CN101685866B - Multilayer fluorine-containing cross-linked ion-exchange membrane and preparation method thereof - Google Patents
Multilayer fluorine-containing cross-linked ion-exchange membrane and preparation method thereof Download PDFInfo
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- CN101685866B CN101685866B CN2009101760006A CN200910176000A CN101685866B CN 101685866 B CN101685866 B CN 101685866B CN 2009101760006 A CN2009101760006 A CN 2009101760006A CN 200910176000 A CN200910176000 A CN 200910176000A CN 101685866 B CN101685866 B CN 101685866B
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 56
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003014 ion exchange membrane Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000004132 cross linking Methods 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000010410 layer Substances 0.000 claims description 53
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 150000002500 ions Chemical class 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 238000007731 hot pressing Methods 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- -1 hempa acid amide Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 14
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 238000007650 screen-printing Methods 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 11
- 238000007766 curtain coating Methods 0.000 claims description 11
- 150000004985 diamines Chemical class 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000004528 spin coating Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 125000002560 nitrile group Chemical group 0.000 claims description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 208000035220 Dyserythropoietic Congenital Anemia Diseases 0.000 claims description 7
- 239000005935 Sulfuryl fluoride Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- 239000004811 fluoropolymer Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229920001002 functional polymer Polymers 0.000 abstract 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 abstract 1
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 48
- 229920000642 polymer Polymers 0.000 description 37
- 230000003252 repetitive effect Effects 0.000 description 30
- 150000003460 sulfonic acids Chemical class 0.000 description 17
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 230000035699 permeability Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 4
- 102100040409 Ameloblastin Human genes 0.000 description 4
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003435 aroyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 150000001451 organic peroxides Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XLDLRRGZWIEEHT-UHFFFAOYSA-N 3-hydroxy-4-nitrobenzoic acid Chemical class OC(=O)C1=CC=C([N+]([O-])=O)C(O)=C1 XLDLRRGZWIEEHT-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical class [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a multilayer fluorine-containing cross-linked ion-exchange membrane and a preparation method thereof, which belongs to the field of functional polymer composite materials. The fluorine-containing cross-linked ion-exchange membrane has a multilayer structure. The ion-exchange membrane with a network structure is formed by taking fluorine-containing ion exchange resin containing cross-linking sites as membrane-forming resin and performing cross-linking reaction under certain conditions. The ion-exchange membrane prepared by the method has the advantages of high proton conductivity and dimensional stability.
Description
The application is 200810138705.4 divides an application
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of exchange membrane containing fluorine and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the TRT of electric energy through electrochemical means, is considered to first-selected cleaning of 21 century, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to PEM.
Though the perfluorinated sulfonic acid PEM that uses is now used for many years, but still exists deficiency not reach the commercialization requirement,, poor dimensional stability low like the high temperature proton conductivity, mechanical strength are not high.Especially dimensional stability aspect, film are also different because of the different swelling ratios of water absorption rate under different humidity.In addition, when the perfluorinated sulfonic acid exchange membrane is worked under higher temperature,, thereby the efficient of fuel cell is descended greatly because the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high working temperature (being higher than 90 ℃) can improve the anti-carbon monoxide property of fuel-cell catalyst greatly.In addition, existing perfluoro sulfonic acid membrane has certain hydrogen or methanol permeability, and especially in DMFC, methanol permeability is very big, becomes fatal problem.Therefore, how to improve perfluorinated sulfonic acid proton exchange film strength, dimensional stability, the permeability of reduction working media etc. is the key subjects that fuel cell industries faces.
The crosslinked thermal stability that can improve polymer, the swelling of minimizing solvent, the mechanical strength of raising polymer has been widely used in fields such as separating absorption and various rubber elastomers.At present, for solving the existing problem of perfluorinated sulfonic acid PEM, a lot of crosslinking technologicals are also explored.The cross-linking method of the crosslinked generation sulphonyl of sulfonic acid chloride acid anhydride has been described like US20070031715; Formed in the method sulphonyl acid anhydride cross-linked structure can effectively improve the mechanical strength of film, is that sulphonyl acid anhydride unit is unsettled to alkali but this cross-linked structure has significant disadvantages.US20030032739 then reaches crosslinked purpose through connecting at the alkyl between strand of the sulfonyl on the macromolecular chain.This crosslinked solvent swell property that can well reduce film.But need the unsuitable course of industrialization of a lot of steps for obtaining this cross-linked structure.The disclosed perfluor sulfonyl fluorine type film that will melt extrude of US6733914 soaks the PEM that forms the sulfimide cross-linked structure in ammoniacal liquor, the perfluoro sulfonic acid membrane of handling like this has good mechanical strength and dimensional stability.But utilizing the resulting film of this patent will be uneven film; Because ammonia gets into film through the method for infiltration; Ammonia meeting and sulfuryl fluoride react in the process of infiltration; The sulfuryl fluoride of reaction will stop ammonia further to the inner diffusion of film, thereby at the very high crosslink density of the surface of film formation, and that the inside of film does not almost take place is crosslinked.The big crosslinked conductivity of film that makes in surface sharply descends.
