CN108864455A - A kind of preparation method of photocatalysis anion-exchange membrane - Google Patents
A kind of preparation method of photocatalysis anion-exchange membrane Download PDFInfo
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- CN108864455A CN108864455A CN201810797232.2A CN201810797232A CN108864455A CN 108864455 A CN108864455 A CN 108864455A CN 201810797232 A CN201810797232 A CN 201810797232A CN 108864455 A CN108864455 A CN 108864455A
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- anion
- exchange membrane
- photocatalysis
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 72
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 54
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 14
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- GOMPLJOPYGQBPL-UHFFFAOYSA-K [F-].[F-].[F-].F.[B+3] Chemical compound [F-].[F-].[F-].F.[B+3] GOMPLJOPYGQBPL-UHFFFAOYSA-K 0.000 claims description 11
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 11
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 239000012989 trithiocarbonate Substances 0.000 claims description 10
- -1 amine Compound Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000008961 swelling Effects 0.000 abstract description 16
- 238000013459 approach Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 101150027801 CTA1 gene Proteins 0.000 description 7
- 101100273295 Candida albicans (strain SC5314 / ATCC MYA-2876) CAT1 gene Proteins 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 150000004880 oxines Chemical class 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000004899 motility Effects 0.000 description 5
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical class ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 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 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000002560 therapeutic procedure Methods 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical group CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F116/14—Monomers containing only one unsaturated aliphatic radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention discloses a kind of preparation method of photocatalysis anion-exchange membrane, includes the following steps：Using 2- chloroethyl vinyl ether as reaction monomers fatty-chain polymers are made using light-operated cationic polymerization technology, as the main chain of membrane material in step S1；The fatty-chain polymers and the polyamine compounds are carried out quaternization reaction, are obtained the photocatalysis anion-exchange membrane by step S2 using polyamine compounds as quaternizing agent and crosslinking agent.The present invention solves the technical problem that the fatty-chain polymers can not form a film by flexible high, the strong bring of viscoplasticity, new approach is opened for the preparation of anion-exchange membrane, the photocatalysis anion-exchange membrane prepared by the present invention is also able to maintain higher resistance to swelling while having compared with high ionic conductivity, so that anion-exchange membrane is with good performance, in addition, reaction condition of the present invention is mild, controllability is high.
Description
Technical field
The present invention relates to fuel cell field of membrane material, and in particular to a kind of preparation side of photocatalysis anion-exchange membrane
Method.
Background technique
The bottleneck problems such as the price faced based on Proton Exchange Membrane Fuel Cells and service life, alkaline anion-exchange membrane combustion
Material battery has gradually developed, and compared with Proton Exchange Membrane Fuel Cells, alkali anion membrane cell has alkaline condition
Down faster redox reactions efficiency, allow non-precious metal catalyst use and due to fuel and transmitting side hydroxy
To on the contrary, many advantages such as fuel leakage therefore can be substantially reduced.However, the hydroxide ion of anion-exchange membrane (AEM)
Trade-off effect between conductivity and resistance to swelling is still the head for hindering alkali anion membrane cell further to develop
Want bottleneck.
The preparation of existing anion-exchange membrane generallys use high molecular polymer as main chain, and ion function base is carried out to it
Anion-exchange membrane is prepared after dough, or from functional monomer, aggregated chaining prepares anion-exchange membrane, existing skill
About the preparation of polymer in art, living polymerisation process is caused using relatively broad with heat, but these reaction process need to heat
Causing, reaction terminating, which needs to freeze, to be quenched, and needs multistep reaction, more purification to operate in synthesis complex configuration polymer,
Severe reaction conditions, reaction process poor controllability.
In addition, the main chain of conventional anion exchange membrane mostly uses greatly aromatics polymer, due to the chain of fragrant quasi polymer
Section rigidity is larger, and motility is poor, prepares anion-exchange membrane for ion functionalization after first forming a film, and is difficult that microfacies point occurs
From, for preparing anion-exchange membrane after homogeneous functionalization, in solvent volatilization process, since the locomitivity of main chain is insufficient,
Microphase-separated is still relatively difficult, and the configuration for being generally taken through adjusting anion-exchange membrane in the prior art to this is micro- to regulate and control
Mutually separation pattern, but the degree of control is limited, the anion exchange film properties of preparation are poor.
