枝可藉照射法完成。例如，聚合物鏈基質及接枝單 體材料可一起接受連續或斷續照射；或更佳爲基質在接觸 單體材料前預先照射。此照射可使用電子束、加馬射線或X _ 射線。此照射因產生自由基而明顯地活化基質（聚合物鏈 )。接枝程度係由許多因素決定，最重要爲聚合物基質藉 照射預先活化之程度、活化聚合物接觸接枝單體材料之時 間長度、單體可穿透聚合物之程度、及聚合物與單體接觸 時之溫度。所得材料之接枝程度希望爲最終重量之2至20% ’更佳爲3至12%，例如，5%或10%。 其他之成分亦可存在於溶液中，例如，黏度改良劑， 如羧甲基纖維素，及表面張力改良劑，如草酸或順丁烯二 -7 - 1312787 酸。 將聚合物混合非溶劑形成漿液，然後加入溶劑形成均 質溶液。一般而言’形成聚合物與非溶劑之漿液且攪拌加 熱至約6 0 °C，較佳爲在非金屬容器中（例如，玻璃，或塑 膠’如聚丙烯），然後快速地加入溶劑（例如，5秒鐘內約 1公升）。 如果聚合物先混合溶劑，然後將非溶劑加入溶液，則 如此產生微凝膠，使得溶液不安定且不產生可再製膜。 非溶劑爲單獨使用時不溶解聚合物之液體。非溶劑應 不僅溶於溶劑中’亦應以實質上所有之比例與溶劑互溶。 —般而言’非溶劑之沸點比溶劑高，較佳爲高2 0 °C，更佳 爲高40 °C或更多。非溶劑之實例包括含6至20個碳原子之 醇類，如辛醇、癸醇與十二碳醇，及其混合物，較佳爲癸 醇、十二碳醇、及其混合物。特佳非溶劑爲十二碳醇與癸 醇之50:50混合物或僅十二碳醇。 溶劑爲可使聚合物溶解或膨脹之液體。此溶劑可選自 ，例如，酮類、醚類、N，N-二甲基甲醯胺（DMF)、N，N -二甲 基乙醯胺（DMA )、N，N-二乙基乙醯胺、N -甲基-2-吡咯啶酮 (NMP)、六甲基磷醯胺、四甲脲、與二甲基亞楓（DM SO)、或 其混合物。DMF與NMP爲較佳溶劑。更佳爲，NMP爲此溶劑 〇 溶液中非溶劑對溶劑之比例可不同。一般而言，溶劑/ 非溶劑混合物中之非溶劑比例爲2至3 0重量％，較佳爲5 至15重量％，更佳爲7至10重量％。 一 8 _ 1312787 溶液中之聚合物量通常爲3至30重量％，較佳爲5至20 重量％，更佳爲8至1 5重量％。 聚合物之溶解係在高溫發生。高溫爲高於室溫（取爲 2〇°C )之溫度。選擇之溫度係與使用之聚合物及溶劑/非溶 劑組合，及發生溶劑合化之時間量有關。一般而言，高溫 爲至少40°C，更常爲至少50°C，例如，55T：。如果溶劑合 化爲發生長期時間’則可使用較低之溫度。 —般而言，溶劑合化發生數日。此溶劑合化過程持續 直到聚合物完全溶劑合化。所需之確實溶劑合化時間視溶 劑/非溶劑混合物、聚合物之選擇、及使用之溫度而不同。 —般而言，溶劑合化發生4至14日，較佳爲5至10曰， 而且最佳爲5至7日。例如，視溶液中之非溶劑對溶劑比 例而定，PVdF (Solvay Solef 6020 / 1 00 1 )於 N-甲基-2-吡 咯啶酮及癸醇與十二碳醇之50:50混合物一般在5至14曰 中完全溶劑合化，一般爲10日。溶劑合化過程時之凝膠形 成緩慢而可忽略。溶劑合化亦爲不形成微凝膠而發生。 一旦聚合物完全溶劑合化，則此溶液在室溫安定數週 。因此，溶液之黏度不隨時間改變，及溶液之顏色維持固 定，而且溶劑或非溶劑不自溶液分離。此外，在流延時， 此溶液形成具一致性質之可再製膜。因此’立即將溶液流 延成膜爲不必要的。 此溶液一般流延於非多孔性基板上，如鋁箔或My 1 a r 膜。鋁箔一般爲約20微米厚，而Mylar膜一般爲約loo微 米厚。如果陽極或陰極係由不太多孔性之材料製成，則此 -9- 1312787 溶液亦可流延於陽極或陰極上。 在流延溶液時，一般在基板上將溶液流延成小於0 . 5 毫米厚，較佳爲小於0.3毫米厚之薄層。
膜係藉由在乾燥機中一般在至少兩個連續乾燥區中乾 燥而形成；此膜不接觸任何液體。較佳爲，乾燥機具有三 或四個乾燥區，最佳爲四個乾燥區。在各區中維持不同之 溫度，而且溫度按膜轉移方向在各區增加。在使用於移動 網上製造膜之刀輥連續法之乾燥區中之典型溫度値如下： 第一區 50°C 至 120°C 第二區 80°C 至 150°C。 典型之溫度配對可爲，例如，第一區爲65 °C及第二區爲 100°C，或第一區爲95°C及第二區爲120t。如果此機器具 有三或四個乾燥區，則各區之溫度變化可更緩和。例如， 在此機器具有四個乾燥區之處，各區可依序設爲65t、75 °C、95°C、及 110°C。 移動網之速度一般範圍爲0.2至5.0米/分鐘。網速視 乾燥區長度及區數量而不同。機器具有越多區，則網可較 快地行進而對膜性質無負面影響。 此溶液係在氣體存在下乾燥形成膜。在一個具體實施 例中，此氣體爲乾燥氣體，例如，乾燥空氣。