CN101171271B - 具有减量羰基端基的氟化离聚物 - Google Patents
具有减量羰基端基的氟化离聚物 Download PDFInfo
- Publication number
- CN101171271B CN101171271B CN2006800154198A CN200680015419A CN101171271B CN 101171271 B CN101171271 B CN 101171271B CN 2006800154198 A CN2006800154198 A CN 2006800154198A CN 200680015419 A CN200680015419 A CN 200680015419A CN 101171271 B CN101171271 B CN 101171271B
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- Prior art keywords
- fluoropolymer
- group
- end group
- salt
- pseudohalogen
- Prior art date
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title description 23
- 230000002829 reductive effect Effects 0.000 title description 7
- 229920000554 ionomer Polymers 0.000 title 1
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 95
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 95
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 27
- 125000002577 pseudohalo group Chemical group 0.000 claims description 21
- 238000010526 radical polymerization reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 150000001768 cations Chemical class 0.000 abstract description 3
- 125000002560 nitrile group Chemical group 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- 229910006127 SO3X Inorganic materials 0.000 abstract 1
- 239000003999 initiator Substances 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 15
- 239000000446 fuel Substances 0.000 description 14
- -1 bromine anions Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004160 Ammonium persulphate Substances 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 235000019395 ammonium persulphate Nutrition 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000004334 fluoridation Methods 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000005502 peroxidation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001774 Perfluoroether Polymers 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000003682 fluorination