CN102336923B - Preparation method of aromatic polymer ion exchange membrane containing fluosulfonic acid on side chain - Google Patents
Preparation method of aromatic polymer ion exchange membrane containing fluosulfonic acid on side chain Download PDFInfo
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- CN102336923B CN102336923B CN 201110173841 CN201110173841A CN102336923B CN 102336923 B CN102336923 B CN 102336923B CN 201110173841 CN201110173841 CN 201110173841 CN 201110173841 A CN201110173841 A CN 201110173841A CN 102336923 B CN102336923 B CN 102336923B
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- aromatic polymer
- fluoropolymer
- sulfonic fluoropolymer
- film
- sulfonic
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 106
- 229920000642 polymer Polymers 0.000 title claims abstract description 103
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 36
- 238000012986 modification Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 229920002313 fluoropolymer Polymers 0.000 claims description 128
- 239000004811 fluoropolymer Substances 0.000 claims description 128
- 239000002904 solvent Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 229910052731 fluorine Inorganic materials 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000011737 fluorine Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 34
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 239000007788 liquid Substances 0.000 claims description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 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
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
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- 229960001701 chloroform Drugs 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- -1 metals ion Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
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- 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
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 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 7
- 238000005266 casting Methods 0.000 claims description 7
- 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
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 238000005191 phase separation Methods 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 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
- 239000000178 monomer Substances 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 238000009832 plasma treatment Methods 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 210000001124 body fluid Anatomy 0.000 claims description 3
- 239000010839 body fluid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 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
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims 3
- 210000004379 membrane Anatomy 0.000 claims 3
- 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
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000000909 electrodialysis Methods 0.000 abstract description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
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- 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
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
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- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- REDPJOZSAHHIAO-UHFFFAOYSA-N butane;pentane Chemical compound CCCC.CCCCC REDPJOZSAHHIAO-UHFFFAOYSA-N 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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Abstract
The invention discloses a preparation method of an aromatic polymer ion exchange membrane containing fluosulfonic acid on the side chain. The low temperature plasma method is used to carry out in-situ grafting modification on the aromatic polymer membrane and introduce fluosulfonic acid group on the side chain. In comparison with the prior art, the preparation method provided by the invention has advantages of low cost, simple process, convenient operation, fast processing speed, good processing effect, no environmental pollution, energy conservation and emission reduction, and is more suitable for industrial production, and can be applied in the fields of new energy technology, various electrolytic preparation devices, electrodialysis, chemical catalysis, gas separation, gas drying, sewage processing, seawater desalination, chlor alkali industry and the like.
Description
Technical field
The invention belongs to high molecular functional membrane technique field, be specifically related to a kind of preparation method of side chain sulfonic fluoropolymer aromatic polymer ion-exchange membrane.
Background technology
In recent years, face the contradiction that becomes increasingly conspicuous between the energy, resource, the environment, the policies and measures that advance new energy technology development are launched respectively in countries in the world.In this strand tide, as the fuel cell of portable portable power source, and the flow battery that is used for extensive electric power storage energy storage has broad application prospects in fields such as communication, military affairs and emergency repairs, especially paid close attention to.These two kinds of cell apparatus all will utilize ion-exchange membrane to separate oxidizing reaction half-cell and reduction reaction half-cell in the same monocell.Just because of this important need, the high-performance ion-exchange membrane is causing closely during the last ten years that as new energy materials scientific and technological circle pay close attention to and obtain remarkable technical progress energetically.In addition, the high-performance ion-exchange membrane also has the irreplaceable effect of other material in such as fields such as electrolytic preparation device, electrodialysis, chemical catalysis, gas delivery, gas drying, WWT, sea water desaltination, chlorine industries.
Compare with ion-exchange membrane in the past; Employed PEM is except requiring to possess the fundamental characteristics of ion-exchange membrane in new forms of energy battery technology field; For example membrane resistance is low, ion selectivity is strong, physical strength is high, also must possess following several respects characteristics: (1) chemicalstability is high, anti-electrochemistry oxygen voltinism is strong; (2) have temperature tolerance and moisture retention; (3) stop gas-permeable.Perfluorinated ionic membrane, Nafion film and the analogous products produced of Dupont company for example, the Dow film that Dow company produces is high and be used widely with its chemicalstability height and physical strength.But also there are some shortcomings in perfluorinated ion-exchange membrane, and for example the temperature rising can cause that specific conductivity reduces, and film is prone to take place chemical degradation during high temperature; The synthetic difficulty of monomer, cost is high; Waste product is hard to manage, costs an arm and a leg etc.In addition; When being used for methanol fuel cell, perfluorinated ionic membrane is prone to take place the methanol leakage problem; The electroconductibility of existing Nafion class fluosulfonic acid PEM also relies on the existence of water strongly simultaneously, therefore can not be used to be higher than 100 ℃ high-efficiency fuel cell or anhydrous lithium cell.