The disclosed triazine ring cross-linked structure perfluoro sulfonic acid membrane that contains of CN200710013624.7 and US7259208 has good mechanical strength and dimensional stability equally.
Summary of the invention
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: stable, high conductivity, high mechanical properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer decline (equivalent value EW value reduces, ion exchange capacity IEC=1000/EW) film strength simultaneously also reduced.Therefore, preparation has a macroion exchange capacity, and the ionic membrane that can keep mechanical strength and high proton conductivity simultaneously is very important.
Deficiency to prior art the objective of the invention is, and a kind of multilayer fluorine-containing cross-linking ion film and preparation method are provided.The exchanger resin that the present invention adopts forms cross-linked structure can reduce the proton conductive that permeability is improved polymer film, and effectively the damaged while of spreading of block film machinery is further reduced gas permeability to adopt sandwich construction.
The present invention provides a kind of multilayer fluorine-containing cross-linking ion film; Be to be the multilayer film of the 2-40 layer that forms of the ion exchange fluoro resin of 600～1300mmol/g with the EW value; Wherein have at least 1 layer to have cross-linked structure, conductivity 40～150mS/cm, hot strength 10～60Mpa; Gross thickness 10～300 μ m;
Said cross-linked structure is selected from one or more as shown in the formula (I), (II), (III), (IV) and/or in the structure (V):
Wherein, G
1=CF
2Or O, G
2=CF
2Or O, R
fBe C2-C10 perfluor carbochain or chloride perfluor carbochain;
Wherein, R is methylene or perfluor methylene, and n is 0～10 integer;
Following formula formula (I), (II), (III), (IV) and/or (V) in sweep and the fluorine-containing carbochain of broken line representative.
Preferably, the EW value of said ion exchange fluoro resin is 700-1200mmol/g; The number of plies of multilayer film is the 2-10 layer, gross thickness 10-50 μ m.
Described ion exchange fluoro resin is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain functional group, or the mixture of above-mentioned copolymer;
Fluorine containing olefine is selected from: tetrafluoroethene, and CTFE, trifluoro-ethylene, hexafluoropropylene, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethene or CTFE;
The fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (VI), (VII) and/or in the structure (VIII):
Wherein, a, b, c are 0～1 integer, but can not be zero simultaneously;
D is 0～5 integer
N is 0 or 1;
R
F1, R
F2And R
F3Be selected from perfluoroalkyl or dichlorodifluoromethan base respectively;
X is selected from F, Cl, Br, or I;
Y
1, Y
2, Y
3Be selected from SO
2M, COOR
3, or PO (OR
4) (OR
5), wherein:
M is selected from F, Cl, OR or NR
1R
2Said R is selected from methyl, ethyl or propyl group, H, Na, Li, K or ammonium root; R
1And R
2Be selected from H, methyl, ethyl or propyl group respectively; R
3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R
4, R
5Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group;
The described fluorine-containing alkene monomer that contains crosslink sites is selected from one or more as shown in the formula (IX) and/or in the structure (X):
Wherein, Y
4, Y
5Can be selected from Cl, Br, I or CN respectively;
A ', b ', c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0;
X
1Be selected from Br, F, Cl, Br, or I;
N ' is 0 or 1;
R
F4, R
F5, R
F6Be selected from perfluoroalkyl respectively;
Preferably, the EW value of said ion exchange fluoro resin is 700-1200mmol/g; The number of plies of multilayer film is the 2-10 layer, gross thickness 10-50 μ m.
In the multilayer fluorine-containing cross-linking ion film each layer can all form cross-linked structure and also allow part layer not form cross-linked structure, also can form cross-linked structure with interlayer by layer.Because layer and interlayer form crosslinked active force between making layer by layer and greatly strengthen, thereby difficult the disengaging.Preferred two skins have cross-linked structure.
The present invention also provides a kind of preparation method of multilayer fluorine-containing cross-linking ion film, each monofilm utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology process; The preparation of multilayer film is through compound between monofilm; Compound between compound or multilayer film and multilayer film between multilayer film and monofilm, also can directly on monofilm that has made or multilayer film, utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology preparation.
