CN102336924B - Method for preparing perfluorosulfonic acid ion exchange membrane - Google Patents
Method for preparing perfluorosulfonic acid ion exchange membrane Download PDFInfo
- Publication number
- CN102336924B CN102336924B CN 201110173854 CN201110173854A CN102336924B CN 102336924 B CN102336924 B CN 102336924B CN 201110173854 CN201110173854 CN 201110173854 CN 201110173854 A CN201110173854 A CN 201110173854A CN 102336924 B CN102336924 B CN 102336924B
- Authority
- CN
- China
- Prior art keywords
- fluoropolymer
- per
- sulfonic acid
- film
- ion exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 53
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 230000004048 modification Effects 0.000 claims abstract description 38
- 238000012986 modification Methods 0.000 claims abstract description 38
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 37
- 229920002313 fluoropolymer Polymers 0.000 claims description 165
- 239000004811 fluoropolymer Substances 0.000 claims description 165
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 150000003460 sulfonic acids Chemical class 0.000 claims description 44
- 229910052731 fluorine Inorganic materials 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 41
- 239000011737 fluorine Substances 0.000 claims description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- -1 metals ion Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960001701 chloroform Drugs 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 8
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002203 pretreatment Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 238000005191 phase separation Methods 0.000 claims description 5
- 238000009832 plasma treatment Methods 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001774 Perfluoroether Polymers 0.000 claims description 3
- 210000001124 body fluid Anatomy 0.000 claims description 3
- 239000010839 body fluid Substances 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- VKFAUCPBMAGVRG-UHFFFAOYSA-N dipivefrin hydrochloride Chemical compound [Cl-].C[NH2+]CC(O)C1=CC=C(OC(=O)C(C)(C)C)C(OC(=O)C(C)(C)C)=C1 VKFAUCPBMAGVRG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000000909 electrodialysis Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000010933 acylation Effects 0.000 abstract 1
- 238000005917 acylation reaction Methods 0.000 abstract 1
- 238000010612 desalination reaction Methods 0.000 abstract 1
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 229920005597 polymer membrane Polymers 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 230000001960 triggered effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229920003303 ion-exchange polymer Polymers 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 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 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- XSLYISNQTJHKMP-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)ethanesulfonyl fluoride Chemical compound FC(F)(I)C(F)(F)OC(F)(F)C(F)(F)S(F)(=O)=O XSLYISNQTJHKMP-UHFFFAOYSA-N 0.000 description 1
- VQUGQIYAVYQSAB-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethanesulfonyl fluoride Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)S(F)(=O)=O VQUGQIYAVYQSAB-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- REDPJOZSAHHIAO-UHFFFAOYSA-N butane;pentane Chemical compound CCCC.CCCCC REDPJOZSAHHIAO-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LWSYSCQGRROTHV-UHFFFAOYSA-N ethane;propane Chemical compound CC.CCC LWSYSCQGRROTHV-UHFFFAOYSA-N 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- AANLSOCSNMYRRR-UHFFFAOYSA-N heptane;octane Chemical compound CCCCCCC.CCCCCCCC AANLSOCSNMYRRR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction 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
- 238000002791 soaking Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Abstract
The invention discloses a method for preparing a perfluorosulfonic acid ion exchange membrane. A fluoride acylation fluorine compound or fluoride sulfonic acid (salt) is triggered in a low temperature plasma method to carry out in situ graft modification on a perfluor polymer membrane, and then a perfluor sulfonic acid ion exchange membrane is obtained through alkalified hydrolysis and/or H+ ion exchange. The preparation method disclosed by the invention has the advantages of convenience in operation, simple process, high processing speed, good processing effect, low cost and the like, environment pollution is not caused easily, and the method can be applied in the fields of chloralkali industry, new energy batteries, other various electrolytic preparation devices, electrodialysis, chemical catalysis, gas separation, gas drying, sewage treatment, sea water desalination and the like.
Description
Technical field
The invention belongs to high molecular functional film field, be specifically related to a kind of method for preparing perfluorinated ion-exchange membrane.
Background technology
The development of perfluorinated ion exchange resin originates in perfluorinated sulfonic acid ion exchange resin, and it is to be molecular skeleton with the tetrafluoroethylene structure, is the perfluorinated sulfonic acid polymer of side chain with the perfluoroalkyl vinyl ether that contains sulfonic acid group.Perfluorinated sulfonic acid ion exchange resin is because carbon-fluorine bond bond distance is short; Bond energy is high, and the fluorine atom volume ratio Wasserstoffatoms of electron rich is big, and polarizable degree is little; Chain rotation through molecule; Fluorine atom closely cover carbon-carbon skeletal chain around, thereby C-C has been formed good resist, therefore have good thermostability and chemicalstability; Simultaneously, because the sulfonic acid group on the side chain dissociates fully, also has good ionic conduction characteristic in water.
Perfluorinated ion-exchange membrane is prepared from perfluorinated ion exchange resin, is the tip materials of fluorine materials industry.It has promoted global chlorine industry to develop towards less energy-consumption, free of contamination direction with its good resistance toheat, mechanical property, chemical property and chemical stability etc.In addition; Fuel cell is classified as the energy conversion device of giving priority to zero release, noiselessness, plurality of advantages such as high-effect by countries in the world in recent years; Key part wherein is exactly an ion-exchange membrane, and perfluorinated sulfonic acid ion exchange membrane is unique business-like ion-exchange membrane in fuel cell at present.In addition, perfluorinated ion exchange resin and exchange membrane thereof have the incomparable advantage of other material also in other field such as fields such as electrolytic preparation device, electrodialysis, chemical catalysis, gas delivery, gas drying, WWT, sea water desaltinations.