To sum up, the preparation of anion-exchange membrane not can effectively solve the lance between ionic conductivity and resistance to swelling yet at present
Shield causes the performance of film poor, significantly limits the application and development of AEM.
In view of the above drawbacks, creator of the present invention obtains the present invention by prolonged research and practice finally.
Summary of the invention
To solve above-mentioned technological deficiency, the technical solution adopted by the present invention is, provides a kind of photocatalysis anion exchange
The preparation method of film, includes the following steps：
Aliphatic chain is made using light-operated cationic polymerization technology using 2- chloroethyl vinyl ether as reaction monomers in step S1
Polymer, as the main chain of membrane material；
Step S2, using polyamine compounds as quaternizing agent and crosslinking agent, by the fatty-chain polymers with it is described
Aminated compounds carries out quaternization reaction, obtains the photocatalysis anion-exchange membrane.
Preferably, the specific synthesis step of fatty-chain polymers described in step S1 is as follows：
S1-1, by the 2- chloroethyl vinyl ether and chain transfer agents and photochemical catalyst under Blue LEDs irradiation into
The light-operated cationic polymerization of row, obtains the first reaction solution；
S1-2 obtains poly- 2- chloroethyl after carrying out revolving processing removal solvent and residual monomer to first reaction solution
Vinyl ethers.
Preferably, the photochemical catalyst includes 2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salts, the chain turns
Moving reagent includes S-1- isobutoxyethy S '-ethyl trithiocarbonate.
Preferably, the 2- chloroethyl vinyl ether, the S-1- isobutoxyethy S '-ethyl trithiocarbonate with
The molar ratio of 2,4,6- tri- (p-methoxyphenyl) the pyrans tetrafluoride boron salt is 100~1000:1:0.02~0.08.
Preferably, the light-operated cationic polymerization carries out at room temperature, reaction time control is 18h~48h.
Preferably, the degree of polymerization of the poly- 2- chloroethyl vinyl ether is 97~600.
Preferably, step S2 specifically comprises the following steps：
The poly- 2- chloroethyl vinyl ether is dissolved in organic solvent by S2-1, and heating heat treatment obtains the second reaction solution；
The polyamine compounds are added into second reaction solution by S2-2, carry out quaternary ammonium reaction, it is anti-to obtain third
Answer liquid；
The third reaction solution is coated on substrate, the photocatalysis anion-exchange membrane is obtained after drying by S2-3.
Preferably, the molar ratio of the poly- 2- chloroethyl vinyl ether and the polyamine compounds is 5~15:1.
Preferably, the polyamine compounds include triethylene diamine, pentamethyl-diethylenetriamine or N, N, N ', N '-four
Dimethyl-p-phenylenediamine.
Preferably, it is 10wt% that the poly- 2- chloroethyl vinyl ether, which is dissolved in the mass percent in the organic solvent,.
Compared with the prior art the beneficial effects of the present invention are：
1, the present invention realizes the fat while quaternized by carrying out quaternized processing to fatty-chain polymers
It is difficult to solve the technology that the fatty-chain polymers can not form a film by flexible high, the strong bring of viscoplasticity for the crosslinking of chain polymerization object
Topic opens new approach for the preparation of anion-exchange membrane；
2, the present invention prepares the fatty-chain polymers using light-operated cationic polymerization technology, realizes function under room temperature
Property monomer light-operated living polymerization, reaction condition is mild, and controllability is high, can by adjusting the chain transfer agents with it is described
The feed ratio of monomer and reaction time control the degree of polymerization of the fatty-chain polymers；
3, photocatalysis anion-exchange membrane prepared by the present invention be also able to maintain while having compared with high ionic conductivity compared with
High resistance to swelling, so that anion-exchange membrane is with good performance.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance of photochemical catalyst 2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salt of the present invention
Spectrum；
Fig. 2 is chain transfer agents S-1- isobutoxyethy S '-ethyl trithiocarbonate nuclear magnetic resonance in the present invention
Hydrogen spectrum；
Fig. 3 is the nuclear magnetic resonance spectroscopy of poly- 2- chloroethyl vinyl ether in the present invention；
Fig. 4 is the gel permeation chromatography of poly- 2- chloroethyl vinyl ether in the present invention；
Fig. 5 is the FTIR spectrum of photocatalysis anion-exchange membrane in the present invention；
Fig. 6 is the chloride conductance variation of photocatalysis anion-exchange membrane at different temperatures in the embodiment of the present invention one
Figure.