Preferably, the step of solution casting, solution casting, silk-screen printing technique, spin coating, spraying or dipping is following:
(1) with ion exchange fluoro resin, crosslinking agent, additives such as acid or radical initiator are distributed to solvent and form mixture; Ion exchange fluoro resin content is 1～80% in the mixture, weight ratio; Used solvent is one or more in dimethyl formamide, dimethylacetylamide, NMF, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerine; Said crosslinking agent is selected from the said material of formula (XI), ammonia, hydrazine, organic diamine or can discharge ammonia through chemical treatment, the material of hydrazine, organic diamine;
(2) utilize the mixture of preparation in the step (1) passing through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming on the flat board or on the single or multiple lift film that has prepared; Will be under 30～300 ℃ temperature during film forming heat treatment 10～100 minutes;
(3) crosslinked in the film forming, or after the film forming, formation be (I), (II), (III), (IV) and/or (V) shown in cross-linked structure.
Preferably, the used solvent of step (1) is one or more in dimethyl formamide, dimethylacetylamide, NMF, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerine; Said crosslinking agent is selected from the said material of formula (XI), ammonia, hydrazine, organic diamine or can discharge ammonia through chemical treatment, the material of hydrazine, organic diamine;
Preferably, will be under 80～250 ℃ temperature during film forming in the step (2) heat treatment 20～60 minutes.
The method that forms the cross-linked structure shown in the formula (I) comprises heat, light, electron radiation, plasma, X ray or radical initiator, also can when one or more crosslinking agents exist, pass through heat, light, electron radiation, plasma, X ray or action of free radical initiator and form cross-linked structure.Wherein the structure of employed crosslinking agent is as shown in the formula shown in (XI):
X
2R
f7X
3
(XI)
X
2, X
3Be selected from Cl, Br, or I; R
F7Be selected from perfluoroalkyl or dichlorodifluoromethan base;
Said radical initiator is organic peroxide, azo-initiator etc., and wherein the general formula of peroxide initiator can be expressed as (XII) and (XIII):
R
1OOR
2
(XII)
R
1, R
2, can be respectively from following groups but be not limited only to choose arbitrarily these groups:
R
1, R
2, can be respectively from following groups but be not limited only to choose these groups: the fluorine-containing or perfluoro acidyl of the fluorine-containing or perfluoroalkyl of the acyl group of the substituted alkyl of the alkyl or aryl of H, C1～C20, C1～C20, the aroyl of C1～C20, C1～C20 or the substituted alkyl of aryl, C1～C20, the fluorine-containing or perfluor aroyl of C1～C20; But R
1, R
2Can not select H simultaneously;
R
3, R
4Can be respectively from following groups but be not limited only to choose arbitrarily these groups:
Fluorine-containing or the perfluoroalkyl of the substituted alkyl of the alkyl or aryl of C1～C20, C1～C20 or the substituted alkyl of aryl;
Azo-initiator is but is not limited only to following several kinds:
Azo-initiator is but is not limited only to following several kinds: Celogen Az, azodiisobutyronitrile, AMBN, ABVN, azo-bis-iso-dimethyl, 1-((cyanic acid-1-Methylethyl) azo) formamide, 1; 1 '-azo (cyclohexyl-1-cyanic acid), 2; 2 '-azo (2-methyl-propyl amidine) dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid) or 3-hydroxyl-4-nitrobenzoic acids.
Form (II) or (III) method of cross-linked structure be: utilize sulfuryl fluoride, sulfonic acid chloride, sulfonic acid bromide type resin and ammonia, hydrazine, organic diamine or can discharge ammonia through chemical treatment, the substance reaction of hydrazine, organic diamine obtains;
Described organic diamine is alkyl or the fluorine-containing alkyl diamine of C1～C10, describedly can discharge ammonia through chemical treatment, and the material of hydrazine, organic diamine includes but not limited to ammonia, organic or inorganic acid hydrochlorate, urea or the guanidine of hydrazine, organic diamine.
The method that forms (IV) cross-linked structure is that the sulfonic fluoropolymer resin utilizes the chlorosulfonic acid processing to obtain;
The method that forms (V) cross-linked structure is that the fluorine-containing sulfuryl fluoride resin in the sulfonic fluoropolymer resin in nitrile group-containing site, nitrile group-containing site, the sulfonic acid bromide resin that contains that contains sulfonic acid chloride resin or nitrile group-containing site in nitrile group-containing site form under hot or sour effect;
Described acid is strong protonic acid or lewis acid; Wherein strong protonic acid is selected from H
2SO
4, CF
3SO
3H or H
3PO
4Lewis acid is selected from ZnCl
2, FeCl
3, AlCl
3, organotin, antimony organic or organic tellurium.
Preferably, melt extrude with the step of pressure sintering following:
(1). according to the suitable ion exchange fluoro resin of needs preparation of each layer formula in the multilayer fluorine-containing cross-linking ion film, crosslinking agent, acid and/or radical initiator mixture utilize double screw extruder, banbury or mill 200～280 ℃ of mixing; Said ion exchange fluoro resin is selected from sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2) resin that step (1) is mixed utilizes screw extruder or vulcanizing press film forming;
(3) crosslinked in the film forming, or after the film forming; Get monofilm;
(4) monofilm is compound, obtains described multilayer film.