The presoma resin of preparation perfluorinated sulfonic acid ion exchange membrane is to be initiator with organo-peroxide, azo cpd or persulphate; Carry out the mass polymerization of perfluor sulfonyl fluorovinyl ether; Perhaps with the perfluor sulfonyl fluorovinyl ether respectively with perfluoroolefine monomer copolymerizables such as tetrafluoroethylene, R 1216, after polymerization is accomplished product is separated, clean oven dry; Melt extrude, promptly contained-SO
2The perfluorinated sulfonic acid presoma resin of F group, hydrolysis proton exchange then obtains perfluorinated sulfonic resin.Wherein, the molecular formula of perfluor sulfonyl fluorovinyl ether is CF
2=CF-O-R
F-SO
2F ,-R
FBe the chain structure of perfluoroalkyl or perfluor ether, as-CF
2-CF (CF
3)-O-CF
2-CF
2--CF
2-CF (CF
3)-O-CF
2-CF
2-CF
2-,-CF
2-CF
2-CF
2-CF
2-,-CF
2-CF
2-etc. structure.
At present, the preparation method of perfluorinated ion-exchange membrane has two kinds: heat fusing is extruded into embrane method and becomes embrane method with solution-cast.Melt extrude into embrane method and be suitable for serialization production; And because film process does not use solvent; Thereby can not work the mischief to environment; But also need film water be separated transition after the film forming in this way, the film planeness that in transformation process, is hard to keep, and only be suitable for the lower ionic polymer of exchange capacity.Solution-cast becomes embrane method at first will under higher temperature and pressure, be configured to the corresponding solution of perfluorinated ion exchange resin, then in the flat formwork top casting, wipes the solvent flashing film forming off.Solution-cast becomes embrane method can directly obtain the goods of ionic; Can intermittent type or serialization production during film forming according to the difference of equipment; Machinable goods kind is more; And can be used for the ionic polymer film forming of loading capacity broad, but the whole technological process of this method is comparatively loaded down with trivial details, need recycle solvent.
In recent decades, perfluorinated sulfonic acid ion exchange membrane is one of hot subject of domestic and international researchist always.At first successfully develop fluosulfonic acid ion-exchange membrane (Nafion in early 1960s by Dupont (Dupont)
TM).Japan Asahi Chemical Industry (ASAHI Chem.) and Asahi Glass (ASAHI Glass) have been developed the perfluorinated sulfonic resin with its same structure subsequently.The Dow Chemical Company, Su Weisu Simon Rex, Eastern Mountain divine boat, 3M have also developed the product with its structural similitude.The preparation of existing perfluorinated sulfonic acid ion exchange membrane is as shown in Figure 1, preparation technology's more complicated.
Summary of the invention
Technical purpose of the present invention is the preparation method to existing perfluorinated sulfonic acid ion exchange membrane, and a kind of novel method for preparing perfluorinated sulfonic acid ion exchange membrane is provided.
The present invention realizes that the technical scheme that above-mentioned technical purpose is taked is: a kind of method for preparing perfluorinated sulfonic acid ion exchange membrane; Utilize low-temperature plasma to cause fluorine-containing sulfonic acid fluoride based compound and carry out the situ-formed graft modification, pass through alkaline hydrolysis and H then at the (per) fluoropolymer porous-film
+IX obtains perfluorinated sulfonic acid ion exchange membrane; Perhaps
Utilize low-temperature plasma to cause sulfonic fluoropolymer or sulfonic fluoropolymer salt (following abbreviate sulfonic fluoropolymer or sulfonic fluoropolymer salt as sulfonic fluoropolymer (salt)) and carry out the situ-formed graft modification, pass through H then at the (per) fluoropolymer porous-film
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
(per) fluoropolymer include but not limited to polytetrafluoroethylene (PTFE), polyhexafluoropropylene (PHFP), tetrafluoroethylene, hexafluoropropylene copolymer (F46) or gather perfluoro alkoxy (PFA) resin.
The structural formula of fluorine-containing sulfonic acid fluoride based compound is CF
2=CFR
FSO
2F or IR
FSO
2F, wherein R
FChain structure for perfluoroalkyl or perfluor ether includes but not limited to-[CF
2CF
2]
nOCF
2CF
2-,-[CF
2C (CF
3)]
nOCF
2CF
2-perhaps-C
nF
2n-etc. structure.
The molecular formula of sulfonic fluoropolymer (salt) is CF
2=CFR
FSO
3M or IR
FSO
3M, wherein R
FChain structure for perfluoroalkyl or perfluor ether includes but not limited to-[CF
2CF
2]
nOCF
2CF
2-,-[CF
2C (CF
3)]
nOCF
2CF
2-perhaps-C
nF
2n-etc. structure; M is H
+Or metals ion, include but not limited to H
+, Li
+, Na
+, K
+, Ca
+, Mg
2+, Fe
3+, Cu
2+Deng.
Technical scheme of the present invention can preferably be taked following three kinds of embodiments, and Fig. 2 is the technological line synoptic diagram of these three kinds of embodiments, and wherein the reaction mechanism of first and second kind embodiment is as shown in Figure 3.
First kind of embodiment is at first the (per) fluoropolymer porous-film to be carried out the plasma body pre-treatment; Carry out the situ-formed graft modification with fluorine-containing sulfonic acid fluoride based compound or sulfonic fluoropolymer (salt) then; Be hydrolyzed as required at last and IX, obtain perfluorinated sulfonic acid ion exchange membrane.