reaction Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- TWIYDBQRYCWOAU-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfinic acid Chemical compound OS(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F TWIYDBQRYCWOAU-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940005989 chlorate ion Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- AAFRWOZIOHGYRT-UHFFFAOYSA-N fluoro butane-1-sulfinate Chemical compound CCCCS(=O)OF AAFRWOZIOHGYRT-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical compound OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
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Abstract
本发明公开了一种含氟聚合物,其包括:多个以-CF2SO3X、-CF2SO2F或其组合封端的侧基,其中X选自H+和一价阳离子;和至少一个-CF2Y端基,其中Y选自:氯原子、溴原子、碘原子、腈基和-SO3X基团。
Description
发明领域
本发明涉及适合用作电化学装置内的电解质膜的含氟聚合物。具体地,本发明涉及具有减量羰基端基的含氟聚合物和氟化离聚物。
发明背景
燃料电池是电化学装置,其通过燃料如氢和氧化剂如氧的催化结合而产生可用的电流。与常规发电装置如内燃发电机相反,燃料电池不利用燃烧方式。由此,燃料电池只产生很少量的有害流出物。燃料电池将氢燃料和氧直接转化为电,与内燃发电机相比,燃料电池能够以更高效率运行。
燃料电池如质子交换膜(PEM)燃料电池典型地包含膜电极组件,该组件由位于一对气体扩散层之间的催化剂涂布膜组成。所述催化剂涂布膜本身典型地包括位于一对催化剂层之间的电解质膜。电解质膜的两侧被称为阳极部分和阴极部分。在典型的PEM燃料电池中,将氢燃料引入阳极部分,氢在这里反应并分解成质子和电子。电解质膜将质子运输到阴极部分,同时允许电子流流过外部回路到达阴极部分,以提供能量。将氧引入阴极部分并与质子和电子反应,以形成水和热量。
另一类电化学装置是电解电池,其中使用电产生化学变化或化学能量。电解电池的一个例子是氯-碱性膜电池,其中通过阳极和阴极之间的电流来电解氯化钠水溶液。电解液被耐受苛刻条件的膜分成阳极液部分和阴极液部分。在氯-碱性膜电池中,在阴极液部分收集苛性氢氧化钠,在阴极部分释放氢气,在阳极从富含氯化钠的阳极液部分释放氯气。
由于它们的离子性质,氟化离聚物适合形成燃料电池、电解电池和其它电化学装置内的电解质膜。典型地通过氟化离子型单体或前体的自由基聚合来制备氟化离聚物。然而,自由基聚合还会在所得氟化离聚物上产生羰基端基(例如-COOH端基、-COO-端基、-COF端基和-CONH2端基)。羰基端基易于受到过氧化物游离基的攻击,这会减少氟化离聚物的氧化稳定性。在燃料电池、电解电池或其它电化学电池的运行过程中,能够形成过氧化物。这会降解氟化离聚物,并相应地减少给定电解质膜的使用寿命。
发明概述
本发明涉及一种含氟聚合物,其包括多个以-CF2SO3X、-CF2SO2F或其组合封端的侧基、和至少一个-CF2Y端基。X选自H+和阳离子。Y选自:氯原子、溴原子、碘原子、腈基和-SO3X基团。所述含氟聚合物具有提高的氧化稳定性,适合形成用于电化学装置的电解质膜。
本发明还涉及一种制备含氟聚合物的方法。所述方法包括:在盐、拟卤素、或盐和拟卤素的组合存在的情况下,使氟化单体进行自由基聚合以制备含氟聚合物。该含氟聚合物包括多个以-CF2SO3X、-CF2SO2F或其组合封端的侧基、和至少一个-CF2Y端基。X选自H+和阳离子。Y选自:氯原子、溴原子、碘原子、腈基和-SO3X基团。
