TWI343143B - Non-perfluorinated resins containing ionic or ionizable groups and products containing the same - Google Patents
Non-perfluorinated resins containing ionic or ionizable groups and products containing the same Download PDFInfo
- Publication number
- TWI343143B TWI343143B TW093102930A TW93102930A TWI343143B TW I343143 B TWI343143 B TW I343143B TW 093102930 A TW093102930 A TW 093102930A TW 93102930 A TW93102930 A TW 93102930A TW I343143 B TWI343143 B TW I343143B
- Authority
- TW
- Taiwan
- Prior art keywords
- polymer
- perfluorinated
- acrylic
- polyelectrolyte
- group
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 22
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 5
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- 229920000867 polyelectrolyte Polymers 0.000 claims description 24
- -1 tridecyloxydecane methacrylate Chemical compound 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 5
- 239000004811 fluoropolymer Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 4
- OMJIIKFXJPEYCZ-UHFFFAOYSA-N 2,5-dimethylhex-2-enamide Chemical compound CC(C)CC=C(C)C(N)=O OMJIIKFXJPEYCZ-UHFFFAOYSA-N 0.000 claims 1
- 150000000703 Cerium Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 55
- 239000000446 fuel Substances 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920002959 polymer blend Polymers 0.000 abstract description 3
- 229920005548 perfluoropolymer Polymers 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000004816 latex Substances 0.000 description 17
- 229920000126 latex Polymers 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 15
- 238000002156 mixing Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 101100152729 Mus musculus Tenm4 gene Proteins 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003014 ion exchange membrane Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000012864 cross