Preferably, can the film of gained be converted in advance acid type and other film is compound, also can be earlier and the compound acid type that transfers to again of other film.
Preferably; Utilize the extrusion by melting cambium layer to be: to contain the resin that can form identical cross-linked structure with two kinds and at high temperature extrude and use and increase that pressure is compound to make two kinds of resin surfaces merge each other, utilize cross-linking method to make it crosslinked then with the method for interlayer cross-linked structure.Also can contain the prior film forming of crosslink sites resin with one, and this film is dipped into to contain in the identical crosslink sites chromoresin solution swelling and do crosslinking Treatment obtains crosslinked layer by layer film.
Preferred; When the casting that utilizes solution or fused mass, extrude, when hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology film forming; Employed radical initiator is the perfluor organic peroxide, will be under 80～250 ℃ temperature during film forming heat treatment 20～60 minutes.
The use of the crosslinked means of use has improved the mechanical strength of ionic membrane in the present invention-multilayer fluorine-containing cross-linking ion film, has also increased the dimensional stability of film simultaneously greatly.We can also find to compare in the past by the fuel permeability of film, and the result of various technology descends the ionic membrane that its effect is traditional head and shoulders above greatly.Studying carefully its possible reason and be cross-linked structure makes conductive ion bunch be limited at the resistance that has increased fuel infiltration in the very little space; Also having our film of invention is a kind of film of sandwich construction; Thereby existing the interface between layer and the layer, the existence at interface makes the infiltration of fuel be suppressed.
In general the existence at interface also can reduce the material conductivity simultaneously greatly, because the interface scattering phenomenon can occur to the charge carrier that conducts electricity.But this phenomenon does not have the high temperature or the conductance under the low humidity of appearance and film to improve significantly than traditional monofilm in our technology.This possibly be because the existence at interface makes the leakage that is kept at the small amount of moisture in the film also be suppressed simultaneously, makes the water holding capacity of film improve greatly compared with simple monofilm.
Embodiment:
Below through embodiment the present invention is further specified, but the present invention is not limited thereto.
Embodiment 1:
With repetitive do
The polymer of EW=1000 is processed the aqueous propanol solution of 5wt%; Be disposed at concentration then and be 5% peroxidating perfluor malonyl DMF solution, be cast in the polytetrafluoroethylene mold of horizontal positioned, through 80 ℃ of vacuumizes after 12 hours; Film is peeled off, and is the H of 0.5M in molar concentration
2SO
4Boil 1 hour in the solution, and use deionized water wash.After the heat treated film use NaOH solution, sulfuric acid solution to handle successively being obtained the individual layer perfluorinated sulfonic acid crosslinked is that (I) plants ionic membrane (monofilm 1#).Carry out hot pressing with above-mentioned two individual layer perfluor cross-linking ion membranes are stacked, make double-deck perfluor cross-linking ion membrane (multilayer film 1#).
Embodiment 2:
With repetitive do
The polymer of EW=800 is extruded for 250 ℃ and is obtained the film that thickness is 15 μ m.With above-mentioned two film high-temp. hot pressing together and be soaked in NH
4In the DMF solution of Cl 5 hours.Then the film that soaks is placed triethylamine 2 hours at 200 ℃, get crosslinked film.The cross-linked structure layer by layer of using KOH solution, hydrochloric acid solution to handle successively this film is the amberplex (duplicature 2#) of (II).
Place repetitive to be above-mentioned ionic membrane
The polymer of EW=1200 and tetraphenyltin be with 200 ℃ of films that are extruded into 50 μ m of double screw extruder, then with film be heated to 230 ℃ 10 hours cross-linked structure be the film that (V) plants.This film is used LiOH successively, and salpeter solution is handled and is obtained cross-linking ion membrane.(monofilm 3#) with duplicature 2#, 3#, hot pressing obtain cross-linked three-layer film (multilayer film 2#), and thickness is 80 μ m.
Embodiment 3:
With repetitive do
The polymer of EW=1100 and urea are through after being hot pressed into 100 μ m films, and behind 170 ℃ of heating 5h, using alkali and acid treatment to obtain cross-linked structure successively is the ionic membrane that (II) plants.(monofilm 4#)
With repetitive do
The polymer of EW=940 is processed 30% DMSO solution, through the casting method at 170 ℃, 60min makes the film (monofilm 5#) of 10 μ m.
With monofilm 4,5# perfluorinated sulfonic acid ionic membrane is stacked to carry out hot pressing, then with multilayer film 2# hot pressing, obtains six layers of cross-linking ion membrane (multilayer film 3#).