The problem that exists to perfluorinated ion-exchange membrane is that the PEM of main chain becomes one of focus of Recent study with the aromatic polymer.Utilize the prepared PEM of polymer materials that contains benzene ring structure in the backbone structure to have Heat stability is good, advantages such as anti-electrochemical etching.Such common polymer materials comprises polyetheretherketone (PEEK), polyethersulfone (PES), ppe (PPO) etc. and corresponding derivant material thereof etc.Through these polymkeric substance of Direct Sulfonation, in side-chain structure, import sulfonic acid group, make it possess the proton exchange function.The advantage of this method is that synthesis step is simple, easy mass preparation, and with respect to the perfluorinated sulfonic acid PEM, cost is lower.But this method needs harsh reaction conditionss such as high temperature and strong sulfonated reagent, is prone to cause the degraded of macromolecular chain and side reaction to take place, thereby influences the chemicalstability of product, anti-electrochemical oxidation characteristic etc.
Fluosulfonic acid is the existence that a kind of super acids and conductivity do not rely on water, can under the situation that does not improve loading capacity, increase the proton electric conductivity of polymeric film at introducing fluosulfonic acid group on the aromatic polymer side chain.Research shows that under low humidity, side chain is that the specific conductivity of fluosulfonic acid base polyaromatic polymeric film is 3 times～60 times of corresponding sulfonated poly aromatic adoption compound film, and therefore, the aromatic polymer membrane that side chain contains the fluosulfonic acid base becomes the focus of research day by day.
At present, contain at side chain that employed presoma resin generally is that series reaction such as coupling obtain through bromination on main polymer chain in the preparation of aromatic polymer membrane of fluosulfonic acid base; Perhaps through bromination coupling on polymerization single polymerization monomer earlier, the method for repolymerization is carried out.But all there is the problem that the preparation process is loaded down with trivial details and efficient is not high to some extent in these two kinds of methods.Consider from the large-scale commercial prodn angle, particularly avoid the use of strong oxidizer or poisonous chemical reagent sets out, need the comparatively gentle friendly process route of exploitation, obtain the more excellent proton exchange membrane material of cost performance.
Summary of the invention
Technical purpose of the present invention is not enough to prior art, and a kind of preparation method of side chain sulfonic fluoropolymer aromatic polymer ion-exchange membrane is provided.
The present invention realizes that the technical scheme that above-mentioned technical purpose is taked is: a kind of preparation method of side chain sulfonic fluoropolymer aromatic polymer 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 aromatic polymer porous-film
+IX obtains the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer; 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 as required at the aromatic polymer porous-film
+IX obtains the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
Aromatic polymer includes but not limited to gather a kind of in biphenyl, polysulfones, polybenzimidazole, polyaryletherketone, polyethersulfone, polyarylsulphone, polyetherketone, ppe, polyphenylene sulfide, poly aromatic acid amides and poly aromatic imide and the verivate thereof.
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
+Perhaps metals ion includes 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. 1 is the technological line synoptic diagram of these three kinds of embodiments.
First kind of embodiment is at first the aromatic polymer porous-film to be carried out the plasma body pre-treatment, carries out the situ-formed graft modification with fluorine-containing sulfonic acid fluoride based compound or sulfonic fluoropolymer (salt) then, is hydrolyzed as required at last and H
+IX obtains the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
First kind of embodiment comprises the steps:
Step 1: the aromatic polymer 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 aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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 aromatic polymer 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 aromatic polymer porous-film is soaked 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: take out the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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; And be 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; Dinethylformamide, N, at least a in N-methylacetamide, methyl-sulphoxide, THF, ETHYLE ACETATE, dioxane, acetonitrile, benzene, toluene and the YLENE.