Specific embodiment
Below in conjunction with attached drawing, the forgoing and additional technical features and advantages are described in more detail.
The present invention provides a kind of preparation method of photocatalysis anion-exchange membrane, uses light-operated cationic polymerization technology first
Fatty-chain polymers are prepared, and as the main chain of membrane material, quaternized processing then are carried out to the fatty-chain polymers,
Photocatalysis anion-exchange membrane is finally made using casting filming therapy.
Wherein, group containing R-Cl in the fatty-chain polymers, wherein R is alkyl.
According to the present invention, first with light-operated cationic polymerization technology synthctic fat chain homopolymer；It is with 2- chloroethyl
Vinyl ethers (ClEVE) is monomer, S-1- isobutoxyethy S '-ethyl trithiocarbonate (CTA1) be chain transfer agents,
2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salts (C1) are photochemical catalyst, are carried out under Blue LEDs irradiation light-operated
Cationic polymerization prepares the poly- 2- chloroethyl vinyl ether (PClEVE) of the aliphatic chain homopolymer.
Specifically, vacuum distillation processing is carried out to the 2- chloroethyl vinyl ether, to remove polymerization inhibitor；
The synthesis of the S-1- isobutoxyethy S '-ethyl trithiocarbonate includes the following steps：
(1) under nitrogen protection, sodium hydride is added in the first dry flask, anhydrous second is added into first flask
Ether forms the first mixed liquor, and first mixed liquor is cooled to 0 DEG C；It is added dropwise into first mixed liquor and newly to steam
Ethyl mercaptan forms suspension, is cooled to 0 DEG C after the suspension is stirred 10min at room temperature；Into the suspension
The carbon disulfide newly steamed is added dropwise, forms dark-yellow suspension, and 2h, system are stirred to the dark-yellow suspension at room temperature
Obtain three thioesters acid sodium suspension of ethyl；
(2) ethereal HCI solution is added in the second dry flask, its liquid nitrogen is cooled to -78 DEG C, to described second
Isobutyl vinyl ether after distillation is added dropwise in flask, obtains pale yellow solution, by the pale yellow solution at -78 DEG C
1h is stirred, then heats to 0 DEG C；
(3) cooling solution obtained in step (2) is added drop-wise to the three thioesters acid sodium of the ethyl in first flask
In suspension, the second mixed liquor is obtained, and be stirred at room temperature 2h, is then diluted with 10mL ether, and be saturated with 10mL
Sodium bicarbonate aqueous solution is quenched, and liquid separation is simultaneously extracted with ether, collects organic phase and uses water, salt water washing respectively, then uses n-hexane
It is dry in dilution, anhydrous sodium sulfate drying and vacuum oven, crude product is made, the crude product column chromatography is obtained
S-1- isobutoxyethy S '-ethyl trithiocarbonate described in pure chain transfer agents, specific synthesis process such as formula (1) institute
Show.
The synthesis process of 2,4,6- tri- (p-methoxyphenyl) the pyrans tetrafluoride boron salt is specific as follows：By 3.4g to first
Oxygroup benzaldehyde and 7.5g are added in 7.5g boron trifluoride ether solution methoxy benzophenone, react 2h at 100 DEG C, obtain
It precipitates to brick-red solid, filter and is washed 3 times with ether, then drying obtains brick-red solid powder at 60 DEG C in vacuum drying oven
End obtains described 2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salts, shown in specific synthesis process such as formula (2).