Embodiment 4:
With repetitive do
The solution of 20% (weight) that the polymer dissolution of EW=700 is made in DMF, the method for utilizing curtain coating then are in 230 ℃, and the thickness of 20min system is the individual layer perfluorinated sulfonic acid cross-linking ion membrane of 50 μ m.It must cross-linked structure be the film (monofilm 6#) of real (IV) that this amberplex impregnated in the chlorosulfonic acid.
Above-mentioned ionic membrane is placed polymer and peroxidating perfluor bay two acyls of embodiment 1 once more, 1, soaked 0.5 hour in the DMF solution of 4-diiodo-octafluorobutane, then film is taken out dryly, repeat above-mentioned steps, film is handled 300min down at 120 ℃.Two above-mentioned films are hot pressed into crosslinked six tunics (multilayer film 4#).
Embodiment 5:
With repetitive do
The polymer of EW=1300, AMBN, 1,4-diiodo-octafluorobutane is dissolved among the DMF, through the casting method at 270 ℃, 10min makes the film of 20 μ m.Re-use perfluorinated sulfonic resin among the embodiment 4 and be dissolved in the N-methyl pyrrolidone and become the film of 30 μ m, prepare three layers of perfluorinated ion-exchange membrane (multilayer film 5#) in the spin coating of the both sides of above-mentioned film.Film is handled 2.4h down at 69 ℃.The cross-linked structure that obtains three layers is the perfluoro sulfonic acid membrane of formula (II).
Above-mentioned ionic membrane is placed above-mentioned polymer, AMBN once more, 1, soaked 0.5 hour in the DMF solution of 4-diiodo-octafluorobutane; Then film is taken out dry; Repeat above-mentioned steps, film is handled 300min, the five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 6#) that obtain down at 120 ℃.
Embodiment 6:
With repetitive do
Through the spraying coating process method, 200 ℃, 30min obtains the film that thickness is 40 μ m to the polymer dissolution of EW=1300 in hempa acid amide (solid content 5%).Film is handled 100min down at 230 ℃.Obtaining cross-linked structure is the individual layer perfluoro sulfonic acid membrane (monofilm 7#) of formula (II).
Both sides at crosslinked perfluoro sulfonic acid membrane are passed through the spraying coating process method once more, make three layers of crosslinked perfluoro sulfonic acid membrane of 60 μ m.At its both sides hot pressing monofilm 7#, make crosslinked five layers of perfluorinated sulfonic acid doping (multilayer film 7#).
Embodiment 7:
With repetitive do
The polymer of EW=1300, benzoyl peroxide, 1,14-diiodo-20 fluorine ten alkane are dissolved in the dimethyl sulfoxide (DMSO) and obtain the film that thickness is 25 μ m through the silk-screen printing technique method.Film is handled 3min down at 160 ℃.Obtain crosslinked perfluoro sulfonic acid membrane.(monofilm 8#)
Above-mentioned ionic membrane is placed the same polymer of formula once more; Zeolite and benzoyl peroxide, 1, soaked 0.5 hour in the dimethyl sulphoxide solution of 14-diiodo-20 fluorine ten alkane; Then film is taken out dry; Repeat above-mentioned steps, film is handled 300min, the three layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 8#) that are enhanced down at 120 ℃.
Carry out hot pressing with three of multilayer film 8# are stacked, make nine layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 9#) of enhancing.
Embodiment 8:
With repetitive do
The EW=1250 polymer dissolution obtains 30% solution in the hempa acid amide, through the spraying coating process method, obtain the film that thickness is 40 μ m.Film is handled 100min down at 230 ℃, obtain crosslinked individual layer perfluoro sulfonic acid membrane (monofilm 9#).
Both sides at crosslinked perfluoro sulfonic acid membrane are passed through the spraying coating process method once more, make three layers of crosslinked perfluoro sulfonic acid membrane of 60 μ m.At its both sides hot pressing monofilm 9#, make crosslinked five layers of perfluoro sulfonic acid membrane (multilayer film 10#).
Embodiment 9:
With repetitive do
The polymer of EW=900 is extruded and is obtained the film that thickness is 30 μ m.Soaked in the DMF solution with NH3 5 hours.Get the film that (II) plants cross-linked structure at 200 ℃.This film is used alkali lye, the cross linking membrane (monofilm 10#) that acid solution is handled.
With repeat unit structure do
The polymer of EW=1200 and tetraphenyltin are extruded into the film of 50 μ m with double screw extruder, then film are heated to 230 ℃ and obtain the films (monofilm 11#) that (V) plants cross-linked structure in 10 hours.With monofilm 10; The hot pressing of 11# high temperature is compound, again this film is placed 35% hydrazine hydrate kind 10 hours, take out the back heating had simultaneously in 5 hours (V) plant cross-linked structure and layer by layer between (III) plant the film of cross-linked structure; This film is used alkali lye, the cross linking membrane (multilayer film 11#) that acid solution is handled.