本发明还涉及一种制备含氟聚合物的方法,该方法包括提供氟化单体,其中至少一种氟化单体包括以-CF2SO2F封端的基团。该方法还包括:在盐、拟卤素、或盐和拟卤素的组合存在的情况下,使氟化单体发生自由基反应以制备含氟聚合物,其中相对于在没有盐或拟卤素存在的情况下制备的类似含氟聚合物,所述含氟聚合物的羰基端基减少了至少约25%。
发明详述
本发明涉及一种含氟聚合物,其包含具有多个侧基的氟化主链和至少一个非羰基端基。所述含氟聚合物的非羰基端基是-CF2Y端基,其中Y是活性的原子或基团,例如氯原子、溴原子、碘原子或腈基(nitrilegroup)。-CF2Y端基取代了羰基端基,否则它将受聚合的影响。用-CF2Y端基代替羰基端基提高了含氟聚合物的氧化稳定性。提高的氧化稳定性保持了含氟聚合物的耐久性,这相应地保持了给定电解质膜的使用寿命。
用于本发明含氟聚合物的特别合适的组合物的-CF2Y端基是-CF2Cl端基(即Y为氯原子)。氯官能团是稳定的,与羰基端基相比能够提供更高的氧化稳定性。
含氟聚合物的侧基由-CF2SO3X、-CF2SO2F或其组合封端,其中X可以是氢离子(H+)、或一价或多价阳离子(例如Li+)。以-CF2SO3X封端的侧基为含氟聚合物提供了离子电导性。由此,具有-CF2SO3X封端侧基的本发明含氟聚合物是适合形成电解质膜的氟化离聚物。以-CF2SO2F封端的侧基是非离子型基团,它随后可以被水解以形成以-CF2SO3X封端的侧基。由此,具有-CF2SO2F封端侧基的本发明含氟聚合物可以是氟化离聚物的前体。
用于含氟聚合物的合适侧基包括具有式-R1-SO3X、-R1-SO2F或其组合的基团,其中R1可以是支化或未支化的全氟烷基、全氟烷氧基或全氟醚基,其中包含一至十五个碳原子和零至四个氧原子。用于含氟聚合物的特别合适的侧基包括-O(CF2)4SO3X、-O(CF2)4SO2F、-OCF2CF(CF3)OCF2CF2SO3X、-OCF2CF(CF3)OCF2CF2SO2F及其组合。
含氟聚合物的主链可以是部分或全部氟化的。按主链的总重量计,主链中合适的氟浓度包括约40wt%或更高重量比。在本发明的一个实施方案中,含氟聚合物的主链是全氟化的。
通过聚合混合物的自由基聚合、然后将侧基水解以提供离子型侧基,可以制备本发明的含氟聚合物。所述聚合混合物包含氟化单体、引发剂、和盐、拟卤素、或盐和拟卤素的组合。通过在盐或拟卤素存在的情况下使用引发剂来引发自由基聚合。氟化单体聚合以形成主链和侧基,其中侧基以-CF2SO2F终止。在这种情况下,侧基是稳定的,在聚合过程中基本上不受盐或拟卤素的影响。所述盐和拟卤素可减少在主链上形成的羰基端基量,并用-CF2Y端基代替羰基端基。
本发明含氟聚合物中,合适的羰基端基浓度减少的例子包括:相对于在没有盐或拟卤素存在的情况下制备的类似含氟聚合物,减少了至少约25%的羰基端基。本发明含氟聚合物中羰基端基的特别合适的浓度减少的例子包括,相对于在没有盐或拟卤素存在的情况下制备的类似含氟聚合物,减少了至少约50%的羰基端基。这提高了含氟聚合物的氧化稳定性。可以使用各种分析技术确定端基的组成。合适的分析技术的例子包括红外检测(参见例如Grootaert等人,美国专利6,825,300号)和F-NMR检测(参见例如Buckmaster等人,美国专利4,742,122号和Schreyer,美国专利3,085,083号)。
用于本发明的合适盐包括具有式MeY的盐,其中Me是一价或多价阳离子,Y是活性的原子或基团,如上所述(即氯阴离子、溴阴离子、碘阴离子或氰阴离子)。盐的适合阳离子包括钠、钾和铵。用于自由基聚合的盐可以是同质的盐或不同盐的共混物。
用于本发明的合适拟卤素包括含腈的拟卤素化合物,其提供腈端基(即Y为腈基)。包含腈的拟卤素化合物具有一个或多个腈基,其功能与用卤素代替腈基的化合物相同。合适的含腈拟卤素化合物的例子包括NC-CN、NC-S-S-CN、NC-Se-Se-CN、NCS-CN、NCSe-CN、Cl-CN、Br-CN、I-CN、NCN=NCN及其组合。
在自由基聚合过程中,盐的活性原子/基团或拟卤素的腈基与含氟聚合物主链的至少一个末端化学结合。这提供了“Y”原子或-CF2Y端基来代替羰基端基。例如,如果在KCl盐存在的情况下进行自由基聚合,则所提供的至少一个端基将为-CF2Cl端基。或者,如果在NC-CN拟卤素存在的情况下进行自由基聚合,则所提供的至少一个端基将为-CF2CN端基。
可以相对于所用引发剂的量选择所用的盐或拟卤素量。通常,含氟聚合物上-CF2Y端基的浓度随着盐/拟卤素相对于引发剂的浓度比而增加。相应地,含氟聚合物上羰基端基的浓度随着盐/拟卤素相对于引发剂的浓度比而下降。盐/拟卤素的活性原子/基团相对于引发剂的合适摩尔比范围为约1/0.1至约0.1/10,特别合适的摩尔比范围为约1/0.5至约0.1/5。