Second kind of embodiment is at first the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
Second kind of embodiment comprises the steps:
Step 1: the aromatic polymer 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 aromatic polymer porous-film, then oven dry;
Step 2: the aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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 aromatic polymer porous-film is soaked in the liquid body of the solution of sulfonic fluoropolymer or sulfonic fluoropolymer, sulfonic fluoropolymer fully is adsorbed on the aromatic polymer porous-film, then oven dry; Perhaps, the aromatic polymer 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 aromatic polymer porous-film, then oven dry;
Step 2: the aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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 aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
The third embodiment comprises the steps:
Step 1: aromatic polymer 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 aromatic polymer porous-film;
Step 2: the aromatic polymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
Perhaps, the third embodiment comprises the steps:
Step 1: aromatic polymer 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 aromatic polymer porous-film; Perhaps, aromatic polymer 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 aromatic polymer porous-film;
Step 2: the aromatic polymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: take out the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
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; Trifluoromethane; Trichloromethane; Methenyl bromide; 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, prepares the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer, has superpower cation activity; Ionic conductivity is good; Mechanical property is high, and chemicalstability is high, and ion-activated ability is low; Be easy to adsorb organic polar solvent and form stable stratiform or tubulose ionic channel, resistant to elevated temperatures advantage.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 technological line synoptic diagram of three kinds of embodiments taking of technical scheme of the present invention;
Fig. 2 is the reaction mechanism synoptic diagram of first and second kind embodiment among Fig. 1.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment 1:
The polysulfones porous-film is immersed liquid ICF
2CF
2OCF
2CF
2SO
2Among the F, soak after 5 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 210W; Treatment time is 3 minutes, removes not at polysulfones grafted ICF with acetone 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 side chain sulfonic fluoropolymer polysulfones ion-exchange membrane after the drying.
Embodiment 2:
Polyphenylene sulfide 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 180W; Treatment time is 5 minutes, and water is removed not at polyphenylene sulfide grafted ICF 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 side chain sulfonic fluoropolymer polyphenylene sulfide ion-exchange membrane after the drying.
Embodiment 3:
To gather fragrant imide porous-film and immerse 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 170W; Treatment time is 4 minutes, removes not at the ICF that gathers in the fragrant imide 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 the side chain sulfonic fluoropolymer after the drying and gathers fragrant imide ion-exchange membrane.
Embodiment 4:
Polyether-ether-ketone 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 200W; Treatment time is 2 minutes, removes not at polyetheretherketone grafted ICF 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 side chain sulfonic fluoropolymer polyetheretherketone ion-exchange membrane after the drying.
Embodiment 5:
To gather the biphenyl porous-film and immerse 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 220W; Treatment time is 1 minute, does not remove with ethanol then and is gathering biphenyl grafted CF
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, with carrying out IX in the dilute hydrochloric acid solution, obtains the side chain sulfonic fluoropolymer after the drying and gathers the biphenyl ion-exchange membrane again.
Embodiment 6:
The ppe 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 2.5 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 not at ppe grafted ICF 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 side chain sulfonic fluoropolymer ppe ion-exchange membrane after the drying.
Embodiment 7:
With polysulfones 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 3 minutes, takes out the back and removes the not CF in the polysulfones 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 side chain sulfonic fluoropolymer polysulfones ion-exchange membrane after the drying.
Embodiment 8:
With polyetheretherketone 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 the polyetheretherketone 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 side chain sulfonic fluoropolymer polyetheretherketone ion-exchange membrane after the drying.
Claims (12)
1. the preparation method of a side chain sulfonic fluoropolymer aromatic polymer 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 aromatic polymer porous-film
+IX obtains the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer, 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 aromatic polymer porous-film
+IX obtains the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer, and the molecular formula of described sulfonic fluoropolymer or sulfonic fluoropolymer salt is CF
2=CFR
FSO
3M or IR
FSO
3M, wherein R
FChain structure for perfluoroalkyl or perfluor ether; M is H
+Perhaps metals ion.
2. the preparation method of side chain sulfonic fluoropolymer aromatic polymer 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. according to the preparation method of claim 1 or 2 described side chain sulfonic fluoropolymer aromatic polymer ion-exchange membranees, it is characterized in that: described metals ion comprises Li
+, Na
+, K
+, Ca
2+, Mg
2+, Fe
3+Perhaps Cu
2+
4. according to the preparation method of claim 1 or 2 described side chain sulfonic fluoropolymer aromatic polymer ion-exchange membranees, it is characterized in that: described aromatic polymer is to gather at least a in biphenyl, polysulfones, polybenzimidazole, polyethersulfone, polyarylsulphone, polyetherketone, ppe, polyphenylene sulfide, poly aromatic acid amides and the poly aromatic imide.