The light-operated cationic polymerization specifically comprises the following steps：The C1 is added into Schlenk reaction flask, takes out
Vacuum-leads to nitrogen circulation 3 times to remove the oxygen in reaction flask, be then added under nitrogen atmosphere corresponding amount the CTA1,
The ClEVE and methylene chloride (DCM) seal bottleneck and reaction flask are placed in described in the lower progress of Blue LEDs irradiation
The controllable cationic polymerization of ClEVE reacts, and obtains the first reaction solution, and reaction carries out at room temperature, and reaction time control exists
18h~48h obtains the polymer PC lEVE after carrying out revolving processing removal solvent to first reaction solution, specific to synthesize
Shown in process such as formula (3).Wherein, the molar ratio of the ClEVE, the CTA1 and the C1 are 100~1000:1:0.02~
0.08, more preferably it is set as 400:1：0.04.
The polymerization process of heretofore described PClEVE is controllable, can be by adjusting the chain transfer agents and the monomer
Feed ratio and the reaction time control the degree of polymerization of the PClEVE.The degree of polymerization of heretofore described PClEVE 97~
600。
Nuclear magnetic resonance spectroscopy test is carried out to the photochemical catalyst, the chain transfer agents and the PClEVE respectively, is surveyed
Test result is shown in Fig. 1-3.The catalyst C1 is that solvent measures nuclear-magnetism as can be seen from FIG. 1 with deuterium dimethyl sulfoxide (2.50ppm)
The spectrum chemical shift of resonance hydrogen and practical structures have good corresponding relationship, wherein the corresponding benzene in peak 1,2,3,4 (7.0-9.0ppm)
Proton on ring, the proton on the corresponding methoxyl group in peak 5,6 (3.97ppm, 3.94ppm), and the integral area ratio at each peak also with reality
Border proton quantity corresponds, it was demonstrated that the successful preparation of the catalyst C1.The chain transfer agents CTA1 is with deuterated chloroform
Solvent, as can be seen from FIG. 2, each proton peak shift have correct ownership, and integral area ratio is also correct, it was confirmed that the chain turns
Move the successful preparation of reagent C TA1.The PClEVE has carried out nuclear magnetic resonance spectroscopy characterization by solvent of deuterated chloroform, according to Fig. 3
It is found that each peak shift and integral area ratio are all corresponded with practical structures proton, it was confirmed that the successful polymerization of monomer, wherein
There is corresponding solvent peak in synthesis resonance hydrogen spectrum 5.30ppm due to residual in polymerization reaction solvent for use methylene chloride.
The PClEVE described in prepared polymer carries out gel permeation chromatography test, and test result is shown in Fig. 4, according to Fig. 4
It can be seen that the retention time of the polymer is about 7.8min, the number of the polymer is measured using polystyrene as reference standard
Average molecular weight is 10274g/mol, weight average molecular weight 14264g/mol, molecular weight distribution 1.39, it was confirmed that the light-operated polymerization
The high controllability of process.
Secondly, using polyamine compounds as quaternizing agent and crosslinking agent, by the fatty-chain polymers and the amine
Class compound carries out quaternization reaction, and prepares the photocatalysis anion-exchange membrane PQEVE using casting filming therapy.
Specifically, in organic solvent by PClEVE dissolution, and the organic solution of the PClEVE is warming up to 150
DEG C~170 DEG C, it is heat-treated 10min~60min, obtains the second reaction solution；Then it is added into second reaction solution described more
Aminated compounds is stirred at room temperature 5min~30min, then reaction temperature is risen to 60 DEG C~90 DEG C progress quaternary ammonium reactions, obtains
Third reaction solution, while the viscosity for monitoring the third reaction solution changes with time, when the third reaction solution viscosity compared with
When big, supplementing solvent is then coated the third reaction solution to substrate with diluting the viscosity of the third reaction solution, then into
The photocatalysis anion-exchange membrane can be obtained in row drying and processing, shown in specific synthesis process such as formula (4).Wherein, it is heat-treated
Temperature is preferably 160 DEG C, and drying temperature is preferably 60 DEG C -90 DEG C.