用于自由基聚合的合适引发剂包括过氧化物、过硫酸盐、过碳酸盐、酯、含镁引发剂、含铈引发剂及其组合。合适引发剂的另外的例子包括通过氧化还原反应产生自由基的引发剂体系,例如氧化剂与还原剂的组合。合适的氧化剂包括过硫酸盐,例如过硫酸铵(APS)、过硫酸钾(KPS)、过硫酸钠及其组合。额外的合适氧化剂包括含有氯酸盐离子、次氯酸盐离子、溴酸盐离子及其组合的化合物。合适的还原剂包括亚硫酸盐如亚硫酸钠、亚硫酸氢钠、偏亚硫酸氢盐(metabisulfite)(例如亚硫酸氢钠和亚硫酸氢钾)、焦亚硫酸盐(pyrosulfite)、硫代硫酸盐及其组合。用作引发剂的合适氧化还原体系的例子包括过氧化硫酸氢盐与亚硫酸氢或二亚硫酸盐(disulphite)的组合、硫代硫酸盐与过氧化硫酸氢盐的组合、过氧化硫酸氢盐与肼或偶氮二碳酰胺的组合、和过氧化二亚硫酸盐与氯化钠的组合。按聚合混合物的总重量计,聚合混合物中引发剂的合适浓度范围为约0.01wt%至约3.0wt%,特别合适的浓度范围为约0.05wt%至约2.0wt%。
用于形成含氟聚合物的氟化单体包括至少一种磺酰氟单体和至少一种全氟化共聚单体。优选地,所述氟化单体包括多种磺酰氟单体和多种全氟化共聚单体。所述氟化单体还可以包括非全氟化的单体,例如1,1-二氟乙烯(VDF)、三氟乙烯、乙烯、丙烯及其组合。
合适的磺酰氟单体包括具有式F2C=CF-R2-SO2F的氟化单体,其中R2可以是支化或未支化的全氟烷基、全氟烷氧基或全氟醚基,其中包含一至十五个碳原子和零至四个氧原子。特别合适的磺酰氟单体包括F2C=CFO(CF2)4SO2F、F2C=CFOCF2CF(CF3)OCF2CF2SO2F及其组合。可以通过任何合适的方法合成磺酰氟单体,包括公开于Guerra,美国专利6,624,328号的方法。磺酰氟单体的R2-SO2F基团通常定义了聚合后所得含氟聚合物的侧基。
合适的全氟化共聚单体包括具有式F2C=CF-R3的氟化单体,其中R3可以是氟原子,或者支化或未支化的全氟烷基、全氟烷氧基或全氟醚基,其中包含一至五个碳原子和零至两个氧原子。合适的全氟化共聚单体的例子包括四氟乙烯(TFE)、六氟丙烯(HFP)、全氟乙基乙烯基醚(PMVE)及其组合。特别合适的全氟化共聚单体是TFE。
聚合混合物还可以包含额外的组分,例如缓冲剂、链转移剂、稳定剂、加工助剂及其组合。可以使用链转移剂如气态烃链转移剂来调整所得含氟聚合物的分子量。
聚合混合物还可以包含二亚硫酸盐,例如二亚硫酸钠,其可以与氧化剂(例如APS、氯酸盐离子、次氯酸盐离子和溴酸盐离子)一起使用以提供主链上的-CF2SO3X端基。由此,用于-CF2Y端基“Y”的另一种合适的活性基团包括基团-SO3X。在将聚合混合物与包括一种或多种二亚硫酸盐和一种或多种氧化剂的组分自由基聚合后,本发明的含氟聚合物可以具有至少一个-CF2SO3H端基。然后可以将端基-CF2SO3H后氟化(post-fluorinated),以提供-CF28O2F端基,然后可以将它水解以提供离子型-CF2SO3X端基。因此,用于本发明含氟聚合物的另一种特别合适的组合物的-CF2Y端基为-CF2SO3X端基(即Y为-SO3X基团)。-SO3X官能团是稳定的,提供了比羰基端基更高的氧化稳定性,还为含氟聚合物提供了额外的离子电导性。
聚合混合物还可以包含氟烷基亚磺酸盐和氟烷基亚磺酸,它们也可以与氧化剂(如APS、氯酸根离子、次氯酸根离子和溴酸根离子)一起使用,以提供除-CF2Y端基外还具有至少一个-CF3端基的本发明含氟聚合物。氟烷基亚磺酸盐和氟烷基亚磺酸的合适氟烷基包括氟化脂族基团和全氟化脂族基团,例如全氟丁基亚磺酸盐和全氟丁基亚磺酸。用于制备本发明含氟聚合物的特别合适的体系的例子包括APS引发剂、KCl盐和全氟丁基亚磺酸。所得含氟聚合物包括至少一个-CF2Cl端基和至少一个-CF3端基。
可以以各种方式进行自由基聚合,例如在有机溶剂中、作为水性悬浮聚合、或作为水性乳液聚合。可以在适合给定引发剂体系的任何pH、温度和压力下进行自由基聚合。然而,为了避免预水解-SO2F基团,希望在约六至七的pH范围内进行聚合。用于聚合的合适温度范围为约10℃至约100℃。用于聚合的合适压力范围为约300千帕(KPa)至约3,000KPa。希望在无氧环境下进行聚合。
在一个实施方案中,自由基聚合反应作为水性乳液聚合反应进行,其中包括在乳液的水相中聚合氟化单体。可以以各种方式获得水乳剂,例如通过使用全氟辛酸铵或其盐,或通过使用全氟聚醚。或者,通过在水中用碱制备磺酰氟单体的预制乳液,可以进行水性乳液聚合。