5. the preparation method of side chain sulfonic fluoropolymer aromatic polymer ion-exchange membrane according to claim 1 is characterized in that: comprise the steps:
Step 1: the aromatic polymer porous-film is carried out the plasma body pre-treatment in the plasma atmosphere district;
Step 2: under protection of inert gas, pretreated aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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 aromatic polymer porous-film is carried out the plasma body pre-treatment in the plasma atmosphere district;
Step 2 ': under protection of inert gas; Pretreated aromatic polymer porous-film is soaked 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 ': the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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, 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 preparation method of side chain sulfonic fluoropolymer aromatic polymer ion-exchange membrane according to claim 5; It 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 preparation method of side chain sulfonic fluoropolymer aromatic polymer ion-exchange membrane according to claim 1 is characterized in that: comprise the steps:
Step 1: the aromatic polymer 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 aromatic polymer porous-film, then oven dry;
Step 2: the aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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 aromatic polymer porous-film is soaked in the liquid body of the solution of sulfonic fluoropolymer or sulfonic fluoropolymer, sulfonic fluoropolymer fully is adsorbed on the aromatic polymer porous-film, then oven dry; Perhaps, the aromatic polymer 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 aromatic polymer porous-film, then oven dry;
Step 2 ': the aromatic polymer 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 aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
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, 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.
8. the preparation method of side chain sulfonic fluoropolymer aromatic polymer 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 preparation method of side chain sulfonic fluoropolymer aromatic polymer ion-exchange membrane according to claim 1 is characterized in that: comprise the steps:
Step 1: aromatic polymer 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 aromatic polymer porous-film;
Step 2: the aromatic polymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer;
Perhaps, comprise the steps:
Step 1: aromatic polymer 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 aromatic polymer porous-film; Perhaps, aromatic polymer is mixed with sulfonic fluoropolymer salt, through stretching method, thermic be separated, extrusion by melting or solution casting method prepare the aromatic polymer porous-film;
Step 2: the aromatic polymer porous-film is carried out plasma body situ-formed graft modified-reaction in the plasma atmosphere district;
Step 3: take out the aromatic polymer 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 the aromatic polymer ion-exchange membrane of side chain sulfonic fluoropolymer.
10. according to the preparation method of claim 5 or 7 described side chain sulfonic fluoropolymer aromatic polymer ion-exchange membranees, it is characterized in that: described infiltration temperature is that 20 ℃～150 ℃, infiltrating time are 1 hour～48 hours.
11. the preparation method according to the described side chain sulfonic fluoropolymer of arbitrary claim aromatic polymer ion-exchange membrane in the claim 1 to 9 is characterized in that: the power of described plasma treatment is preferably 10W～1500W, plasma treatment time and is preferably 0.5 minute～and 60 minutes.
12. the preparation method according to the described side chain sulfonic fluoropolymer of arbitrary claim aromatic polymer ion-exchange membrane in the claim 1 to 9 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, trifluoromethane, trichloromethane, methenyl bromide, silane, siloxanes, water, methyl alcohol, ethanol, vinylformic acid and the methacrylic acid vapour.
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| CN103881042B (en) * | 2012-12-21 | 2016-08-03 | 中国科学院宁波材料技术与工程研究所 | A kind of polyether-ether-ketone resin of sulfonic fluoropolymer side chain and preparation method thereof |
| CN105085847B (en) * | 2014-05-23 | 2018-05-04 | 中国科学院宁波材料技术与工程研究所 | A kind of sulfuryl amine aromatic polymer, its preparation method and application |
| CN105694455B (en) * | 2016-04-13 | 2017-12-29 | 武汉纺织大学 | A kind of material modified preparation method of polyphenylene sulfide |
| CN109631957A (en) * | 2019-01-14 | 2019-04-16 | 南方科技大学 | A kind of stretchable hypersensitive electronic skin and its preparation method and application |
| CN113314747B (en) * | 2021-05-26 | 2022-04-22 | 上海大学 | Sulfonated poly biphenyl proton exchange membrane with nano phase separation structure and preparation method thereof |
| CN114377556B (en) * | 2022-01-19 | 2022-10-14 | 西南石油大学 | Temperature-resistant composite water treatment membrane and preparation method thereof |
| CN115304748B (en) * | 2022-09-02 | 2023-06-23 | 沈阳师范大学 | Preparation method of porous polymer material |
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