The crosslinked eleventh floor film (multilayer film 12#) of multilayer film 11# and the overlapping hot pressing of multilayer film 7# film, thickness is 300 μ m
Embodiment 10:
With repetitive do
The polymer of EW=700 and repetitive do
20% the solution that the polymer of EW=1300 (the resin quality ratio is 1: 0.2) and AMBN mixed dissolution are made in DMF; Then through curtain coating; Heat to such an extent that thickness is that the individual layer perfluorinated sulfonic acid of 45 μ m contains (I) and plants cross-linked structure, again this amberplex is put in the film (monofilm 12#) that obtains (IV) cross-linked structure in the chlorosulfonic acid again.
With monofilm 12# and multilayer film 2# hot pressing, make five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 13#).
Embodiment 11:
With repetitive do
The polymer of EW=1200 and triphenyl tin hydroxide are scattered among the DMF, and the method through casting is at 170 ℃, and 60min makes the film that the having of 20 μ m (V) planted cross-linked structure.Re-use perfluorinated sulfonic resin among the embodiment 4 and be dissolved in the N-methyl pyrrolidone and become the film of 30 μ m, prepare three layers of perfluorinated ion-exchange membrane in the spin coating of the both sides of above-mentioned film.Film is handled 2.4h down at 190 ℃.Obtain three layers cross-linked perfluorinated sulfonate film (multilayer film 14#).
Embodiment 12:
With repetitive do
The polymer of EW=1200 prepares monofilm with the method that melt extrudes, and this film is at high temperature handled obtaining the monofilm 13# that cross-linked structure is formula II in 3 hours then.On the two sides of monofilm 13# folded on multilayer film 12# and 120 ℃ of hot-pressing processing, hydrolysis acidification obtains 23 layers of cross-linked perfluorinated sulfonate film (multilayer film 15#) then.
Embodiment 13:
With repetitive do
Polymer and repetitive be:
Polymer be that mixed mixed melting in sieve bar extruder of 2: 3 extrudes that to obtain thickness be 50 microns film (monofilm 13#) with mass ratio.
With repetitive do
Polymer be dissolved in the hempa acid amide that to form solid content be 50% dispersion. the method through curtain coating is at the monofilm of 150 ℃ of systems. place the DMF solution of peroxidating perfluorocarboxylic acid to soak the cross-linked structure monofilm 14#. that heating obtains the formula that forms (I) this film
Monofilm 13# is placed between two monofilm 7# and two the compound hot pressing posthydrolysis of monofilm 14# acidifyings again, obtain multilayer film 16#.
Embodiment 14:
With repetitive do
Polymer dispersed in the N-methyl pyrrolidone, to form solid content be 30% dispersion liquid. utilize method film forming on plate glass of spraying. (monofilm 15#).
With above-mentioned polymer do with repetitive
The polymer of
is to be scattered among the DMSO after 1: 5 the mixed by mass ratio; Again to above-mentioned mixed liquor, form triazine crosslinked rings through the The tape casting film forming and with film at 230 ℃ after adding a spot of antimony organic catalyst again. (monofilm 16#).
It is 300 microns 15 tunics (multilayer film 17#) that monofilm 16# and monofilm 15# are stacked alternately the compound thickness that obtains of hot pressing.
Embodiment 15:
With repetitive do
The EW=1250 polymer obtains 19% solution in the hempa acid amide, through the silk-screen printing technique method, at multilayer film 14# upper layer film.Film is handled 300min under the irradiation of ultraviolet light, obtaining cross-linked structure is the multi-layer perfluor sulfonate film (multilayer film 18#) of I.
Embodiment 16:
With repetitive do
Polymer, tertbutanol peroxide, 1,4-diiodo-octafluoro fourth is dissolved among the DMF, obtains the film that thickness is 25 μ m through the silk-screen printing technique method.Film is handled 3min down at 160 ℃.Obtain crosslinked perfluoro sulfonic acid membrane.(monofilm 17#)
Above-mentioned ionic membrane is placed same polymer, benzoyl peroxide, 1 once more; Soaked 0.5 hour in the dimethyl sulphoxide solution of 14-diiodo-20 fluorine ten alkane, then film is taken out drying, repeat above-mentioned steps; Film is handled 300min down at 120 ℃, obtain three layers of perfluorinated sulfonic acid cross-linking ion membrane.
Carry out hot pressing with above-mentioned three individual layer perfluorinated sulfonic acid cross-linking ion membranes are stacked, make nine layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 19#).。
Embodiment 17:
With repetitive do
Polymer and repetitive be:
Polymer be to be scattered in after 1: 4 the mixed to form 22% solution among the NMP with mass ratio, going out to obtain thickness through curtain coating is 50 microns film (monofilm 18#).