contamination Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920003936 perfluorinated ionomer Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- FRFUQJFVJRYYDZ-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)prop-2-enamide Chemical compound CC(C)CNC(=O)C(C)=C FRFUQJFVJRYYDZ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XMEJDFDNYQYNBF-UHFFFAOYSA-N C(C(=C)C)(=O)O.COC(CCCCCCCCC)(OC)OC Chemical compound C(C(=C)C)(=O)O.COC(CCCCCCCCC)(OC)OC XMEJDFDNYQYNBF-UHFFFAOYSA-N 0.000 description 1
- LLSGMJLKTCFEOX-UHFFFAOYSA-N C(C=C)(=O)N(OCC(C)C)CCCCCCCCCC Chemical compound C(C=C)(=O)N(OCC(C)C)CCCCCCCCCC LLSGMJLKTCFEOX-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NCGDAXSZZUDOCZ-UHFFFAOYSA-N ethene;sulfane Chemical compound S.C=C NCGDAXSZZUDOCZ-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- AWKZQVYCCQCKBH-UHFFFAOYSA-N hydrazine 1-methylpyrrolidin-2-one Chemical compound CN1C(CCC1)=O.NN AWKZQVYCCQCKBH-UHFFFAOYSA-N 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JKTHTZCPLANQBH-UHFFFAOYSA-N n,n-dimethylthiohydroxylamine Chemical compound CN(C)S JKTHTZCPLANQBH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- OEMHEHNEYRBFCZ-UHFFFAOYSA-N prop-1-ene sulfane Chemical compound S.C=CC OEMHEHNEYRBFCZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
- A47F8/00—Dummies, busts or the like, e.g. for displaying garments
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
- A47F13/00—Shop or like accessories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
- B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
- B01D71/4011—Polymethylmethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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Description
玖、發明說明: 【發明所屬之技術領域】 本發月係合物樹脂’更特別地係關於包含離子及/ 或可離子化基之非全氟化聚合物樹㈣並相當於,,非全氣化 k電解貝)’其可用於各種產物中,h聚電解質隔膜及其 他熱塑性物品。本發明另關於製造這些樹脂以及利用這些 樹脂之方法。 【先前技術】 全氟碳離子交換隔膜提供高陽離子運送並已廣泛地用作 離子乂換隔膜。聚合物離子交換隔膜係相當於固體聚合物 電解質或聚合物交換隔膜(PEM)。因為迫切需要,最常用並 ° 商業A 1構付之隔膜係由全敗項酸化Nafion®及