在这后一种替代方案中,预制乳液中水与磺酰氟单体的合适重量比范围为约0.1/1至约1/0.01,其中特别合适的重量比范围为约0.2/1至约1/0.1。可以使用任何合适的碱,例如碱金属的氢氧化物(例如NaOH、KOH和LiOH)、碱土金属的氢氧化物、III族金属的氢氧化物、NH4OH及其组合。预制乳液中碱的合适浓度范围为约0.01摩尔当量至约0.5摩尔当量,其中特别合适的浓度范围为约0.02摩尔当量至约0.3摩尔当量,其中所述摩尔当量是相对于预制乳液中的磺酰氟单体。
可以以常规方式混合预制乳液,例如用均化器、高速搅拌机、胶体磨混合机或超声装置。合适的混合时间范围为约一分钟至约六十分钟,其中特别合适的混合时间范围为约一分钟至约二十分钟。
一旦制备了预制乳液,就将聚合成分(即预制乳液、共聚单体、引发剂、盐/拟卤素和任何额外的组分)投入反应容器中,以引发自由基聚合。可以以连续法、或分批或半分批法进行水乳液聚合。连续法涉及在最佳压力和温度条件下,将成分连续供应到搅拌的反应容器中,同时连续除去所得乳液。分批或半分批方法包括将成分供应到搅拌的反应容器中,并允许它们在给定的温度下反应特定的时间,或者通过将成分投入反应容器中并将共聚单体供应到反应器中,以保持恒定的压力,直到形成所需量的含氟聚合物。可以在用于气态氟化单体乳液聚合的标准或常规容器中进行聚合。自由基聚合产生含氟聚合物胶乳,其中胶乳的含氟聚合物具有以-CF2SO2F封端的侧基和至少一个-CF2Y端基。优选地,含氟聚合物的大量端基为-CF2Y端基。
如上所述,可以将以-CF2SO2F封端的侧基水解,以形成以-CF2SO3X封端的离子型侧基。可以以任何常规的方式进行水解。例如,最初可以使含氟聚合物与碱如LiOH、NaOH、KOH或其组合反应。然后可以使含氟聚合物与酸或离子交换树脂反应,以提供-CF2SO3X,其中X基于所用的酸或离子交换树脂。因此,在聚合和水解后,含氟聚合物是具有以-CF2SO2X封端的侧基和至少一个-CF2Y端基的氟化离聚物。在这种情况下,含氟聚合物具有离子电导性,可用于形成用于电化学装置的电解质膜。还可以以相同的方式水解在主链上形成的任何-CF2SO2F端基,以形成-CF2SO3X端基。或者,可以将聚合的含氟聚合物挤压以形成膜,然后水解。
在本发明的替代实施方案中,含氟聚合物可以经受后氟化处理,以将-CF2Y端基转化为极稳定的-CF3端基。希望在聚合之后但在水解之前进行后氟化处理,以保护侧基。可以以任何常规的方式进行后氟化处理。例如,可以用氟和氮气混合物处理含氟聚合物胶乳,其中按气体混合物的总重量计,气体混合物中氟的浓度为约10wt%至约25wt%。合适的后氟化条件包括:温度范围为约150℃至约250℃,压力范围为约100KPa至约1,000Kpa,反应时间范围为约四小时至约十六小时。还可以搅拌含氟聚合物胶乳,以将新表面连续暴露至气体混合物。
本发明的含氟聚合物特别适合后氟化处理。-CF2Y端基的活性原子/基团“Y”可与氟气体反应,这会减少后氟化所述含氟聚合物所需的时间和能量。当端基包括在高温(例如高于280℃)下较不稳定的活性原子/基团如溴原子、碘原子或腈基时,尤其如此。可容易地后氟化这些端基以提供-CF3端基。具有在高温(例如高于280℃)下稳定的端基如-CF2Cl端基或SO3X端基的含氟聚合物可以不经后氟化步骤而使用,但如果需要,它们也适合进行后氟化。
与本发明的含氟聚合物相反,后氟化具有羰基端基的含氟聚合物需要大量的时间和能量,以将羰基端基转化为-CF3端基。而且,后氟化具有羰基端基的含氟聚合物会形成-COF端基,它们是不合意的,因为它们可能在水存在的情况下回复为羧酸端基。然而,-CF2Y端基是后氟化处理的有效位置,在水存在的情况下不会回复为羧酸端基。
在后氟化处理后,大量含氟聚合物具有以-CF2SO2F封端的侧基和至少一个-CF3端基。优选地,基本上所有的含氟聚合物端基均为-CF3端基。然后可以将含氟聚合物水解,如上所述,以形成以-CF2SO3X5封端的侧基,同时保留-CF3端基。然后含氟聚合物可具有离子电导性,同时还具有高水平的氧化稳定性。
通过任何合适的方法,包括铸塑、塑模、挤压等,可以使本发明的含氟聚合物形成电解质膜。例如,可以从含氟聚合物的胶乳或悬浮液中铸塑电解质膜,然后干燥,退火,或干燥和退火。当含氟聚合物被水解并包含离子型侧基时,这尤其合适。通常,与具有以-CF2SO3X封端的侧基的含氟聚合物相比,具有以-CF2SO2F封端的侧基的含氟聚合物更易于进行熔融处理(例如挤压或热压成各种形状,例如薄膜或膜)。由此,形成电解质膜的替代方法包括熔融处理具有以-CF2SO2F封端的侧基的含氟聚合物,然后水解成型的膜以赋予它们离子性。