With monofilm 18# place between two monofilm 7# again with two compound hot pressing of monofilm 14# after sodium type multilayer amberplex (multilayer film 20#).
Embodiment 18:
With repetitive do
The polymer of EW=700 and repetitive do
The polymer of EW=1300 (the resin quality ratio is 1: 0.5) is dissolved in 22% the solution of making among the DMF; Then through curtain coating; Heating and X ray are handled to such an extent that thickness is that the individual layer perfluorinated sulfonic acid of 45 μ m contains (I) and plants cross-linked structure, again this amberplex are put in the film (monofilm 19#) that obtains (IV) cross-linked structure in the chlorosulfonic acid again.
With monofilm 19# and multilayer film 2# hot pressing, make five layers of perfluorinated sulfonic acid cross-linking ion membrane (multilayer film 21#).
Embodiment 19:
With repetitive do
Polymer melt extrude. (monofilm 20#).
Monofilm 16# and monofilm 20# are stacked alternately hot pressing, and compound to obtain thickness be 100 microns 5 tunics and the hydrolysis in acid of this film is got multilayer film (multilayer film 22#).
Embodiment 20:
With repetitive do
Polymer and repetitive be:
Polymer be that 0.5: 5 mixed is scattered in and forms 24% solution among the NMP with mass ratio, going out to obtain thickness through curtain coating is 50 microns film (monofilm 21#).
With monofilm 21# place between two monofilm 7# again with two compound hot pressing of monofilm 14# after acidifying get multilayer amberplex (multilayer film 23#).
Embodiment 21: with repetitive do
EW=900 polymer-extruded obtains the film that thickness is 30 μ m.Soak and 1 in the DMF solution of 2-ethylenediamine 5 hours.Get the film that (III) plants cross-linked structure at 200 ℃.This film is used alkali lye, the cross linking membrane (monofilm 22#) that acid solution is handled.
With monofilm 22#, crosslinked 16 tunics (multilayer film 24#) of monofilm 11# and multilayer film 11# and the overlapping hot pressing of multilayer film 7# film, thickness is 300 μ m
Comparative example 22:
The method of utilizing 10%nafion DMF soln using to pour into a mould obtains the amberplex of 60 micron thick 170 ℃ of processing.
Embodiment 23
Performance to various films characterizes, and the result sees table 1.Can find out that by table 1 performances such as 100 ℃ of conductivity of multilayer fluorine-containing cross-linking ion film, hot strength, hydrogen permeate electric current all are superior to common exchange membrane containing fluorine.
The various films of table 1 characterize
Claims (8)
1. multilayer fluorine-containing cross-linking ion film is to be the multilayer film of the 2-40 layer that forms of the ion exchange fluoro resin of 600～1300g/mol with the EW value, wherein has at least 1 layer to have cross-linked structure, conductivity 40～150mS/cm, hot strength 10～60MPa; Gross thickness 10～300 μ m; Layer forms cross-linked structure with interlayer;
Said cross-linked structure is selected from as shown in the formula shown in (V):
It is characterized in that: described ion exchange fluoro resin is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer and one or more fluorine-containing alkene monomer copolymerization that contain crosslink sites that contain functional group, or the mixture of above-mentioned copolymer;
Fluorine containing olefine is selected from: tetrafluoroethene, and CTFE, trifluoro-ethylene, one or more in hexafluoropropylene or the vinylidene,
The fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (VI), (VII) or in the structure (VIII):
Wherein, a, b, c are 0～1 integer, but can not be zero simultaneously;
D is 0～5 integer;
N is 0 or 1;
R
F1, R
F2And R
F3Be selected from perfluoroalkyl or dichlorodifluoromethan base respectively;
X is selected from F, Cl, Br, or I;
Y
1, Y
2, Y
3Be selected from SO
2M, COOR
3, or PO (OR
4) (OR
5), wherein:
M is selected from Br, F, Cl, OR or NR
1R
2Said R is selected from methyl, ethyl, propyl group, H, Na, Li, K or ammonium root; R
1And R
2Be selected from H, methyl, ethyl or propyl group respectively; R
3Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group; R
4, R
5Be selected from H, Na, Li, K, ammonium root, methyl, ethyl or propyl group;
The described fluorine-containing alkene monomer that contains crosslink sites is selected from one or more as shown in the formula (IX) and/or in the structure (X):
Wherein, Y
4, Y
5Can be selected from Cl, Br, I or CN respectively;
A ', b ', c ' are respectively 0 or 1, but a '+b '+c ' ≠ 0;
X
1Be selected from F, Cl, Br, or I;
N ' is 0 or 1;
R
F4, R
F5, R
F6Be selected from perfluoroalkyl respectively.
2. a kind of multilayer fluorine-containing cross-linking ion film as claimed in claim 1 is characterized in that: Fluorine containing olefine is selected from tetrafluoroethene or CTFE.