First kind of embodiment comprises the steps:
Step 1: the (per) fluoropolymer porous-film is carried out the plasma body pre-treatment in the plasma atmosphere district;
Step 2: under nitrogen or protection of inert gas, pretreated (per) fluoropolymer porous-film is soaked in the solution of fluorine-containing sulfonic acid fluoride based compound, perhaps soak into and in the liquid body of fluorine-containing sulfonic acid fluoride based compound, cause the situ-formed graft modification;
Step 3: the (per) fluoropolymer porous-film after the taking-up graft modification, the fluorine-containing sulfonic acid fluoride based compound in the not grafting is removed in washing, carries out alkaline hydrolysis then, last and H
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
Wherein, In the solution of the fluorine-containing sulfonic acid fluoride based compound of step 2; Solvent is the good solvent of fluorine-containing sulfonic acid fluoride based compound and is the poor solvent of (per) fluoropolymer resin; Can be selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N as required; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
Perhaps, first kind of embodiment comprises the steps:
Step 1: the (per) fluoropolymer porous-film is carried out the plasma body pre-treatment in the plasma atmosphere district;
Step 2: cause the situ-formed graft modification soaking under nitrogen or the protection of inert gas, with pretreated (per) fluoropolymer porous-film in the solution of the solution of sulfonic fluoropolymer or sulfonic fluoropolymer salt; Perhaps, soak in the liquid body of the liquid body of sulfonic fluoropolymer or sulfonic fluoropolymer salt and cause the situ-formed graft modification;
Step 3: sulfonic fluoropolymer or the sulfonic fluoropolymer salt in the not grafting is removed in (per) fluoropolymer porous-film, the washing of taking out after the graft modification, then as required with H
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
Wherein, In the solution of the sulfonic fluoropolymer of step 2; Solvent is the good solvent of sulfonic fluoropolymer and is the poor solvent of (per) fluoropolymer resin; Can be selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N as required; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.In the solution of the sulfonic fluoropolymer salt of step 2; Solvent is the good solvent of sulfonic fluoropolymer salt and is the poor solvent of (per) fluoropolymer resin; Can be selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N as required; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
Second kind of embodiment is at first the (per) fluoropolymer porous-film to be soaked in the solution or liquid this body fluid of fluorine-containing sulfonic acid fluoride based compound; Perhaps soak in the solution or liquid body of sulfonic fluoropolymer (salt); Utilize the low-temperature plasma body method to carry out the situ-formed graft modification then; Be hydrolyzed as required at last and IX, obtain perfluorinated sulfonic acid ion exchange membrane.
Second kind of embodiment comprises the steps:
Step 1: the (per) fluoropolymer porous-film is soaked in the solution of fluorine-containing sulfonic acid fluoride based compound, perhaps soak in this body fluid of fluorine-containing sulfonic acid fluoride based compound, fluorine-containing sulfonic acid fluoride based compound fully is adsorbed on the (per) fluoropolymer porous-film, then oven dry;
Step 2: the (per) fluoropolymer porous-film that will adsorb fluorine-containing sulfonic acid fluoride based compound is put into plasma producing apparatus, carries out the modification of plasma body situ-formed graft in the plasma atmosphere district;
Step 3: the (per) fluoropolymer porous-film after the taking-up graft modification, the fluorine-containing sulfonic acid fluoride based compound in the not grafting is removed in washing, carries out alkaline hydrolysis then, last and H
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
Wherein, In the solution of the fluorine-containing sulfonic acid fluoride based compound of step 1; Solvent is the good solvent of fluorine-containing sulfonic acid fluoride based compound and is the poor solvent of (per) fluoropolymer resin; Can be selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N as required; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
Perhaps, second kind of embodiment comprises the steps:
Step 1: the (per) fluoropolymer porous-film is soaked in the liquid body of the solution of sulfonic fluoropolymer or sulfonic fluoropolymer, sulfonic fluoropolymer fully is adsorbed on the (per) fluoropolymer porous-film, then oven dry; Perhaps, the (per) fluoropolymer porous-film is soaked in the liquid body of the solution of sulfonic fluoropolymer salt or sulfonic fluoropolymer salt, sulfonic fluoropolymer salt fully is adsorbed on the (per) fluoropolymer porous-film, then oven dry;
Step 2: the (per) fluoropolymer porous-film that absorption contains sulfonic fluoropolymer or adsorbs sulfonic fluoropolymer salt is put into plasma producing apparatus, carry out the modification of plasma body situ-formed graft in the plasma atmosphere district;
Step 3: take out the (per) fluoropolymer porous-film after the graft modification, sulfonic fluoropolymer or the sulfonic fluoropolymer salt in the not grafting is removed in washing, then as required with H
+IX obtains perfluorinated sulfonic acid ion exchange membrane;
Wherein, in the solution of the sulfonic fluoropolymer of step 1; Solvent is the good solvent of sulfonic fluoropolymer and is the poor solvent of (per) fluoropolymer resin; Can be selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N as required; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.In the solution of the sulfonic fluoropolymer salt of step 1; Solvent is the good solvent of sulfonic fluoropolymer salt and is the poor solvent of (per) fluoropolymer resin; Can be selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N as required; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
The third embodiment and first; Two kinds of embodiment differences; Be at first (per) fluoropolymer to be mixed with fluorine-containing sulfonic acid fluoride based compound or sulfonic fluoropolymer (salt), through stretching method, thermic be separated, liquid causes phase separation method, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film, utilizes the low-temperature plasma body method to carry out the situ-formed graft modification then; Be hydrolyzed as required at last and IX, obtain perfluorinated sulfonic acid ion exchange membrane.