例如，可使 用具低於-20 °C之露點之空氣’例如，-35 °C至-37 °C。然而 ，此氣體不需爲無水。此氣體亦可爲潮濕空氣，例如，在 1 6 °C於3 4%相對濕度之周圍條件供應之空氣。然而，如果空 氣濕度改變，則膜之滲透力亦改變。 -10- 1312787 所得多孔性聚合物膜可藉由改變非溶劑對溶劑之比例 、聚合物對溶劑/非溶劑之比例、第一與第二乾燥區之溫度 、及移動網之速度而控制其多孔性。 製造之膜之多孔性可在G u r 1 e y機上測量。如此產生使 用此機器測量不同膜之相對多孔性之指標。此機器測量1 00 立方米之空氣在小標準壓力差（i.215 kP a)通過一平方英 吋（6 . 45平方公分）膜之時間秒數。如此造成已知爲Gur ley 數或Gurley値之讀數。其亦可表示成具有單位Gurley秒 數。產生400至600之Gurley數（Gurley秒數）之商業膜 爲可得的。具<60之Gur 1 ey數之膜在用於電池組時趨於縮 短。然而，其適合用於燃料電池。具50至200，更佳爲60 至100之Gurley數之膜在本發明之內容中較佳。隨Gurley 數增加，膜之多孔性降低，表示空氣難以通過膜。視孔之 分布而定，其係由於具較小孔或較少較大孔之膜所造成。 依照本發明可製造薄至5微米之膜。因此，此膜具有 至少5微米，較佳爲1〇至30微米，更佳爲15至25微米 ，最佳爲17至22微米之厚度。 本發明之一個優點爲可製造具適合用於電池組之強度 之薄膜。此薄膜亦不縮短。 在第二態樣中，本發明提供一種包括含氟亞乙烯之聚 合物之膜’其具有5至30微米之厚度及5至300之Gurley 數（Gur 1 ey秒數）。此膜較佳爲具有50至200，更佳爲60 至100’最佳爲70至90之Gurley數。此膜迄今尙不可得 -11- 1312787 本發明亦提供本發明之膜或依照本發明製造之膜在電 池組中作爲分隔件之用途。此膜適合用於一定範圍之不同 型式電池組，例如，鎳-鎘、鎳金屬氫化物、鋰離子、與鋰 聚合物電池組。膜之可控制多孔性與厚度及這些膜之高強 度使其對此用途特別有利。 本發明亦提供本發明之膜或依照本發明製造之膜在燃 料電池中之用途。本發明亦提供含本發明膜之層壓物及此 層壓物在燃料電池中之用途。 (四）實施方式 本發明現在藉實例更詳細地敘述。 實例 這些實例中所述之膜所示之Gu r 1 ey數係在美國紐約州 Troy ， 514 Fulton Street 之 Gurley Instruments 之 Automatic Densometer 4340 型上得到。 實例1 將100克具有0.210公升/克之固有黏度（DMF，25t )之PVdF (Solef 6020 )分散於70克辛醇中。將漿液攪拌 且加入900克之DMF。將混合物在55°C攪拌1日且在55°C 維持又6日，直到達成完全溶劑合化。 使用刀輥塗覆系統，將此溶液流延於以0 · 5米/分鐘移 動之聚酯網上。將刀葉間隙設爲0.32毫米，而且第1區之 乾燥區溫度爲651及第2區爲1〇〇 °C。如此造成具17微米 厚度及3 2 Gu r 1 e y秒數之空氣滲透力之最終微多孔性膜。 將第1區之乾燥溫度增至80°C及第2區爲l〇5°C，而製 -12- 1312787 造具17微米厚度及85 Gurley秒數之空氣滲透力之膜。 進一步將第1區之乾燥溫度增至95°C及第2區爲1 10°C ，而製造具17微米厚度及93 Gurley秒數之空氣滲透力之 膜。 實例2 將100克具有0.210公升/克之固有黏度（DMF，25 °C )之PVdF (Solef 6020 )分散於80克癸醇中。將漿液攪拌 且加入900克之NMP。如實例1所述，將混合物攪拌及加熱 直到達成完全溶劑合化。 使用刀輥流延系統，將此溶液流延於以0 . 5米/分鐘移 動之聚酯網上。將刀葉間隙設爲0.32毫米。乾燥區溫度及 膜性質敘述於以下表1。 表1 實例2.1 實例2.2 乾燥區溫度，第1區（°c) 95 110 乾燥區溫度，第2區（°C) 110 130 膜厚（微米） 14 16 空氣滲透力（Gurley秒數） 12 40 實例3 將100克具有0.210公升/克之固有黏度（DMF，25°C )之PVdF (Solef 6020 )分散於70克之癸醇與十二碳醇之 1 : 1 (重量比）混合物中。將漿液攪拌且加入900克之NMP 。將混合物在5 5 °C攪拌1日且在5 5 °C維持又1 0日，直到達 成完全溶劑合化。 -13- 1312787 ......." 使用刀輥塗覆系統，將此溶液流延於以0 . 5米/分鐘移 動之聚酯網上。將刀葉間隙設爲0 · 3 2毫米。乾燥區溫度及 膜性質敘述於以下表2。 ^_2. 