Aciplex®*合物製得。但是’報告及文獻描述這些隔膜運 作良好,但顯示數項限制阻礙商業化技術進一步發展◊另 外,其在氣態燃料的運作情m態燃料好,可能主要是 因為燃料交又污染而降低電池性能1膜㈣化學性及機 械強度疋燃料電池應用之重要性質。實際上,隔膜經常處 於尚差壓、吸水-脫水循環以及其他條件下。而且,當隔膜 是非常薄,如小於5〇微米時,機械強度變得重要。此外, 用於燃料電池或蓄電池應料,由於金屬離子的存在及偶 爾存在之溶劑,隔膜係處於可達20(TC之溫度下非常酸的媒 "裏氧化及/或還原環境中,這環境需要耐化學及耐電化學 以及熱安定之隔膜。 〇A90\90872 DOC4 -6- 1343143 目前,許多含氟隔膜具有下列缺點中之一或多項: I) 高液體及氣體交叉通過隔膜; II) 氟化聚合物與其他導致較差性質之聚合物間之異相 換合; Π1)在某些液體燃料的存在下耐化學性不夠; iv) 耐電化學性差; v) 磺酸化基缺乏異相分布; vi) 機械性質差;及/或 vii) 熱安定性差。 頒予Nora等人之美國專利第4,295,952號係關於陽離子隔 膜,其具有苯乙烯、二乙烯基苯與2-乙烯基吡啶、4-乙烯基 吡啶及/或丙烯酸中至少一種之部分磺酸化三聚物。 頒予Ehrenberg等人之美國專利第5,679 482號係關於摻 有含離子基之離子導電隔膜的燃料電池。形成隔臈之聚合 物包含已利用磺酸化試劑磺酸化之苯乙烯。磺酸化可以單 體或聚合物發生。 美國專利第5,795,668號描述一種含]^£八及利用1^0〇11™ 型聚合物之強化聚合物離子交換隔膜(pEM)的燃料電池。 PEM係以氟化多孔支撐層及當量為約5〇〇至2〇〇〇且較佳離 子交換容量為〇·5至2毫當量/克乾樹脂之強化離子交換隔膜 為基材。多孔支撐層係由特定PTFE及PTFE共聚物製成。隔 膜是側鏈包含_CF2CF2S〇3H之全氟化聚合物。由文獻已知 Nafion®型聚合物在甲醇燃料電池中可能有機械故障的問 題以及液體交又污染的問題。 0 \90\90872 D0C4 1343143 頒予Rusch之WO 97/41 168係關於一種多層離子交換複合 隔膜,其具有離子交換樹脂,如氟化或非氟化聚苯乙烯基 質之磺酸鹽及磺酸化聚四氟乙烯。 WO 98/205 73 A1描述一種含有高氟化鋰離子交換聚合物 電解質隔膜(PEM)之燃料電池。PEM係以浸泡非質子溶劑之 離子父換隔膜為基材。
WO 98/22989描述一種含有聚苯乙烯磺酸及聚(氟化亞乙 烯)之聚合物隔膜,其提供直接甲醇燃料電池(DMFC)用途 較低甲醇交叉污染。但是,所述聚合物摻合程序無法提供 可接受摻合物,而且磺酸化步驟複雜。
Holmberg 等人(J. Material Chem.(1996 6(8), 1309))描述 藉由輻射接枝苯乙烯於PVDF薄膜上,接著以氣磺酸進行磺 酸化以製備質子導電隔膜。在本發明中,不需要磺酸化步 驟,因為磺酸化基可利用磺酸化單體摻入。
美國專利第6,252,000號係關於一種氟化離子交換/非官 能基聚合物之摻合物。特殊實例包括全氟化磺醯氟聚合物/ 聚(CTFE-共-全氟二氧戊環)摻合物。 WO 99/67304係關於一種磺酸化芳族全氟化單體與丙烯 酸系單體共聚合所製得之芳族全氟化離聚物。所存在的磺 酸化基係位於聚合物之氟化芳族鍵中。 美國專利第6,025,092號係關於一種全氟化離聚物,其中 VDF單體係與磺酸化單體聚合。 此外,描述續酸化丙稀酸系或績酸化乙稀系聚合物用於 ,例如超吸收體、尿布及隱形眼鏡(J. Meter. Chem. 1996, Ο \90V90872 DOC4 1343143 6(a),1309及I0nic 3, 214(1997))。但是,未曾描述此類型產 物在用作聚電解質隔獏及類似物之隔膜方面的應用。將上 面及整個本申請案所提所有專利、公告案及申請案全文以-引用方式併入本文中並形成本申請案之一部分。 因此,有必要克服這些限制令之一或多項並發展一種可 用於液體燃料電池之隔膜。因此,有必須克服這些限制中 之一或多項並發展一種可用於液體燃料電池之隔膜。更特 別地,有必要發展一種非全氟化聚電解質以直接從水性或 非水性分散液製造隔膜。而且,有必要提供合成組合物及· 合成方法以及利用具有磺酸化或其他官能度之非全氟化聚 電解質之水或非水性分散液的方法。此外,有必要提供一 種車又令易且環保的方法。而且,熟諳此技者將偏好具有較- 向耐化學性及機械強度之聚電解質隔膜。