在被形成为膜后,还可以使用各种交联技术例如光化学、热和电子束技术来交联本发明的含氟聚合物。合适的交联技术的例子包括电子束交联,该技术通过将含氟聚合物暴露至电子束辐射来完成。合适的电子束辐射剂量包括至少约一兆拉德(megarad),其中特别合适的剂量包括至少约三兆拉德,其中甚至更特别合适的剂量包括至少约五兆拉德,其中最特别合适的剂量包括至少约十五兆拉德。可以使用任何合适的仪器来提供电子束辐射。合适仪器的例子包括商品名为“EnergySciences CB300”的电子束体系,其可购自Energy Sciences,Inc.Wilmington,MA。
还可以在一种或多种交联剂存在的情况下进行交联。用于本发明含氟聚合物的合适交联剂包括多官能化合物如多官能烯烃和其它不饱和交联剂。交联剂可以是未氟化的、氟化程度低的、高度氟化的、或者更优选全氟化的。可以通过任何常规方式将交联剂引入含氟聚合物中。用于引入交联剂的合适技术包括在将含氟聚合物成型为膜前,将交联剂与含氟聚合物共混。或者,可以将交联剂应用至含氟聚合物膜,例如通过将含氟聚合物膜浸入交联剂的溶液中。
由本发明含氟聚合物形成的燃料电池膜的合适厚度包括小于约九十微米,其中特别合适的厚度为小于约六十微米,其中甚至尤其更合适的厚度为小于约三十微米。对于电解应用,由本发明含氟聚合物形成的膜的合适厚度包括约100微米至约300微米。可以通过挤压工艺制备这些膜。
尽管已经参考优选实施方案描述了本发明,但本领域技术人员将意识到,在不背离本发明精神和范围的情况下,可以对形式和细节进行改变。
实施例
在下面的实施例中更具体地描述了本发明,这些实施例仅用于说明目的,因为在本发明范围内的许多修改和变化对本领域技术人员将是显而易见的。除非另有说明,下面实施例中报告的所有份数、百分比和比率均为按重量计,实施例中所用的所有试剂均获自或可购自Aldrich Chemical Company,Milwaukee,WI.,或者可以通过常规技术合成。在下列实施例中使用下列组成简写:
“MV4S”:具有式CF2=CFO(CF2)4SO2F的磺酰氟单体,分子量为378.11。
“TFE”:具有式CF2=CF2的气态四氟乙烯共聚单体,分子量为100.02。
“LiOH·H2O”:氢氧化锂一水合物,分子量为41.97。
“APS”:过氧化硫酸氢铵引发剂。
“KCl”:氯化钾盐。
“二亚硫酸钠”:具有式NaS2O5的二亚硫酸钠。
通过添加4克LiOH·H2O乳化153克MV4S的170克去离子水溶液,制备第一预制乳液。使用以商品名“ULTRA-TURRAX”T25型分散机S25KV-25F购自IKA-Werke GmbH&Co.KG,Staufen,Germany的分散机,在高剪切(24,000rpm)下乳化两分钟。
通过添加11克LiOH·H2O乳化423克MV4S的473克去离子水溶液,制备第二预制乳液。仍然使用分散机在高剪切(24,000rpm)下乳化两分钟。
向装有推进搅拌器体系的4升无氧聚合釜中投入2.8升去离子水和50克KCl。将釜加热到高至60℃,然后将第一预制乳液投入釜中。在60℃下再向釜中投入172克TFE,到达800千帕(KPa)的绝对反应压力。通过向釜中添加引发剂溶液,引发自由基反应,其中引发剂溶液包含5克二亚硫酸钠和6克APS,两者均溶于30毫升去离子水中。
在反应过程中,搅拌器以240rpm运行,反应温度保持在60℃,反应压力保持在800KPa绝对压力。然后在331分钟内,将800克TFE和905克第二预制乳液供应到釜内。然后关闭单体阀门,中断单体供应。连续的聚合将单体气相的压力减至300KPa。此时,将釜排空并用氮气冲洗。
所得含氟聚合物胶乳的固含量为32wt%,其在-18℃冻结。然后在130℃干燥冻结的含氟聚合物。19F-NMR分析显示含氟聚合物组成为88.4mol%TFE、11.6mol%MV4S。19F-NMR分析还显示主链组成为2.7mol%CF2Cl。CF2Cl峰序列的化学位移范围为-77.5份/百万(ppm)至-66.2ppm。元素分析显示含氟聚合物胶乳的氯含量为0.94wt%,根据19F-NMR分析结果。由此,自由基聚合在所得含氟聚合物的主链上提供了CF2Cl端基。MV4S浓度结果显示所得含氟聚合物具有以-CF2SO2F封端的侧基。
Claims (9)
1.一种含氟聚合物,包括:
多个以-CF2SO3X、-CF2SO2F或其组合封端的侧基,其中X选自H+和阳离子;和
至少一个-CF2Y端基,其中Y选自:氯原子、溴原子、碘原子、腈基和-SO3X基团,其中含氟聚合物还包括至少一个-CF3端基。
2.如权利要求1所述的含氟聚合物,其中Y包括氯原子或-SO3X基团。
3.如权利要求1所述的含氟聚合物,还包括全氟化的主链。
4.如权利要求1至3中任一项所述的含氟聚合物,其中所述侧基选自:-O(CF2)4SO3X、-O(CF2)4SO2F、-OCF2CF(CF3)OCF2CF2SO3X、-OCF2CF(CF3)OCF2CF2SO2F及其组合。
5.一种电解质膜,包括权利要求1至3中任一项的含氟聚合物。
6.如权利要求5中任一项所述的电解质膜,其中所述电解质膜是交联的。
7.一种制备含氟聚合物的方法,所述方法包括:在盐、拟卤素或盐和拟卤素的组合存在的情况下,使氟化单体进行自由基聚合以制备含氟聚合物,其中所述含氟聚合物包括多个以-CF2SO2F封端的侧基和至少一个-CF2Y端基,其中Y选自:氯原子、溴原子、碘原子、腈基和-SO3X基团,其中X选自H+和阳离子,该方法还包括后氟化所述含氟聚合物,其中后氟化基本上将-CF2Y端基转化为-CF3端基。
8.如权利要求7所述的方法,还包括水解所述含氟聚合物,其中水解基本上将以-CF2SO2F封端的侧基转化为以-CF2SO3X封端的侧基。
9.如权利要求7或8所述的方法,其中自由基聚合还在一种或多种如下化合物存在的情况下发生,所述化合物选自:二亚硫酸盐、氟烷基亚磺酸盐、氟烷基亚磺酸及其组合。
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2005
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2006
- 2006-05-02 EP EP06752039.5A patent/EP1877454B1/en not_active Not-in-force
- 2006-05-02 JP JP2008510114A patent/JP5166248B2/ja not_active Expired - Fee Related
- 2006-05-02 CN CN2006800154198A patent/CN101171271B/zh not_active Expired - Fee Related
- 2006-05-02 KR KR1020077025468A patent/KR20080003857A/ko not_active Application Discontinuation
- 2006-05-02 WO PCT/US2006/016696 patent/WO2006119224A1/en active Application Filing
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- 2007-04-03 US US11/695,654 patent/US20070185220A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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JP5973319B2 (ja) | 2016-08-23 |
EP1877454A1 (en) | 2008-01-16 |
WO2006119224A1 (en) | 2006-11-09 |
JP2016104854A (ja) | 2016-06-09 |
JP2013232393A (ja) | 2013-11-14 |
EP1877454B1 (en) | 2014-01-22 |
US20060252888A1 (en) | 2006-11-09 |
CN101171271A (zh) | 2008-04-30 |
JP5166248B2 (ja) | 2013-03-21 |
JP2008540738A (ja) | 2008-11-20 |
US20070185220A1 (en) | 2007-08-09 |
KR20080003857A (ko) | 2008-01-08 |
US7214740B2 (en) | 2007-05-08 |
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