實例3.1 實例3.2 乾燥區溫度，第1區（°c) 75 110 乾燥區溫度，第2區（°C) 110 130 膜厚（微米） 13 18 空氣滲透力（Gurley秒數） 70 180 眚例4 將100克具有0.210公升/克之固有黏度（DMF，25°C )之PVdF (Solef 6020 )分散於100克之癸醇與十二碳醇之 1 : 1 (重量比）混合物中。將槳液攪拌且加入900克之NMP 。如實例3所述，將混合物攪拌及加熱直到達成完全溶劑 合化。 使用刀輥塗覆系統，將此溶液流延於以0.5米/分鐘移 動之聚酯網上。將刀葉間隙設爲〇 . 3 2毫米。乾燥區溫度及 膜性質敘述於以下表3。 1312787 實例4.1 實例4.2 乾燥區溫度，第1區（°c) 75 110 乾燥區溫度，第2區（°C) 110 130 膜厚（微米） 22 24 空氣滲透力（Gurley秒數） 9 55 由以上之實例可了解，如果乾燥器爲較高之溫度’及 如果非溶劑之比例變小，則多孔性變小（即，Gu r 1 ey數增 加）。如果非溶劑與溶劑間之沸點差大於25°C，則膜品質 通常改良。 實例5 將1〇〇克具有0.210公升/克之固有黏度（DMF，25°C )之PVdF (Solef 6020 )分散於100克十二碳醇中。將漿液 攪拌且加入900克之NMP。如實例1所述，將混合物攪拌及 加熱直到達成完全溶劑合化。 使用刀輥塗覆系統，將此溶液流延於以〇 . 5米/分鐘移 動之聚酯網上。將刀葉間隙設爲0.30毫米。乾燥區溫度及 膜性質敘述於以下表4。 表 4 實例5 乾燥區溫度，第1區（°c) 75 乾燥區溫度，第2區（°C) 110 膜厚（微米） 24 空氣滲透力（Gurley秒數） 76 實例6 1312787 將100克具有0.210公升/克之固有黏度（DMF，25°C )之PVdF (Solef 6020 )分散於80克十二碳醇中。將漿液 攪拌且加入9 00克之NMP。如實例1所述，將混合物攪拌及 加熱直到達成完全溶劑合化。 使用刀輥塗覆系統，將此溶液流延於以0 . 5米/分鐘移 動之聚酯網上。將刀葉間隙設爲0 . 3 2毫米。乾燥區溫度及 膜性質敘述於以下表5。 表5 實例6 乾燥區溫度，第1區（°c) 85 乾燥區溫度，第2區rc) 110 膜厚（微米） 22 空氣滲透力（Gurley秒數） 146 實例7
將100克具有0.210公升/克之固有黏度（DMF，25°C )之PVdF (Solef 6020 )分散於60克十二碳醇中。將漿液 攪拌且加入900克之NMP。如實例1所述，將混合物攪拌及 加熱直到達成完全溶劑合化。 使用刀輥塗覆系統，將此溶液流延於以〇 . 5米/分鐘移 動之聚酯網上。將刀葉間隙設爲〇.3〇毫米。乾燥區溫度及 膜性質敘述於以下表6。
-16- 1312787 實例7 乾燥區溫度，第1區rc) 85 乾燥區溫度，第2區（°C) 110 膜厚（微米） 19 空氣滲透力（Gurley秒數） 88
% -17
Claims (1)
- rBnm i公苦积 ί 第 92 1 1 78 07 號 年4 月 3〇Γ ./ί.Χ 多孔性聚合物膜之製法」專利案 (2 009年4月修正） 拾、申請專利範圍： 1· 一種製造多孔性聚合物膜之方法，此方法包括·· a) 在溶劑/非溶劑混合物中製備含有含氟亞乙烯之聚合物 之溶液’該非溶劑之比例爲2至3 0重量％，其係藉由 在加入溶劑前將聚合物分散於非溶劑中，其中非溶劑 之沸點比溶劑高； b) 使此溶液保持在至少40 °C之高溫直到聚合物完全溶劑 鲁 合化（solvated); c) 流延此溶液形成薄層；及 d) 將此薄層乾燥形成膜。 2 .如申請專利範圍第1項乞方法，其中此溶液包括聚氟亞 乙烯（PVdF)。 3 .如申請專利範圍第1項之方法，其中溶劑爲N，N-二甲基 甲醯胺（DMF)、N，N-二甲基乙醯胺（DMA)、或N-甲基-2-吡咯啶酮（NMP)。 · 4.如申請專利範圍第1項之方法，其中非溶劑爲辛醇、癸 醇、十二碳醇、或其混合物。 5 .如申請專利範圍第1項之方法’其中此溶液溶劑合化至 多14日。 6 .如申請專利範圍第1項之方法，其中在氟亞乙烯上接枝 單不飽合羧酸、磺酸或磷酸、酯、或醯胺基。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0216834.2A GB0216834D0 (en) | 2002-07-19 | 2002-07-19 | Porous polymeric membrane |
Publications (2)
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| TW200404823A TW200404823A (en) | 2004-04-01 |