而且,熟諳此技 者將偏好具有較高耐化學性及機械強度之聚電解質隔獏。 【發明内容】 因此,本發明一項特點係提供具有離子官能度之非全氟 化聚電解質。 霉 本發明另一項特點係提供一種具有高耐化學性及/或機 械強度之非全氟化聚電解質隔膜。 本發明另一項特點係提供可形成非全氟化聚電解質隔膜 之、’且伤的聚合物,其中該聚電解質隔膜可避免上述一或多 項缺點’如避免高液體交叉通過隔獏。 本發明另一項特點係提供可由聚合物分散液直接製得之 隔膜。 〇\9〇\90872.D〇C4 •9- 1343143 本發明另—項特點係提供非全氟化^:電解質而無另外績 酸化步驟。 — 為達到纟文具體化及廣泛描述之這些及其他優點並根據 本發明㈣,本發明係、關於—種含有至少—個丙稀酸系樹 脂及/或乙烯基樹脂之聚合物或聚合物摻合物,其中丙烯酸 系及/或乙烯基樹月旨具有至少一個離子或可離子化基,如磺 酸化基,其中聚合物的當量係從約200至約4,〇〇〇。 本發明也關於-種組合物,其包括摻合下列聚合物之聚合 物產物.a)至少一種具有丙烯酸系及/或乙烯基單位及至少一 個離子或可離子化基之聚合物;和…選用至少一種附加聚合 物’其中a)與b)S不同的。附加聚合物可為任何相容聚合物 ,如熱塑性聚合物(如熱塑性非氟聚合物或氟聚合物)。 本發明另關於一種組合物,其包含:勾至少一種含可聚 合丙烯酸系及/或含乙烯基之單體與至少一種含有至少一 個離子或可離子化基或兩者之單體在分散媒介的存在下之 聚合物產物,其中此聚合物的Ew係從約2〇〇至約4,〇〇〇,較 佳係從約200皇約1,400。 而且,本發明係關於一種製造上述組合物之較佳方法, 其包括至少一種含可聚合丙烯酸系及/或乙烯基之單體與 至少一種含有至少一個離子或可離子化基之單體在分散媒 介中進行聚合反應。 本發明另關於一種含有本發明聚合物或組合物之非全氟 化聚電解質隔膜,也關於含有本發明隔膜之燃料電池及 電池。 0 \90\90872 DOC4 -10· 1343143 而且, 並關於一 本發明係關於_ I rr- ^ '種包含上述隔膜之隔膜電極套 種利用此隔膜電極套組之燃料電池。 組 【實施方式】 全氟化聚電解質_係用於提供高陽離子運送並已廣泛 用作離子父換1¾膜q合物離子交換隔膜係相當於固體聚 &物電解貝或聚合物交換隔膜(pEM)。 最常用並可由商業公司購得之隔膜是Να〇η⑧及
Aci^ex®。但是,文獻中極少摇述非全氟化聚電解質隔膜 。這是由於隔膜的耐化學性、耐電化學性及機械強度是燃 料電池應用之重要性f的事實。實際上,隔膜經常處於高 差[下而且,S隔膜是非常薄(小於50微米)時,機械強度 變仔重要。用於燃料電池或蓄電池應用時,隔膜係處於可 達200t之溫度下非常酸的媒介中和金屬離子、溶劑和類似 物的存在下,因此需要高耐化學性以及耐電化學性。使用 齓化鹼時’因為氟化物質具有天生固有耐化學性及耐電化 學性’因此經常可符合這些要求。但是,這些隔膜顯示包 括,但不限於高溫(70、_200t:範圍)下機械性質差 '交又污染 及重複吸水-脫水循環後機械故障等限制。另外,製備這些 全氟化聚電解質需要數個步驟並包括造成高成本之化學程 序毛展谷易且便且的化學程序將進一步解決燃料電池商 業化的屏障。 本發明係關於一種非全氟化聚電解質,其包含至少一種 丙烯酸系及/或乙烯基樹脂或聚合物,其中此樹脂或聚合物 可有至少一個離子或可離子化基,如磺酸化及/或膦酸化基 O:\90\90872 DOC4 • 11- 1343143 丙烯酸系樹脂之混合物或可另外包含非丙烯酸系樹脂,如 乙烯基單體及苯乙烯系單體β ' 可用於非全氟化聚電解質之乙烯基單體實例包括,但不 限於苯乙烯、乙酸乙烯酯、乙烯基醚、乙烯基酯如購自shell 之VeoVa 9及Ve〇Va 1〇、丙烯酸乙烯酯、新戊酸乙烯酯、苯 甲酸乙烯酯、硬脂酸乙烯酯及類似物和其任何組合物。 此外’非全氟化聚電解質包含至少一個離子(如績酸鹽或 膦酸鹽)或可離子化基如磺酸化或膦酸化基或磺醯基。可離 子化基是一個可形成離子基之基團,如環狀胺基酸、礦内 8曰、順丁烯一酸針、硫醇、硫化物、ph〇Sphaiane及類似基 團。這些基團可藉任何方式如在一或多種含有離子或可離 子化基之單體的存在下摻合丙烯酸系及/或乙烯系樹脂成 為非全氟化聚電解質的一部分。在另一實例中,一或多種 用於形成非全氟化聚電解質之單體可包含離子或可離子化 基。 除了上述有關丙烯酸系及/或乙烯系樹脂之組份外,丙烯 西文糸及/或乙稀糸樹脂可另包含或另在一或多種附加單體 的存在下形成’只要這些單體可與整體形成之丙烯酸系及/ 或乙烯系樹脂相容,其中這些附加單體視情況具有任何官 能基類型。 