Heretofore described polyamine compounds include triethylene diamine (DABCO), pentamethyl-diethylenetriamine or N, N,
N ', N '-tetramethyl-para-phenylene diamine, the organic solvent include N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) or N, N-
Dimethylformamide (DMF)；The molar ratio of the PClEVE and the polyamine compounds is 5~15:1, more preferably it is set as
10:1, the PClEVE, which are dissolved in the organic solvent, obtains the solution of mass ratio 10wt%.
FTIR spectrum test is carried out to the photocatalysis anion-exchange membrane of preparation, test result is shown in Fig. 5, by
Fig. 5 can be seen that because the presence of quaternary ammoniated group make prepared by anion-exchange membrane have stronger water imbibition, adsorb water
In 3400cm-1Locate the stretching vibration peak with absorption water, show the success of the quaternization reaction of heretofore described polymer into
Row.
The ion exchange capacity (IEC) of the photocatalysis anion-exchange membrane prepared by the present invention be 1.24mmol/g~
1.94mmol/g；The present invention can by control the quaternizing agent feed intake and the reaction time controls the photocatalysis
The ion exchange capacity (IEC) of anion-exchange membrane, controllability is high, and easy to operate.
Chloride conductance, moisture content and linear swelling ratio is carried out to the photocatalysis anion-exchange membrane obtained to survey
Examination, test result is as follows shown in table：
As can be seen from the above table, it is aqueous while the photocatalysis anion-exchange membrane is had compared with high ionic conductivity
Rate and linear swelling ratio are lower, ensure that higher water swell resistance.
The present invention is based on aromatics polymer chain motility is poor, it is unfavorable for that microphase-separated occurs, selects fatty chain polymerization
Main chain of the object as membrane material, and aliphatic chain aiming at the problem that flexibility is excessively high, viscoplasticity is too strong to form a film, design makes
It uses tertiary amine compounds as quaternizing agent, while carrying out quaternized, realizes the crosslinking of fatty-chain polymers, formed empty
Between reticular structure, limit the motility of flexible chain to a certain extent, in addition, the present invention is when select quaternizing agent, use
Bridge of the stronger tertiary amine molecule of molecule rigidity as connection polymer chain itself, can further limit flexible polymer chain
Movement, to improve the rigidity for being used to prepare the ionomer of anion-exchange membrane, the present invention solves fatty-chain polymers
Because of the technical problem that flexible high, the strong bring of viscoplasticity can not form a film, new approach is opened up for the preparation of anion-exchange membrane；
PClEVE described in flexible aliphatic chain is introduced into the main chain of anion-exchange membrane by the present invention, significantly increases curtain coating
The motility of segment in method film forming procedure, so that PQEVE described in ionomer is prone to hydrophilic-hydrophobic nanometer microfacies point
From being self-assembled into the ion channel of perforation, promote the transmission of anion, realize higher ionic conductivity.Further, since institute
The IEC for stating photocatalysis anion-exchange membrane is lower, and the photocatalysis anion-exchange membrane has cross-linked structure, so that film
Free volume it is smaller, so as to inhibit film to absorb excess water so that the moisture content of film is lower, it is corresponding it is water-swellable also compared with
It is low.
In addition, the present invention uses light-operated cationic polymerization technology, the light-operated work of functional monomer is realized at room temperature
Property polymerization, the aliphatic chain homopolymer is made, causes activity polymerizating technology, preparation method condition of the present invention compared to traditional heat
Mildly, reaction rate controllability is high, and uses visible light, from a wealth of sources and environmentally protective.
