CN108864455B - Preparation method of photocatalytic anion exchange membrane - Google Patents
Preparation method of photocatalytic anion exchange membrane Download PDFInfo
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- CN108864455B CN108864455B CN201810797232.2A CN201810797232A CN108864455B CN 108864455 B CN108864455 B CN 108864455B CN 201810797232 A CN201810797232 A CN 201810797232A CN 108864455 B CN108864455 B CN 108864455B
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- exchange membrane
- anion exchange
- photocatalytic
- reaction
- vinyl ether
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 75
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 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 38
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 20
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000010538 cationic polymerization reaction Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- LBIHDFCPWCRUPD-UHFFFAOYSA-N ethylsulfanyl-[2-(2-methylpropoxy)ethylsulfanyl]methanethione Chemical compound CCSC(=S)SCCOCC(C)C LBIHDFCPWCRUPD-UHFFFAOYSA-N 0.000 claims description 11
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- NQMRYYAAICMHPE-UHFFFAOYSA-N (4-methoxyphenyl)boron Chemical compound [B]C1=CC=C(OC)C=C1 NQMRYYAAICMHPE-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 5
- -1 amine compounds Chemical class 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 230000008961 swelling Effects 0.000 abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- DCSWAZWYPDWOHY-UHFFFAOYSA-N C1OC=CC=C1.F.F.F.F Chemical compound C1OC=CC=C1.F.F.F.F DCSWAZWYPDWOHY-UHFFFAOYSA-N 0.000 description 10
- 101150027801 CTA1 gene Proteins 0.000 description 10
- 101100273295 Candida albicans (strain SC5314 / ATCC MYA-2876) CAT1 gene Proteins 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 8
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- 238000007306 functionalization reaction 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
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-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
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LVOMNGNQELCIPK-UHFFFAOYSA-M S(=O)(=O)(OCC)SS(=O)(=O)[O-].[Na+] Chemical compound S(=O)(=O)(OCC)SS(=O)(=O)[O-].[Na+] LVOMNGNQELCIPK-UHFFFAOYSA-M 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- IKPFWPMVFYNXTD-UHFFFAOYSA-N [B].COC1=CC=C(C=C1)C1OC(=CC(=C1)C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC Chemical compound [B].COC1=CC=C(C=C1)C1OC(=CC(=C1)C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC IKPFWPMVFYNXTD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- JEZVXCNJDYRCCE-UHFFFAOYSA-M sodium;ethylsulfanylmethanedithioate Chemical compound [Na+].CCSC([S-])=S JEZVXCNJDYRCCE-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
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- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- 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]
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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Abstract
The invention discloses a preparation method of a photocatalytic anion exchange membrane, which comprises the following steps: step S1, preparing an aliphatic chain polymer by using 2-chloroethyl vinyl ether as a reaction monomer and adopting a light-operated cationic polymerization technology, wherein the aliphatic chain polymer is used as a main chain of a membrane material; and step S2, using polyamine compounds as quaternizing agents and crosslinking agents, and carrying out quaternization reaction on the aliphatic chain polymer and the polyamine compounds to obtain the photocatalytic anion exchange membrane. The photocatalytic anion exchange membrane prepared by the invention has high ionic conductivity and can keep high swelling resistance, so that the anion exchange membrane has good performance, and in addition, the reaction condition is mild and the controllability is high.
Description
Technical Field
The invention relates to the field of fuel cell membrane materials, in particular to a preparation method of a photocatalytic anion exchange membrane.
Background
Based on the bottleneck problems of price, service life and the like of the proton exchange membrane fuel cell, the alkaline anion exchange membrane fuel cell is gradually developed, and compared with the proton exchange membrane fuel cell, the alkaline anion exchange membrane fuel cell has the advantages of higher oxygen reduction reaction efficiency under an alkaline condition, permission of use of a non-noble metal catalyst, capability of greatly reducing fuel leakage and the like due to the fact that the transfer directions of fuel and hydroxyl are opposite. However, the trade-off effect between hydroxide ion conductivity and swelling resistance of Anion Exchange Membranes (AEMs) is still a primary bottleneck impeding further development of alkaline anionic membrane fuel cells.
The preparation of the existing anion exchange membrane usually adopts a high molecular polymer as a main chain, and prepares the anion exchange membrane after carrying out ion functional group formation on the high molecular polymer, or starts from a functional monomer and prepares the anion exchange membrane through polymerization and chain formation.
In addition, the main chain of the traditional anion exchange membrane mostly adopts aromatic polymers, and as the chain segment of the aromatic polymers has higher rigidity and poorer mobility, the micro-phase separation is difficult to occur when the anion exchange membrane is prepared by firstly forming a membrane and then performing ion functionalization, and for the anion exchange membrane prepared after performing homogeneous functionalization, the micro-phase separation is still difficult due to the insufficient mobility of the main chain in the solvent volatilization process, and for the micro-phase separation morphology is generally regulated and controlled by regulating the configuration of the anion exchange membrane in the prior art, but the regulation and control force is limited, and the prepared anion exchange membrane has poorer performance.