如早先所述’最好丙烯酸系及/或乙烯系樹脂是數種單體 聚合的結果,其中之一包含離子或可離子化基,另一個係 包含丙烯酸系及/或乙烯系樹脂之丙烯酸系及/或乙烯系單 位。更佳係丙烯酸系及/或乙烯系樹脂係由(1)丙烯酸烷基酯 0 \90\908?2 D〇C4 -13- 1343143 體實例包括異丁基甲基丙烯醯胺、曱基丙烯酸去水甘油酯 、二甲基丙烯酸二乙二醇酯及三甲氧基矽烷甲基丙烯酸酯 。可能希望交聯以獲得較佳機械性質及耐溶劑性。 對於某些特定應用’可利用低分子量可共聚合聚合物或 募聚物。再者,使用丙烯酸烧基酯(1)與曱基丙烯酸烷基酯 (2)之混合物時,可適當地調整其比例以達到所需性質。 包含至少一個離子或可離子化基之單體(5)實例包括,但 不限於丙烯酿胺橫酸丙酯、乙烯基膦酸、乙稀基績酸、曱 基丙烯酸項酸丙酯、曱基丙稀酸項酸乙酯》較佳係使用這 些單體之酸型態或鹽衍生物。例如,在粒種乳化聚合中, 可在第一階段或第二階段或兩階段都摻入磺酸化單體。離 子基的含量最好係從約2 0 0至約2 5 0 0 E W,較佳係從約2 〇 〇 至約1100 EW,其中EW是當量,而且是每磺酸化單位之聚 合物克數。 本發明包含至少一種丙烯酸系或乙烯基樹脂或兩者之聚 合物中丙烯酸系或乙烯基樹脂相關當量最好係從約2〇〇至 約4,000 ’較佳係從約2〇〇至約ι,4〇〇,其中該聚合物具有至 少一個離子或可離子化基。此較佳當量範圍提供較佳隔膜 形成性質及避免氟聚合物需求之能力。本發明聚合物視情 況可以摻合物形式形成。較佳地,本發明聚合物係利用慣 用交聯技術進行交聯。 交聯可經由慣用方法完成,包括,但不限於自縮合、第 二交聯劑之添加或輻射交聯。這些係完整描述於文獻中並 為热知技術。可進行自縮合交聯之單體實例包括Ν_羥甲基 O:\90\90872. DOC4 -15- 丙烯醯胺、異丁氧基曱基丙烯醯胺、N -亞甲基雙丙烯醯胺 及曱基丙烯酸去水甘油酯。第二交聯劑實例包括異氰酸酯 、二聚氱胺、環氧化物、羧酸酯、烷氧基矽烷、矽酮、吖 %丙烷及碳二亞胺。輻射交聯之實例包括電子束、紫外光 及γ-射線。 s可水合乙烯基及/或丙烯酸系單體之混合物的聚合反 應可分開進行,然後與一或多種聚合物摻合在一起或在一 或多種聚合物的存在下進行聚合。含乙烯基及/或丙烯酸系 單體之聚合反應可藉溶液、整體、乳化聚合或任何其他已 知聚合方法達到。 若含可聚合乙烤基及/或丙婦酸系離子之單體混合物的 聚合反應是分開進行,然後與一或多種聚合物摻合在一起 ,此摻合可經由各種慣用方式進行,其包括,但不限於溶 液掺合、擠壓摻合、乳膠摻合及類似方法。對於溶液摻合 ’聚合物可溶解或分散在溶劑中。聚合物所用溶劑可類似 或異於含丙烯酸系/乙烯基離子之聚合物所用溶劑。例如, 摻合可包含兩種溶劑溶液/分散液或將粉末加入溶劑溶液/ 分散液中或兩種聚合物溶於相同溶劑或任何其他組合物中 。典型所用溶劑包括四氫呋喃、丙酮、二甲基亞硬、二曱 基甲酿胺、Ν-甲基吡咯酮。對於熔化擠壓摻合,典型擠壓 溫度範圍係介於約l〇〇t與約30(TC之間,較佳係從約yo °C至約250°C。材料可被擠壓成如顆粒或薄膜形狀。對於乳 膠掺合例子,可在數種慣用方式下產生混合:丙稀酸系/乙 烯基乳膠可與聚合物乳膠混合或丙烯酸系/乙稀基聚合物 〇\90\90872.DOC4 •16- 1343143 可分散或溶於聚合物乳膠中或任何其他已知混合方式a混 合可包含超過兩種乳膠。各乳膠之用量及性質係依獲得預 期物理及化學性質和獲得預期EW的方式調整。在水性隔膜 例子(如直接乳膠製得之例子)中,可針對所需性質調整一或 多種乳膠之粒徑及固體含量。 對於溶劑聚合反應,聚合反應可利用慣用技術發生。在 含有另一種聚合物之摻合物例子中,聚合物摻合物所用溶 劑可類似或異於丙烯酸系/乙烯基聚合物所用溶劑。例如, 摻合可包括兩種溶劑溶液/分散液或將粉末加入溶劑溶液/ 分散液中或兩種聚合物溶於相同溶劑或任何其他組合物中 典型所用;谷劑包括二曱基亞硬、二甲基甲酿胺、Ν·甲基 口比嘻明、異丙醇、甲醇及類似溶劑。 乳化聚合反應可在與慣用乳化聚合相同之條件下進行。 最好將界面活性劑、聚合起始劑、鏈轉移劑、{)^1調整劑並 最後將溶劑和鉗合劑加入粒種乳膠中,反應係在足夠壓力 、溫度及時間之適合反應條件下進行,如在大氣壓力及一 般從約20至約150°C,更佳係從約40至約80。(:之溫度下進.行 約0.5至約6小時。 