The third embodiment comprises the steps:
Step 1: (per) fluoropolymer is mixed with fluorine-containing sulfonic acid fluoride based compound, through stretching method, thermic be separated, liquid causes phase separation method, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film;
Step 2: the (per) fluoropolymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: the (per) fluoropolymer film porous-film after the taking-up graft modification, the fluorine-containing sulfonic acid fluoride based compound in the not grafting is removed in washing, carries out alkaline hydrolysis then, last and H
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
Perhaps, the third embodiment comprises the steps:
Step 1: (per) fluoropolymer is mixed with sulfonic fluoropolymer, through stretching method, thermic be separated, liquid causes phase separation method, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film; Perhaps, (per) fluoropolymer is mixed with sulfonic fluoropolymer salt, through stretching method, thermic be separated, liquid causes phase separation method, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film;
Step 2: the (per) fluoropolymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: take out the (per) fluoropolymer film porous-film after the graft modification, sulfonic fluoropolymer or the sulfonic fluoropolymer salt in the not grafting is removed in washing, then as required with H
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
In above-mentioned first and second kind embodiment, infiltration temperature is preferably 20 ℃～150 ℃, and infiltrating time is preferably 1 hour～and 48 hours.
In the above-mentioned various embodiment, the power of plasma treatment is preferably 10W～1500W, and plasma treatment time is preferably 0.5 minute～and 60 minutes.Plasma atmosphere is an air; Rare gas element; Ammonia; Oxygen; Hydrogen; Nitrogen; Carbonic acid gas; Sulfurous gas; Methane; Ethane; Propane; Butane; Pentane; Hexane; Heptane; Octane; Nonane; Decane; Undecane; Dodecyl; Ethene; Propylene; Butylene; Amylene; Hexene; Propadiene; Divinyl; Isoprene; Acetylene; Propine; Butine; Hexafluoroethylene; Trifluoromethane; Trichloromethane; Methenyl bromide; Nitrogen protoxide; Tetrafluoromethane; Silane; Siloxanes; Water; Methyl alcohol; Ethanol; At least a in vinylformic acid and the methacrylic acid vapour.Wherein rare gas element is argon gas, helium, neon or krypton gas etc.
The present invention adopts Low Temperature Plasma Treating to carry out the situ-formed graft modification to prepare perfluorinated sulfonic acid ion exchange membrane; Following physicochemical change takes place perfluor IX porous-film after plasma treatment: (1) perfluor IX porous-film part chemical bond breaks off, and forms the high radical of chemically reactive; (2) the rapid combined with radical of sloughing generation with the olefinic double bonds disconnection or the functional group of fluorine-containing sulfonic acid fluoride based compound or sulfonic fluoropolymer (salt) of radical that exists with plasmoid forms new chemical bond and introduces fluorine-containing sulfonyl group or sulfonic fluoropolymer (salt) group; (3) through hydrolysis and/or H
+IX obtains fluosulfonic acid functional group, because the dissociating property of height of fluosulfonic acid acidic group has good ionic conduction characteristic.
Compared with prior art; Preparing method's cost of the present invention is low, technology is simple, easy to operate, process velocity is fast, treatment effect good; And be difficult for causing environmental pollution, energy-saving and emission-reducing, be more suitable for suitability for industrialized production, can be applied to fields such as new energy technology, various electrolytic preparation device, electrodialysis, chemical catalysis, gas delivery, gas drying, WWT, sea water desaltination, chlorine industry.
Description of drawings
Fig. 1 is the preparation synoptic diagram of existing perfluorinated sulfonic acid ion exchange membrane;
Fig. 2 is the technological line synoptic diagram of three kinds of embodiments taking of technical scheme of the present invention;
Fig. 3 is the reaction mechanism synoptic diagram of first and second kind of technical scheme embodiment of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1:
PTFE (per) fluoropolymer porous-film is immersed liquid ICF
2CF
2OCF
2CF
2SO
2Among the F, soak after 3 hours under the room temperature and take out, oven dry; Put it into then in the plasma producing apparatus, carry out the plasma grafting modification in the plasma atmosphere district, processing power is 200W; Treatment time is 1 minute, removes the not ICF in the tetrafluoroethylene grafting with ethanol then
2CF
2OCF
2CF
2SO
2F, the gained modified membrane is taken out sodium type polymeric film with placing 50 ℃ of hydrolysis reaction of aqueous sodium hydroxide solution 5 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains PTFE base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 2:
PTFE (per) fluoropolymer porous-film is immersed liquid ICF
2CF
2OCF
2CF
2SO
3In 50% aqueous solution of K, 40 ℃ are soaked taking-up after 5 hours, oven dry down; Put it into then in the plasma producing apparatus, carry out the plasma grafting modification in the plasma atmosphere district, processing power is 200W; Treatment time is 2 minutes, and water is removed the not ICF in the PTFE grafting then
2CF
2OCF
2CF
2SO
3K, gained potassium type ion exchange polymer film again with carrying out IX in the dilute hydrochloric acid solution, obtains PTFE base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 3:
PHFP base (per) fluoropolymer porous-film is immersed liquid ICF
2CF
2OCF
2CF
2SO
2Among the F, soak after 8 hours under the room temperature and take out, oven dry; Put it into then in the plasma producing apparatus, carry out the plasma grafting modification in the plasma atmosphere district, processing power is 250W; Treatment time is 1.5 minutes, removes the not ICF in the PHFP grafting with ethanol then
2CF
2OCF
2CF
2SO
2F, the gained modified membrane is taken out sodium type polymeric film with placing 50 ℃ of hydrolysis reaction of aqueous sodium hydroxide solution 6 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains PHFP base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 4:
FEP base (per) fluoropolymer porous-film is immersed liquid ICF
2CF
2OCF
2CF
2SO
2Among the F, soak after 8 hours under the room temperature and take out, oven dry; Put it into then in the plasma producing apparatus, carry out the plasma grafting modification in the plasma atmosphere district, processing power is 250W; Treatment time is 4 minutes, removes the not ICF in the FEP grafting with ethanol then
2CF
2OCF
2CF
2SO
2F, the gained modified membrane is taken out potassium type ion exchange polymer film with placing 50 ℃ of hydrolysis reaction of potassium hydroxide aqueous solution 6 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains FEP base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 5:
PHFP base (per) fluoropolymer porous-film is immersed liquid CF
2=CFOCF
2CF
2SO
2Among the F, 40 ℃ are soaked taking-up after 8 hours, oven dry down; Put it into then in the plasma producing apparatus, carry out the plasma grafting modification in the plasma atmosphere district, processing power is 250W; Treatment time is 7 minutes, removes the not CF in the PHFP grafting with ethanol then
2=CFOCF
2CF
2SO
2F, the gained modified membrane is taken out sodium type polymeric film with placing 50 ℃ of hydrolysis reaction of aqueous sodium hydroxide solution 6 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains PHFP base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 6:
FEP base (per) fluoropolymer porous-film is put into plasma producing apparatus, carry out the plasma body pre-treatment in the plasma atmosphere district, processing power is 300W, and the treatment time is 2 minutes, then with it under nitrogen protection, immerse liquid ICF
2CF
2OCF
2CF
2SO
2Among the F, 50 ℃ of reactions were taken out after 16 hours, then it were removed the not ICF in the FEP grafting with ethanol then
2CF
2OCF
2CF
2SO
2F, the gained modified membrane is taken out potassium type ion exchange polymer film with placing 60 ℃ of hydrolysis reaction of potassium hydroxide aqueous solution 6 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains FEP base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 7:
PTFE base (per) fluoropolymer porous-film is put into plasma producing apparatus, carry out the plasma body pre-treatment in the plasma atmosphere district, processing power is 250W, and the treatment time is 3 minutes, then with it under nitrogen protection, immerse liquid CF
2=CFOCF
2CF
2SO
2Among the F, 50 ℃ of reactions were taken out after 16 hours, then it were removed the not CF in the PTFE grafting with ethanol then
2=CFOCF
2CF
2SO
2F, the gained modified membrane is taken out potassium type ion exchange polymer film with placing 60 ℃ of hydrolysis reaction of potassium hydroxide aqueous solution 6 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains PTFE base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 8:
PHFP base (per) fluoropolymer porous-film is put into plasma producing apparatus, carry out the plasma body pre-treatment in the plasma atmosphere district, processing power is 200W, and the treatment time is 6 minutes, then with it under nitrogen protection, immerse liquid ICF
2CF
2OCF
2CF
2SO
3Among the K, 60 ℃ of reactions were taken out after 24 hours, then it were removed the not ICF in the PHFP grafting with ethanol then
2CF
2OCF
2CF
2SO
3K, gained potassium type ion exchange polymer film again with carrying out IX in the dilute hydrochloric acid solution, obtains PHFP base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 9:
With PTFE base (per) fluoropolymer and CF
2=CFOCF
2CF
2SO
2F mixes, and through melt extruding or the solution-cast film forming, puts into plasma body then, carries out the plasma grafting modification in the plasma atmosphere district, and processing power is 220W, and the treatment time is 5 minutes, takes out the back and removes the not CF in grafting with ethanol
2=CFOCF
2CF
2SO
2F, the gained modified membrane is taken out potassium type ion exchange polymer film with placing 60 ℃ of hydrolysis reaction of potassium hydroxide aqueous solution 6 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains PTFE base (per) fluoropolymer ion-exchange membrane after the drying.
Embodiment 10:
With FEP base (per) fluoropolymer and ICF
2CF
2OCF
2CF
2SO
2F mixes, and through melt extruding or the solution-cast film forming, puts into plasma body then, carries out the plasma grafting modification in the plasma atmosphere district, and processing power is 230W, and the treatment time is 2 minutes, takes out the back and removes the not ICF in grafting with ethanol
2CF
2OCF
2CF
2SO
2F, the gained modified membrane is taken out sodium type ion exchange polymer film with placing 60 ℃ of hydrolysis reaction of aqueous sodium hydroxide solution 8 hours, again with carrying out IX in the dilute hydrochloric acid solution, obtains FEP base (per) fluoropolymer ion-exchange membrane after the drying.