| TWI312787B true TWI312787B (en) | 2009-08-01 |
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| TW092117807A TWI312787B (en) | 2002-07-19 | 2003-06-30 | Process for producing a porous polymeric memberane |
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| US (1) | US7166644B2 (zh) |
| EP (1) | EP1523515B1 (zh) |
| JP (1) | JP4264415B2 (zh) |
| KR (1) | KR100982905B1 (zh) |
| CN (1) | CN1668680A (zh) |
| AU (1) | AU2003250374A1 (zh) |
| GB (1) | GB0216834D0 (zh) |
| TW (1) | TWI312787B (zh) |
| WO (1) | WO2004009684A1 (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005123599A2 (en) * | 2004-01-20 | 2005-12-29 | Boundless Corporation | Highly microporous polymers and methods for producing and using the same |
| US8173713B2 (en) | 2006-05-25 | 2012-05-08 | Drexel University | Filled nanoporous polymer membrane composites for protective clothing and methods for making them |
| FR2921518B1 (fr) * | 2007-09-26 | 2009-12-11 | Commissariat Energie Atomique | Procede d'elaboration de membranes conductrices de protons de pile a combustible par radiogreffage |
| EP2106801A1 (en) | 2008-04-04 | 2009-10-07 | Giuliani International Limited | IL-25 for use in the treatment of inflammatory diseases |
| EP2130547A1 (en) | 2008-06-06 | 2009-12-09 | Giuliani International Limited | IL-25 for use in the treatment of inflammatory diseases |
| KR101921876B1 (ko) * | 2016-11-29 | 2018-11-23 | 닛토덴코 가부시키가이샤 | 층을 전사하기 위한 전사 시트 및 전극 촉매층이 부착된 시트 |
| FR3089226B1 (fr) * | 2018-11-30 | 2021-08-06 | Arkema France | Procédé de préparation de films de polymère fluoré poreux |
| JP7240608B2 (ja) * | 2019-08-29 | 2023-03-16 | トヨタ自動車株式会社 | 非水溶性高分子の多孔質体の製造方法 |
| JP7281086B2 (ja) * | 2019-10-09 | 2023-05-25 | トヨタ自動車株式会社 | 多孔質体の製造方法 |
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| US3620895A (en) * | 1969-01-03 | 1971-11-16 | Polaroid Corp | Corrugated micropermeable membrane |
| GB1552942A (en) * | 1975-07-17 | 1979-09-19 | Sumitomo Electric Industries | Process for producing a porous material having a fine pore size |