The present invention is based on the photocatalysis anion-exchange membrane that the aliphatic chain homopolymer is prepared, have it is higher from
Also higher resistance to swelling energy is maintained while electron conductivity, realizes ionic conductivity and the double of water swell resistance energy mention
It rises, using the anion-exchange membrane as the electrolyte of fuel cell, the work of anion-exchange membrane fuel cells can be improved
Performance.
Embodiment one
1.1 raw material preparation；2- chloroethyl vinyl ether (ClEVE) is subjected to vacuum distillation processing, and is respectively synthesized S-1-
Isobutoxyethy S '-ethyl trithiocarbonate (CTA1) and 2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salt
(C1)；
The 1.2 poly- 2- chloroethyl vinyl ethers (PClEVE) of synthesis；C1 described in 0.04mmol is added into Schlenk reaction flask,
After vacuumizing-leading to nitrogen circulation 3 times, it is separately added into ClEVE described in CTA1,400mmol described in 1mmol and molten under nitrogen atmosphere
Agent methylene chloride (DCM) seals bottleneck, and reaction flask is placed in Blue LEDs irradiation and is reacted for 24 hours under room temperature, obtains
First reaction solution obtains the polymer after carrying out revolving processing removal solvent and residual monomer to first reaction solution
PClEVE, the degree of polymerization of the PClEVE is 350 after tested；
1.3 prepare the photocatalysis anion-exchange membrane；The PClEVE is dissolved in the N-Methyl pyrrolidone (NMP)
In, the first solution that mass ratio is 10wt% is obtained, first solution is placed in 160 DEG C of oil bath pans and is heat-treated
25min obtains the second reaction solution；By the triethylene diamine (DABCO) be added the second reaction solution in, wherein the PClEVE and
The molar ratio of the DABCO is 10:1,30min is stirred under room temperature, reaction temperature is then increased to 75 DEG C, carries out quaternary amine
Change reaction, obtains third reaction solution, the viscosity for monitoring the third reaction solution changes with time, when the third reaction solution
When viscosity is larger, supplementing solvent is then coated the third reaction solution to described with diluting the viscosity of the third reaction solution
It on substrate, is dried at 75 DEG C, obtains the photocatalysis anion-exchange membrane.
The IEC of the photocatalysis anion-exchange membrane made from the present embodiment is 1.75mmol/g.To the photocatalysis yin
The ionic conductivity of amberplex at different temperatures is tested, and test result is shown in Fig. 6, as seen from Figure 6, the present invention
The chloride conductance of the photocatalysis anion-exchange membrane up to 83.60mS/cm at 30 DEG C is higher than commercial standard (CS) Nafion
The proton conductivity (80mS/cm or so) of film；And with the continuous raising of temperature, the ion of the photocatalysis anion-exchange membrane
Conductivity is continuously improved, and after 70 DEG C, the ionic conductivity of the photocatalysis anion-exchange membrane almost no longer changes.
The test of moisture content and linear swelling ratio is carried out to the photocatalysis anion-exchange membrane, wherein 60 DEG C of whens light
The moisture content of catalyzed anionic exchange membrane is 19.61wt%, and linear swelling ratio is 2.22%, water swell resistance with higher
Can, and ionic conductivity of the photocatalysis anion-exchange membrane at 60 DEG C is up to 180.31mS/cm, show superelevation from
Electron conductivity；The moisture content of the photocatalysis anion-exchange membrane is 11.76wt% at other 30 DEG C, and linear swelling ratio is
1.13%.This is primarily due to, the main chain present invention introduces flexible aliphatic chain as film, compared to the prior art the middle virtue used
Fragrant chain significantly increases the motility of segment in the tape casting film forming procedure, so that microphase-separated easily occurs for ionomer and shape
At the ion channel of perforation, promote the transmission of anion, improves ionic conductivity；In addition, in order to reduce flexible polymer chain mistake
The degree movement stronger viscoplasticity of bring film, the present invention uses the stronger tertiary amine molecule of rigidity as quaternizing agent, to improve
The rigidity of ionomer is able to suppress film and absorbs excess water simultaneously because the film of preparation has cross-linked structure, so that
Film has good water swell resistance energy.