Claims (12)
1. method for preparing perfluorinated sulfonic acid ion exchange membrane is characterized in that:
Utilize low-temperature plasma to cause fluorine-containing sulfonic acid fluoride based compound and carry out the situ-formed graft modification, pass through alkaline hydrolysis and H then at the (per) fluoropolymer porous-film
+IX obtains perfluorinated sulfonic acid ion exchange membrane, and the molecular formula of described fluorine-containing sulfonic acid fluoride based compound is CF
2=CFR
FSO
2F or IR
FSO
2F, wherein R
FChain structure for perfluoroalkyl or perfluor ether; Perhaps
Utilize low-temperature plasma initiation sulfonic fluoropolymer or sulfonic fluoropolymer salt to carry out the situ-formed graft modification, pass through H then at the (per) fluoropolymer porous-film
+IX obtains perfluorinated sulfonic acid ion exchange membrane, and the molecular formula of described sulfonic fluoropolymer or sulfonic fluoropolymer salt is CF
2=CFR
FSO
3M or IR
FSO
3M, wherein R
FRefer to the chain structure of perfluoroalkyl or perfluor ether, M is H
+Or metals ion.
2. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 1 is characterized in that: described R
FComprise-[CF
2CF
2]
nOCF
2CF
2-,-[CF
2CF (CF
3)]
nOCF
2CF
2-perhaps-C
nF
2n-, n repeateding unit number wherein, value is a nonnegative integer.
3. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 1 and 2 is characterized in that: described metals ion comprises Li
+, Na
+, K
+, Ca
2+, Mg
2+, Fe
3+Perhaps Cu
2+
4. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 1 and 2 is characterized in that: described (per) fluoropolymer is the multipolymer of tetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene and R 1216, perhaps gathers perfluoroalkoxy resin.
5. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 1 is characterized in that:
Comprise the steps:
Step 1: the (per) fluoropolymer porous-film is carried out the plasma body pre-treatment in the plasma atmosphere district;
Step 2: under protection of inert gas, with pretreated (per) fluoropolymer porous-film infiltration, in the solution of fluorine-containing sulfonic acid fluoride based compound, perhaps soak into and in the liquid body of fluorine-containing sulfonic acid fluoride based compound, cause the situ-formed graft modification;
Step 3: the (per) fluoropolymer porous-film after the taking-up graft modification, the fluorine-containing sulfonic acid fluoride based compound in the not grafting is removed in washing, carries out alkaline hydrolysis then, last and H
+IX obtains perfluorinated sulfonic acid ion exchange membrane;
Wherein, in the solution of the fluorine-containing sulfonic acid fluoride based compound of step 2, solvent is the good solvent of fluorine-containing sulfonic acid fluoride based compound and is the poor solvent of (per) fluoropolymer resin;
Perhaps, comprise the steps:
Step 1 ': the (per) fluoropolymer porous-film is carried out the plasma body pre-treatment in the plasma atmosphere district;
Step 2 ': under protection of inert gas, with pretreated (per) fluoropolymer porous-film, soak in the solution of the solution of sulfonic fluoropolymer or sulfonic fluoropolymer salt and cause the situ-formed graft modification; Perhaps, soak in the liquid body of the liquid body of sulfonic fluoropolymer or sulfonic fluoropolymer salt and cause the situ-formed graft modification;
Step 3 ': take out (per) fluoropolymer porous-film, washing after the graft modification remove sulfonic fluoropolymer or sulfonic fluoropolymer salt in the not grafting, then with H
+IX, obtain perfluorinated sulfonic acid ion exchange membrane;
Wherein, step 2 ' the solution of sulfonic fluoropolymer in, solvent is the good solvent of sulfonic fluoropolymer and is the poor solvent of (per) fluoropolymer resin; Step 2 ' the solution of sulfonic fluoropolymer salt in, solvent is the good solvent of sulfonic fluoropolymer salt and is the poor solvent of (per) fluoropolymer resin.
6. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 5 is characterized in that:
Described step 2 and step 2 ' solution in; Solvent is selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
7. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 1 is characterized in that:
Comprise the steps:
Step 1: the (per) fluoropolymer porous-film is soaked in the solution of fluorine-containing sulfonic acid fluoride based compound, perhaps soak in this body fluid of fluorine-containing sulfonic acid fluoride based compound, fluorine sulphonyl monomer fully is adsorbed on the (per) fluoropolymer porous-film, then oven dry;
Step 2: the (per) fluoropolymer porous-film that will adsorb fluorine-containing sulfonic acid fluoride based compound is put into plasma producing apparatus, carries out the modification of plasma body situ-formed graft in the plasma atmosphere district;
Step 3: the fluorine-containing sulfonic acid fluoride based compound in the not grafting is removed in (per) fluoropolymer porous-film, washing after the taking-up graft modification, carries out alkaline hydrolysis then, last and H
+IX obtains perfluorinated sulfonic acid ion exchange membrane;
Wherein, in the solution of the fluorine-containing sulfonic acid fluoride based compound of step 1, solvent is the good solvent of fluorine-containing sulfonic acid fluoride based compound and is the poor solvent of (per) fluoropolymer resin;
Perhaps, comprise the steps:
Step 1 ': the (per) fluoropolymer porous-film is soaked in the liquid body of the solution of sulfonic fluoropolymer or sulfonic fluoropolymer, sulfonic fluoropolymer fully is adsorbed on the (per) fluoropolymer porous-film, then oven dry; Perhaps, the (per) fluoropolymer porous-film is soaked in the liquid body of the solution of sulfonic fluoropolymer salt or sulfonic fluoropolymer salt, sulfonic fluoropolymer salt fully is adsorbed on the (per) fluoropolymer porous-film, then oven dry;
Step 2 ': the (per) fluoropolymer porous-film that absorption contains sulfonic fluoropolymer or adsorbs sulfonic fluoropolymer salt is put into plasma producing apparatus, carry out the modification of plasma body situ-formed graft in the plasma atmosphere district;
Step 3 ': the (per) fluoropolymer porous-film after the taking-up graft modification, sulfonic fluoropolymer or the sulfonic fluoropolymer salt in the not grafting is removed in washing, then with H
+IX obtains perfluorinated sulfonic acid ion exchange membrane;
Wherein, step 1 ' the solution of sulfonic fluoropolymer in, solvent is the good solvent of sulfonic fluoropolymer and is the poor solvent of (per) fluoropolymer resin; Step 1 ' the solution of sulfonic fluoropolymer salt in, solvent is the good solvent of sulfonic fluoropolymer salt and is the poor solvent of (per) fluoropolymer resin.
8. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 7; It is characterized in that: described step 1 and step 1 ' solution in; Solvent is selected from water, methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-Octanol, acetone, butanone, chloroform, methylene dichloride, ether, dithiocarbonic anhydride, 1-Methyl-2-Pyrrolidone, N; At least a in dinethylformamide, DMAC N,N, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
9. the method for preparing perfluorinated sulfonic acid ion exchange membrane according to claim 1 is characterized in that:
Comprise the steps:
Step 1: (per) fluoropolymer is mixed with fluorine-containing sulfonic acid fluoride based compound, through stretching method, thermic be separated, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film;
Step 2: the (per) fluoropolymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: the (per) fluoropolymer film porous-film after the taking-up graft modification, the fluorine-containing sulfonic acid fluoride based compound in the not grafting is removed in washing, carries out alkaline hydrolysis then, last and H
+IX obtains perfluorinated sulfonic acid ion exchange membrane;
Perhaps, comprise the steps:
Step 1 ': (per) fluoropolymer is mixed with sulfonic fluoropolymer, through stretching method, thermic be separated, liquid causes phase separation method, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film; Perhaps, (per) fluoropolymer is mixed with sulfonic fluoropolymer salt, through stretching method, thermic be separated, extrusion by melting or solution casting method prepare the (per) fluoropolymer porous-film;
Step 2 ': the (per) fluoropolymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3 ': the (per) fluoropolymer film porous-film after the taking-up graft modification, sulfonic fluoropolymer or the sulfonic fluoropolymer salt in the not grafting is removed in washing, then with H
+IX obtains perfluorinated sulfonic acid ion exchange membrane.
10. according to claim 5 or the 7 described methods that prepare perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: described infiltration temperature is that 20 ℃～150 ℃, infiltrating time are 1 hour～48 hours.
11. according to the described method for preparing perfluorinated sulfonic acid ion exchange membrane of arbitrary claim in the claim 1 to 9, it is characterized in that: the power of described plasma treatment is that 10W～1500W, plasma treatment time are 0.5 minute～60 minutes.
12. according to the described method for preparing perfluorinated sulfonic acid ion exchange membrane of arbitrary claim in the claim 1 to 9, it is characterized in that: described plasma atmosphere is at least a in air, rare gas element, ammonia, oxygen, hydrogen, carbonic acid gas, sulfurous gas, methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecyl, ethene, propylene, butylene, amylene, hexene, propadiene, divinyl, isoprene, acetylene, propine, butine, hexafluoroethylene, trifluoromethane, trichloromethane, methenyl bromide, nitrogen protoxide, tetrafluoromethane, silane, siloxanes, water, methyl alcohol, ethanol, vinylformic acid and the methacrylic acid vapour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110173854 CN102336924B (en) | 2011-06-24 | 2011-06-24 | Method for preparing perfluorosulfonic acid ion exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110173854 CN102336924B (en) | 2011-06-24 | 2011-06-24 | Method for preparing perfluorosulfonic acid ion exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102336924A CN102336924A (en) | 2012-02-01 |
| CN102336924B true CN102336924B (en) | 2012-12-05 |
Family
ID=45512901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110173854 Active CN102336924B (en) | 2011-06-24 | 2011-06-24 | Method for preparing perfluorosulfonic acid ion exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102336924B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585857B (en) * | 2017-09-29 | 2021-09-03 | 国家电网公司 | Preparation method of nitrogen-doped carbon-supported platinum-based catalyst for fuel cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10149587A1 (en) * | 2001-10-09 | 2003-04-17 | Geesthacht Gkss Forschung | Preparation of photoreactive coated polymer membranes by surface functionalization useful for separation of specific substances, e.g. by membrane adsorption, solid phase extraction, membrane chromatography |
| WO2004051782A1 (en) * | 2002-06-28 | 2004-06-17 | Dubitsky Yuri A | Fuel cell incorporating a polymer electrolyte membrane grafted by irradiation |
| CN101205305A (en) * | 2007-12-05 | 2008-06-25 | 天津工业大学 | Negative electric charge polyvinylidene fluoride modified film and preparation thereof |
| CN101463164A (en) * | 2009-01-14 | 2009-06-24 | 天津大学 | Method for preparing polymer in situ alloy by alkene monomer polymerization initiated by plasma surface |
| CN101890314A (en) * | 2010-07-20 | 2010-11-24 | 东华大学 | Surface hydrophilic modification method for polytetrafluoroethylene bulked membrane |
-
2011
- 2011-06-24 CN CN 201110173854 patent/CN102336924B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10149587A1 (en) * | 2001-10-09 | 2003-04-17 | Geesthacht Gkss Forschung | Preparation of photoreactive coated polymer membranes by surface functionalization useful for separation of specific substances, e.g. by membrane adsorption, solid phase extraction, membrane chromatography |
| WO2004051782A1 (en) * | 2002-06-28 | 2004-06-17 | Dubitsky Yuri A | Fuel cell incorporating a polymer electrolyte membrane grafted by irradiation |
| CN101205305A (en) * | 2007-12-05 | 2008-06-25 | 天津工业大学 | Negative electric charge polyvinylidene fluoride modified film and preparation thereof |