| US4267364A (en) * | 1977-04-20 | 1981-05-12 | E. I. Dupont De Nemours And Company | Fluorinated ion exchange polymer containing carboxylic groups, process for making same, and film and membrane thereof |
| US4384047A (en) * | 1980-03-28 | 1983-05-17 | Pennwalt Corporation | Porous vinylidene fluoride polymer membrane and process for its preparation |
| US4399025A (en) * | 1980-10-28 | 1983-08-16 | Delta Central Refining, Inc. | Solvent extraction process for rerefining used lubricating oil |
| US4433082A (en) * | 1981-05-01 | 1984-02-21 | E. I. Du Pont De Nemours And Company | Process for making liquid composition of perfluorinated ion exchange polymer, and product thereof |
| JPS6211521A (ja) | 1985-07-09 | 1987-01-20 | Fuji Photo Film Co Ltd | カ−トリツジ型ミクロフイルタ−の製造方法 |
| FR2614214B1 (fr) * | 1987-04-23 | 1993-02-12 | Commissariat Energie Atomique | Membrane semi-permeable organominerale et son procede de fabrication. |
| EP0335805A3 (en) * | 1988-04-01 | 1990-04-25 | Terumo Kabushiki Kaisha | Method of manufacturing porous membrane and porous membrane manufactured by the same method |
| US5158721A (en) * | 1989-11-30 | 1992-10-27 | Millipore Corporation | Porous membrane formed from interpenetrating polymer network having hydrophilic surface |
| US6013688A (en) * | 1992-05-06 | 2000-01-11 | Corning Costar Corporation | PVDF microporous membrane and method |
| US5384047A (en) * | 1993-01-22 | 1995-01-24 | Refractron Technologies Corporation | Filter dryer body |
| US5296318A (en) * | 1993-03-05 | 1994-03-22 | Bell Communications Research, Inc. | Rechargeable lithium intercalation battery with hybrid polymeric electrolyte |
| TW342537B (en) | 1995-03-03 | 1998-10-11 | Atochem North America Elf | Polymeric electrode, electrolyte, article of manufacture and composition |
| GB2309701B (en) * | 1996-01-31 | 1999-06-16 | Aea Technology Plc | Organic electrolyte composition |