3. a kind of multilayer fluorine-containing cross-linking ion film as claimed in claim 1 is characterized in that: the EW value of said ion exchange fluoro resin is 700-1200g/mol; The number of plies of multilayer film is the 2-10 layer, gross thickness 10-50 μ m.
4. the preparation method of a kind of multilayer fluorine-containing cross-linking ion film as claimed in claim 1 is characterized in that, each monofilm utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology process; The preparation of multilayer film is through compound between compound between compound between monofilm, multilayer film and monofilm or multilayer film and multilayer film, also can directly on monofilm that has made or multilayer film, utilize solution or fused mass casting, extrude, hot pressing, spin coating, curtain coating, silk-screen printing technique, spraying or impregnation technology preparation.
5. the preparation method of a multilayer fluorine-containing cross-linking ion film as claimed in claim 4 is characterized in that, the step of solution casting, solution-cast, silk-screen printing technique, spin coating, spraying or dipping is following:
(1) with ion exchange fluoro resin, crosslinking agent, acid and/or radical initiator are distributed to solvent and form mixture; Ion exchange fluoro resin content is 1～80% in the mixture, weight ratio;
(2) utilize the middle preparation of step (1) solution passing through solution casting, solution casting, silk-screen printing technique, spin coating, spraying or impregnation technology film forming on the flat board or on the single or multiple lift film that has prepared; Will be under 30～300 ℃ temperature during film forming heat treatment 10～100 minutes;
(3) crosslinked in the film forming, or after the film forming, form the cross-linked structure shown in the formula (V).
6. the preparation method of a multilayer fluorine-containing cross-linking ion film as claimed in claim 5; It is characterized in that the used solvent of step (1) is one or more in dimethyl formamide, dimethylacetylamide, NMF, dimethyl sulfoxide (DMSO), N-methyl pyrrolidone, hempa acid amide, acetone, water, ethanol, methyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol or the glycerine; Said crosslinking agent is selected from the said material of formula (XI), ammonia, hydrazine, organic diamine or can discharges the material of ammonia, hydrazine, organic diamine through chemical treatment; Will be under 80～250 ℃ temperature during film forming in the step (2) heat treatment 20～60 minutes;
X
2R
f7X
3
(XI)；
X
2, X
3Be selected from Cl, Br, or I; R
F7Be selected from perfluoroalkyl or dichlorodifluoromethan base.
7. the preparation method of a multilayer fluorine-containing cross-linking ion film as claimed in claim 4 is characterized in that, melt extrudes with the step of pressure sintering following:
(1). according to the suitable ion exchange fluoro resin of needs preparation of each layer formula in the multilayer fluorine-containing cross-linking ion film, crosslinking agent, acid and/or radical initiator mixture utilize double screw extruder, banbury or mill 200～280 ℃ of mixing; Said ion exchange fluoro resin is selected from sulfuryl fluoride, sulfonic acid chloride or sulfonic acid bromide resin;
(2) resin that step (1) is mixed utilizes screw extruder or vulcanizing press film forming;
(3) crosslinked in the film forming, or after the film forming; Form the cross-linked structure shown in the formula (V), get monofilm;
(4) monofilm is compound, obtains described multilayer fluorine-containing cross-linking ion film.
8. the preparation method like claim 5 or 7 described multilayer fluorine-containing cross-linking ion films is characterized in that,
The method that forms (V) cross-linked structure is that the fluorine-containing sulfuryl fluoride resin in the sulfonic fluoropolymer resin in nitrile group-containing site, nitrile group-containing site, the sulfonic acid bromide resin that contains that contains sulfonic acid chloride resin or nitrile group-containing site in nitrile group-containing site form under hot or sour effect;
Described acid is strong protonic acid or lewis acid; Wherein strong protonic acid is selected from H
2SO
4, CF
3SO
3H or H
3PO
4Lewis acid is selected from ZnCl
2, FeCl
3, AlCl
3, organotin, antimony organic or organic tellurium.
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| CN1477990A (en) * | 2000-10-21 | 2004-02-25 | �����ɷ� | Novel membranes having improved mechanical properties, for use in fuel cells |
| US6733914B1 (en) * | 2000-02-18 | 2004-05-11 | Ion Power, Inc. | Fuel cell membranes |
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| US6733914B1 (en) * | 2000-02-18 | 2004-05-11 | Ion Power, Inc. | Fuel cell membranes |
| CN1477990A (en) * | 2000-10-21 | 2004-02-25 | �����ɷ� | Novel membranes having improved mechanical properties, for use in fuel cells |
| CN1694290A (en) * | 2005-05-20 | 2005-11-09 | 武汉理工大学 | Composite proton exchange membrane for high temperature proton exchange membrane fuel cell and preparation method |
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