| CN101463164A (en) * | 2009-01-14 | 2009-06-24 | 天津大学 | Method for preparing polymer in situ alloy by alkene monomer polymerization initiated by plasma surface |
| CN101890314A (en) * | 2010-07-20 | 2010-11-24 | 东华大学 | Surface hydrophilic modification method for polytetrafluoroethylene bulked membrane |
Non-Patent Citations (2)
| Title |
|---|
| 离子体法制备强酸性离子交换纤维;刘丽; 刘廷岳;《北京服装学院学报(自然科学版)》;20090430;第28卷(第4期);第7-11页 * |
| 等离子体法制备强碱性离子交换纤维;张道武, 刘廷岳;《北京服装学院学报》;20091031;第29卷(第4期);1-12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102336924A (en) | 2012-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102336923B (en) | Preparation method of aromatic polymer ion exchange membrane containing fluosulfonic acid on side chain | |
| Winardi et al. | Sulfonated poly (ether ether ketone)-based proton exchange membranes for vanadium redox battery applications | |
| CN103517912B (en) | Sulfonates compound, the polymer dielectric film comprising the compound and the fuel cell comprising the polymer dielectric film | |
| CN103337649B (en) | A kind of modified graphene/sulfonated poly (phenylene oxide) PEM and preparation method thereof | |
| Xu et al. | Synthesis and properties of a novel side-chain-type hydroxide exchange membrane for direct methanol fuel cells (DMFCs) | |
| JP5862372B2 (en) | Production method of polymer, production method of electrolyte membrane for polymer electrolyte fuel cell, and production method of membrane electrode assembly | |
| CN104624067A (en) | Imidazole functionalized polyether sulfone anion-exchange membrane and preparation method thereof | |
| CN104672481A (en) | Metal-organic framework (MOF) modified graphene/polymer hybrid proton exchange membrane and preparation method thereof | |
| CN103159973B (en) | New process for preparing porous high polymer reinforced perfluorinated sulfonic acid resin composite membrane | |
| CN101367903A (en) | Enhancement type composite proton exchanging film based on semi-interpenetrating network | |
| CN104140545A (en) | Ionic liquid/polymer electrolyte membrane and preparation method thereof | |
| Yan et al. | Anion exchange membranes by bromination of tetramethylbiphenol-based poly (sulfone) s | |
| JP2003288916A (en) | Direct methanol fuel cell membrane and its manufacturing method | |
| CN102336924B (en) | Method for preparing perfluorosulfonic acid ion exchange membrane | |
| CN105860113A (en) | Sulphonated naphthalene ether grafted fluorinated polyether containing proton exchange membrane and preparation method thereof | |
| CN107522266B (en) | Preparation method of hierarchical porous carbon material capacitive desalination electrode material | |
| JP2009185250A (en) | Manufacturing method of isolated polymer | |
| CN115991823B (en) | Mixed perfluorinated proton exchange membrane and preparation method thereof | |
| CN113381046B (en) | Preparation method of enhanced fluorine-containing composite membrane or membrane electrode | |
| CN110975653B (en) | Dinitrogen-containing spiro quaternary ammonium salt cross-linked anion exchange membrane material, and preparation method and application thereof | |
| CN113097549B (en) | High-enhancement type fluorine-chlorine-containing alkaline fuel cell membrane | |
| Mandanipour | Chemical Modification of Proton Exchanger Sulfonated Polystyrene with Sulfonated Graphene Oxide for Application as a New Polymer Electrolyte Membrane in Direct Methanol Fuel Cell | |
| JP5842919B2 (en) | Method for producing organic compound having sulfo group, method for producing liquid composition, and method for hydrolyzing organic compound having fluorosulfonyl group | |
| CN112403293A (en) | Sulfonated polyaryletherketone-inorganic composite membrane and preparation method thereof | |
| CN113896923A (en) | Asymmetric ion exchange membrane based on polyether sulfone main chain and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120201 Assignee: YUYAO PURO WATER PURIFICATION EQUIPMENT CO.,LTD. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980033215 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230306 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120201 Assignee: Ningbo Weiwei Intelligent Technology Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980034354 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230331 Application publication date: 20120201 Assignee: Ningbo Wayne Automation Technology Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980034353 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230331 Application publication date: 20120201 Assignee: NINGBO WEILONG TRANSMISSION MACHINERY Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980034351 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230331 Application publication date: 20120201 Assignee: TIANXING AUTO PARTS Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980034355 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230331 Application publication date: 20120201 Assignee: NINGBO LIQIANG MACHINERY CO.,LTD. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980034350 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230331 Application publication date: 20120201 Assignee: Ningbo Xinweilong Machinery Manufacturing Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980034352 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20230331 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120201 Assignee: NINGBO ZHAOBAO MAGNET Co.,Ltd. Assignor: NINGBO INSTITUTE OF MATERIALS TECHNOLOGY & ENGINEERING, CHINESE ACADEMY OF SCIENCES Contract record no.: X2023980046124 Denomination of invention: A method for preparing perfluorosulfonic acid ion exchange membranes Granted publication date: 20121205 License type: Common License Record date: 20231107 |