| EP0793286B1 (en) * | 1996-01-31 | 1999-03-31 | AEA Technology plc | Grafted polyvinylidene fluoride as a solid polymer electrolyte for eletrochemical cells, and electrochemical cell incorporating same |
| GB9708365D0 (en) * | 1997-04-25 | 1997-06-18 | Johnson Matthey Plc | Proton conducting membranes |
| US6248469B1 (en) * | 1997-08-29 | 2001-06-19 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
| KR20020076246A (ko) * | 1999-12-23 | 2002-10-09 | 액센투스 피엘씨 | 미세다공성 막 |
| GB0014464D0 (en) * | 2000-06-15 | 2000-08-09 | Aea Technology Plc | A cell incorporating a porous membrane |
| GB0018635D0 (en) * | 2000-07-31 | 2000-09-13 | Aea Technology Plc | Polymer electrolyte |
| GB0024347D0 (en) * | 2000-10-05 | 2000-11-22 | Aea Technology Plc | Electrolyte for a secondary cell |
-
2002
- 2002-07-19 GB GBGB0216834.2A patent/GB0216834D0/en not_active Ceased
-
2003
- 2003-06-23 WO PCT/GB2003/002682 patent/WO2004009684A1/en active Application Filing
- 2003-06-23 KR KR1020057000969A patent/KR100982905B1/ko active IP Right Grant
- 2003-06-23 AU AU2003250374A patent/AU2003250374A1/en not_active Abandoned
- 2003-06-23 CN CNA038170825A patent/CN1668680A/zh active Pending
- 2003-06-23 US US10/520,943 patent/US7166644B2/en not_active Expired - Lifetime
- 2003-06-23 EP EP03765144.5A patent/EP1523515B1/en not_active Expired - Lifetime
- 2003-06-23 JP JP2004522283A patent/JP4264415B2/ja not_active Expired - Lifetime
- 2003-06-30 TW TW092117807A patent/TWI312787B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005533884A (ja) | 2005-11-10 |
| GB0216834D0 (en) | 2002-08-28 |
| WO2004009684A1 (en) | 2004-01-29 |
| CN1668680A (zh) | 2005-09-14 |
| KR20050021518A (ko) | 2005-03-07 |
| EP1523515A1 (en) | 2005-04-20 |
| KR100982905B1 (ko) | 2010-09-20 |
| EP1523515B1 (en) | 2019-09-04 |
| TW200404823A (en) | 2004-04-01 |
| JP4264415B2 (ja) | 2009-05-20 |
| AU2003250374A1 (en) | 2004-02-09 |
| US20060148911A1 (en) | 2006-07-06 |
| US7166644B2 (en) | 2007-01-23 |
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