Embodiment two
2.1 raw material preparation；2- chloroethyl vinyl ether (ClEVE) is subjected to vacuum distillation processing, and is respectively synthesized S-1-
Isobutoxyethy S '-ethyl trithiocarbonate (CTA1) and 2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salt
(C1)；
The 2.2 poly- 2- chloroethyl vinyl ethers (PClEVE) of synthesis；C1 described in 0.02mmol is added into Schlenk reaction flask,
After vacuumizing-leading to nitrogen circulation 3 times, it is separately added into ClEVE described in CTA1,100mmol described in 1mmol and molten under nitrogen atmosphere
Agent methylene chloride (DCM) seals bottleneck, and reaction flask is placed in Blue LEDs irradiation and reacts 18h under room temperature, obtains
First reaction solution obtains the polymer after carrying out revolving processing removal solvent and residual monomer to first reaction solution
PClEVE, the degree of polymerization of the PClEVE is 97 after tested；
2.3 prepare the photocatalysis anion-exchange membrane；The PClEVE is dissolved in the dimethyl sulfoxide (DMSO), is obtained
The first solution for being 10wt% to mass ratio, first solution is placed in 150 DEG C of oil bath pans and carries out heat treatment 60min, is obtained
To the second reaction solution；The pentamethyl-diethylenetriamine is added in the second reaction solution, wherein the PClEVE and five first
The molar ratio of base diethylenetriamine is 15:1,5min is stirred under room temperature, reaction temperature is then increased to 60 DEG C, carries out season
Aminating reaction obtains third reaction solution, and the viscosity for monitoring the third reaction solution changes with time, when the third reaction solution
Viscosity it is larger when, supplementing solvent is then coated the third reaction solution to institute with diluting the viscosity of the third reaction solution
It states on substrate, is dried at 60 DEG C, obtain the photocatalysis anion-exchange membrane.
The IEC of the photocatalysis anion-exchange membrane made from the present embodiment is 1.24mmol/g.To the photocatalysis yin
Amberplex carries out the test of chloride conductance, moisture content and linear swelling ratio respectively, the chloride ion electricity at 30 DEG C
Conductance is 31.21mS/cm, and moisture content 6.11wt%, linear swelling ratio is 0.42%；Chloride conductance at 60 DEG C is
50.08mS/cm, moisture content 11.0wt%, linear swelling ratio are 1.1%.
Embodiment three
3.1 raw material preparation；2- chloroethyl vinyl ether (ClEVE) is subjected to vacuum distillation processing, and is respectively synthesized S-1-
Isobutoxyethy S '-ethyl trithiocarbonate (CTA1) and 2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salt
(C1)；
The 3.2 poly- 2- chloroethyl vinyl ethers (PClEVE) of synthesis；C1 described in 0.08mmol is added into Schlenk reaction flask,
After vacuumizing-leading to nitrogen circulation 3 times, be separately added under nitrogen atmosphere ClEVE described in CTA1,1000mmol described in 1mmol and
Methylene chloride (DCM) seals bottleneck, and reaction flask is placed in Blue LEDs irradiation and reacts 48h under room temperature, obtains
The polymer is obtained after carrying out revolving processing removal solvent and residual monomer to first reaction solution to the first reaction solution
PClEVE, the degree of polymerization of the PClEVE is 600 after tested；
3.3 prepare the photocatalysis anion-exchange membrane；The PClEVE is dissolved in the N,N-dimethylformamide
(DMF) in, the first solution that mass ratio is 10wt% is obtained, first solution is placed in 170 DEG C of oil bath pans and carries out hot place
10min is managed, the second reaction solution is obtained；By the N, N, N ', N '-tetramethyl-para-phenylene diamine is added in the second reaction solution, wherein institute
State PClEVE and the N, N, N ', the molar ratio of N '-tetramethyl-para-phenylene diamine is 5:1,15min is stirred under room temperature, then
Reaction temperature is increased to 90 DEG C, quaternary ammonium reaction is carried out, obtains third reaction solution, monitor the viscosity of the third reaction solution with
The variation of time, when the viscosity of the third reaction solution is larger, supplementing solvent to dilute the viscosity of the third reaction solution, and
The third reaction solution is coated to the substrate afterwards, is dried at 90 DEG C, the photocatalysis anion-exchange membrane is obtained.