此粒子的粒徑係從約9〇至約5〇〇毫微米,較佳係從約5〇 至約300毫微米,其中聚合物的用量係從約5至約95重量% ’丙稀酸系或乙烯系樹脂的用量係從約95至約5重量%。乳 化聚合反應可依照標準方法完成:從一開始利用單體分散 液進行之批次聚合反應;半連續聚合反應,其中連續戒分 批餵入部分單體混合物;及連續聚合反應,其中在反應期 〇 \90\90872 DOC4 -17- 。亥樹月曰,®為離子或可離子化基,如績酸化基已存在於單 體上。此外,因為最好聚合離子或可離子化基,其沿聚合 物鏈之分布可容易地藉由技術中已知慣用方式,如注射添 加、連續進料、晚添加及類似方式控制。因此,可比先前 更奋易控制所得離子或可離子化基纟聚合物推纟物所形成 隔膜中之分布。因此,可達到各種性質如均化度、亂度、 非均化度及類似性質的調整。 此外,由於上述這些各項優點,本發明申請案可包括, 但不限於隔膜、燃料電池、塗料、離子交換樹脂、油回收 、生物隔膜、蓄電池及類似物。 聚合物離子隔膜或聚電解質隔獏可由本發明聚合物製成 。聚合物離子隔膜可由慣用薄膜製備方法製得,如溶化擠 壓、溶劑澆鑄、乳膠膠澆鑄及類似方法。隔膜電極套組可 由本發明隔膜及可用於製備隔膜電極套組之燃料電池製成 。利用本發明聚合物形成隔膜時,就聚合物中所存在之離 子丙稀酸系或乙烯基樹脂而言,聚合物可具有任何當量, 較佳係其當量為從約200至約4,000,較佳係從約2〇〇至約 1,500,極佳係從約200至約1,400。 更詳細地’本發明組合物在燃料電池、蓄電池及類似物 上是特別有用的。燃料電池及蓄電池中所用設計或組份將 與慣用燃料電池及蓄電池相同,除了利用本發明組合物形 成聚合物離子交換隔膜之外。因此,本發明可使用如美國 專利第5,795,668號和PCT公告案WO 98/22989以及W〇 98/20573中所述製造燃料電池及蓄電池的設計及方式並將 0 \90\90872 OOC4 •20- 1343143 其全文以引用方式完整地併入本文中。此隔膜可單獨使用 或與慣用填料’如矽石及類似物一起使用。燃料電池可使 用液態或氣態燃料如液態烴如甲醇。本發明燃料電池可在 寬廣操作條件範圍下操作。本發明燃料電池可具有多孔支 樓層及離子交換樹脂,其中該離子交換樹脂係受載於多孔 支標層至少一側上。本發明可用於直接曱醇燃料電池或其 他燃料電池中。較佳地,本發明燃料電池具有低燃料交又 污染、高導電率及/或高機械強度。隔膜厚度可能是慣用的 ’但最好是從約1至約1 〇密耳,較佳係從約3密耳至約5密耳 。此外,隔膜的當量最好是從約200至約2,500,較佳係約 200至約1,4〇〇。多孔支撐層可由任何慣用材料如含氟聚合 物或其他含烴聚合物如聚烯烴製成。多孔支撐層具有孔徑 '孔隙率及厚度相關慣用參數。本發明燃料電池最好具有 極佳電性質及極低電阻。 藉由下列實例使本發明更清楚,其中這些實例係被解釋 成本發明純示範例。 實例 在所有表中,除非另外指示,單體量係以重量份數表示。 本發明組合物係利用下列材料及反應條件製得: 原料 無另外純化地使用單體(ATOFINA化學試劑公司,
Aldrich)、起始劑(Aldrich,DuPont)、界面活性劑(Aldrich) 及緩衝液(Aldrich)。 反應 O:\90\90872 DOC4 -21- 1343143 預先將過硫酸銨0.3克、月桂基硫酸鈉1克及去離子水300 克裝入500毫升裝有冷凝器、高純度氮氣及單體入口和機械 攪拌器之四頸鍋中。將反應器加熱高達65°C並以所需速率 利用針筒式泵浦將單體混合物[曱基丙烯酸甲酯(MMA) 46 克及甲基丙烯酸磺酸丙酯9克]送入反應器中。視情況可在 反應期間之前,將一部分單體混合物加入預載物中。然後 藉保持反應溫度並攪拌1 20分鐘以聚合剩餘單體。然後,將 媒介冷卻至室溫、排氣並經紗布過濾最終分散液。最終固 體含量為15重量%。 表1 : 包含磺酸化單體之樹脂的代表性合成樹脂 實例 MMA TPMS BA S IBMA HEMA SPM EW 1 56.6 24 2.2 17.2 1140 2 40 39 2.4 18.5 1330 3 28.6 19 19 9.5 23.8 1035 4 31.5 21.1 21.1 10.5 15.8 1560 5 28.6 19 19 9.5 23.8 1035 6 31.7 21 21 10.5 15.8 1560 7 31.6 21 21 10.5 15.8 1535 8 39.9 39.2 2.4 18.5 1330 9 37.8 3.4 11.8 27.5 19.5 1266 10 33 32.5 2 32.5 758 0 \9〇\g〇872.DOC4 -22- 表2 : 質子導電率測量之實例 實例 澆鑄類型 質子導電率 来 5 乳膠澆鑄 25 6 乳膠澆鑄 34 7 乳膠澆鑄 *---- 22 8 乳膠澆鑄 13 9 溶液澆鑄 20 10 溶液澆鑄 60 2 溶液澆鑄 9 1343143 實驗: 導電率測量係藉電化學阻抗頻譜分析儀以四探針構型完 成。