The IEC of the photocatalysis anion-exchange membrane made from the present embodiment is 1.94mmol/g.To the photocatalysis yin
Amberplex carries out the test of chloride conductance, moisture content and linear swelling ratio respectively, the chloride ion electricity at 30 DEG C
Conductance is 100.17mS/cm, and moisture content 15.2wt%, linear swelling ratio is 1.8%；Chloride conductance at 60 DEG C is
240.15mS/cm, moisture content 24wt%, linear swelling ratio are 3.2%.
The foregoing is merely presently preferred embodiments of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive
's.Those skilled in the art understand that in the spirit and scope defined by the claims in the present invention many changes can be carried out to it,
It modifies or even equivalent, but falls in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of photocatalysis anion-exchange membrane, which is characterized in that include the following steps：
Fatty chain polymerization is made using light-operated cationic polymerization technology using 2- chloroethyl vinyl ether as reaction monomers in step S1
Object, as the main chain of membrane material；
Step S2, using polyamine compounds as quaternizing agent and crosslinking agent, by the fatty-chain polymers and the amine
Compound carries out quaternization reaction, obtains the photocatalysis anion-exchange membrane.
2. the preparation method of photocatalysis anion-exchange membrane as described in claim 1, which is characterized in that rouge described in step S1
The specific synthesis step of fat chain polymerization object is as follows：
The 2- chloroethyl vinyl ether and chain transfer agents and photochemical catalyst are carried out light under Blue LEDs irradiation by S1-1
Cationic polymerization is controlled, the first reaction solution is obtained；
S1-2 obtains poly- 2- chloroethyl vinyl after carrying out revolving processing removal solvent and residual monomer to first reaction solution
Base ether.
3. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 2, which is characterized in that the photochemical catalyst packet
2,4,6- tri- (p-methoxyphenyl) pyrans tetrafluoride boron salts are included, the chain transfer agents include S-1- isobutoxyethy S '-
Ethyl trithiocarbonate.
4. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 3, which is characterized in that the 2- chloroethyl second
Alkene ether, the S-1- isobutoxyethy S '-ethyl trithiocarbonate and 2,4,6- tri- (p-methoxyphenyl) pyrrole
The molar ratio for tetrafluoride boron salt of muttering is 100~1000:1:0.02~0.08.
5. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 2, which is characterized in that the light-operated cation
Polymerization reaction carries out at room temperature, and reaction time control is 18h~48h.
6. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 2, which is characterized in that the poly- 2- chloroethyl
The degree of polymerization of vinyl ethers is 97~600.
7. such as the preparation method of the described in any item photocatalysis anion-exchange membranes of claim 2-6, which is characterized in that step S2
Specifically comprise the following steps：
The poly- 2- chloroethyl vinyl ether is dissolved in organic solvent by S2-1, and heating heat treatment obtains the second reaction solution；
The polyamine compounds are added into second reaction solution by S2-2, carry out quaternary ammonium reaction, obtain third reaction
Liquid；
The third reaction solution is coated on substrate, the photocatalysis anion-exchange membrane is obtained after drying by S2-3.
8. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 7, which is characterized in that the poly- 2- chloroethyl
The molar ratio of vinyl ethers and the polyamine compounds is 5~15:1.
9. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 7, which is characterized in that the polyamines class chemical combination
Object includes triethylene diamine, pentamethyl-diethylenetriamine or N, N, N ', N '-tetramethyl-para-phenylene diamine.
10. the preparation method of photocatalysis anion-exchange membrane as claimed in claim 8, which is characterized in that the poly- 2- chloroethene
It is 10wt% that base vinyl ethers, which is dissolved in the mass percent in the organic solvent,.
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