測量係以Gamry儀器(電位儀-Galvanostat zrapC4/750 及EIS 300軟體)在5X105與1 Hz之間進行。在此所示值係在 室溫下浸沒條件下獲得。 調配物的製備如下: 進行乳膠之調配如下: 將2克Baybond 116及1克Acrysol 275溶於4克丁讀中。溶 液與2克TEP混合,在固定攪拌下將所得溶液緩慢地加入1〇〇 克乳膠中。 利用刮刀型塗佈器將薄膜澆鑄在玻璃基板上並在烘箱中 範圍從80C至l〇〇C之溫度下固化1至Η分鐘。 溶劑調配物的製備如下: 乾燥丙烯酸系乳膠並回收所得粉末。然後,將1 〇至2〇克 〇 ^90872 DOC4 -23-
Claims (1)
1343143 第093102930號專利申請案 中文申請專利範圍替換本(99年12月) 拾、申請專利範圍的if人 1. 一種包含非全氟化聚電解質之隔膜,其中該非全氟化聚 電解質包含至少-種具有至少—個離子基或可離子化基 之丙烯酸系、樹脂或乙缔基樹脂或其兩者,其中該非全氟 化ΛΚ電解貝不含氟聚合物,其中該離子基或可離子化基 為續酸化基或膦酸化基或其兩者,其中該丙烯酸系樹脂 或乙烯基樹脂或其兩者包含至少一具有可交聯之官能基 的可共聚合單體,其中該隔膜係已交聯,且其中該可共 聚合單體包含異丁基甲基丙烯醯胺、曱基丙烯酸去水甘 油S曰一甲基丙烯酸二乙二醇酯或三曱氧基矽烷曱基丙 烯酸酯。 2. 如申請專利範圍第丨項之隔膜,其中該非全氟化聚電解質 在交聯前具有約200至約4,〇〇〇之當量(EW)。 3‘如申請專利範圍第旧之隔膜,其中該非全氣化聚電解質 在交聯前具有約200至約ι,5〇〇之當量。 90872-991215.doc
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- 2004-01-26 CA CA2456224A patent/CA2456224C/en not_active Expired - Fee Related
- 2004-02-06 CN CNA2004100040433A patent/CN1526758A/zh active Pending
- 2004-02-09 TW TW093102930A patent/TWI343143B/zh not_active IP Right Cessation
- 2004-02-09 KR KR1020040008364A patent/KR20040079842A/ko not_active Application Discontinuation
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2007
- 2007-06-26 US US11/768,448 patent/US20070259240A1/en not_active Abandoned
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CN1526758A (zh) | 2004-09-08 |
CA2456224C (en) | 2012-01-24 |
JP2004269875A (ja) | 2004-09-30 |
EP1455407A3 (en) | 2010-04-14 |
KR20040079842A (ko) | 2004-09-16 |
US20070259240A1 (en) | 2007-11-08 |
US20040175625A1 (en) | 2004-09-09 |
EP1455407A2 (en) | 2004-09-08 |
JP4864292B2 (ja) | 2012-02-01 |
CA2456224A1 (en) | 2004-09-06 |
TW200418226A (en) | 2004-09-16 |
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