In conclusion, the current anion exchange membrane preparation still cannot effectively solve the contradiction between the ionic conductivity and the swelling resistance, the performance of the produced membrane is poor, and the application and development of AEM are greatly limited.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a preparation method of a photocatalytic anion exchange membrane, which comprises the following steps:
step S1, preparing an aliphatic chain polymer by using 2-chloroethyl vinyl ether as a reaction monomer and adopting a light-operated cationic polymerization technology, wherein the aliphatic chain polymer is used as a main chain of a membrane material;
and step S2, using polyamine compounds as quaternizing agents and crosslinking agents, and carrying out quaternization reaction on the aliphatic chain polymer and the amine compounds to obtain the photocatalytic anion exchange membrane.
Preferably, the specific synthetic steps of the aliphatic chain polymer in step S1 are as follows:
s1-1, carrying out light-controlled cationic polymerization reaction on the 2-chloroethyl vinyl ether, a chain transfer reagent and a photocatalyst under the irradiation of Blue LEDs to obtain a first reaction solution;
and S1-2, performing rotary evaporation treatment on the first reaction liquid to remove the solvent and the residual monomers to obtain the poly-2-chloroethyl vinyl ether.
Preferably, the photocatalyst comprises 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride pyran salt, and the chain transfer agent comprises S-1-isobutoxyethyl S' -ethyl trithiocarbonate.
Preferably, the molar ratio of the 2-chloroethyl vinyl ether, the S-1-isobutoxyethyl S' -ethyl trithiocarbonate and the 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride pyran salt is 100-1000: 1: 0.02-0.08.
Preferably, the light-controlled cationic polymerization reaction is carried out at room temperature, and the reaction time is controlled to be 18-48 h.
Preferably, the polymerization degree of the poly-2-chloroethyl vinyl ether is 97-600.
Preferably, the step S2 specifically includes the following steps:
s2-1, dissolving the poly 2-chloroethyl vinyl ether in an organic solvent, and heating and thermally treating to obtain a second reaction solution;
s2-2, adding the polyamine compound into the second reaction solution, and carrying out quaternization reaction to obtain a third reaction solution;
and S2-3, coating the third reaction solution on a substrate, and drying to obtain the photocatalytic anion exchange membrane.
Preferably, the molar ratio of the poly-2-chloroethyl vinyl ether to the polyamine compound is 5-15: 1.
Preferably, the polyamine compound comprises triethylene diamine, pentamethyl diethylene triamine or N, N, N ', N' -tetramethyl p-phenylenediamine.
Preferably, the mass percentage of the poly 2-chloroethyl vinyl ether dissolved in the organic solvent is 10 wt%.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method disclosed by the invention has the advantages that the fatty chain polymer is subjected to quaternization treatment, and the crosslinking of the fatty chain polymer is realized while quaternization is carried out, so that the technical problem that the fatty chain polymer cannot be formed into a film due to high flexibility and strong viscoelasticity is solved, and a new way is opened up for the preparation of an anion exchange membrane;
2, the aliphatic chain polymer is prepared by adopting a light-controlled cationic polymerization technology, light-controlled active polymerization of a functional monomer is realized at room temperature, the reaction condition is mild, the controllability is high, and the polymerization degree of the aliphatic chain polymer can be controlled by adjusting the feeding ratio and the reaction time of the chain transfer reagent and the monomer;
3, the photocatalytic anion exchange membrane prepared by the invention has higher ionic conductivity and can keep higher swelling resistance, so that the anion exchange membrane has good performance.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a photocatalyst, 2,4, 6-tris (p-methoxyphenyl) pyranoboron tetrafluoride salt according to the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the chain transfer agent S-1-isobutoxyethyl S' -ethyl trithiocarbonate of the present invention;
FIG. 3 is a NMR spectrum of poly-2-chloroethyl vinyl ether of the present invention;
FIG. 4 is a gel permeation chromatogram of poly-2-chloroethyl vinyl ether in accordance with the present invention;
FIG. 5 is a Fourier transform infrared spectrum of a photocatalytic anion exchange membrane of the present invention;
FIG. 6 is a graph showing the change of the conductivity of chloride ions at different temperatures in a photocatalytic anion exchange membrane according to an embodiment of the present invention.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
The invention provides a preparation method of a photocatalytic anion exchange membrane, which comprises the steps of firstly preparing an aliphatic chain polymer by adopting a light-operated cationic polymerization technology, taking the aliphatic chain polymer as a main chain of a membrane material, then carrying out quaternization treatment on the aliphatic chain polymer, and finally preparing the photocatalytic anion exchange membrane by adopting a tape casting membrane forming method.
Wherein the aliphatic chain polymer contains R-Cl groups, wherein R is a hydrocarbon group.
According to the invention, firstly, a light-operated cationic polymerization technology is utilized to synthesize a fatty chain homopolymer; the preparation method comprises the following steps of carrying out light-operated cationic polymerization reaction on 2-chloroethyl vinyl ether (ClEVE) serving as a monomer, S-1-isobutoxyethyl S' -ethyl trithiocarbonate (CTA1) serving as a chain transfer reagent and 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride salt (C1) serving as a photocatalyst under the irradiation of Blue LEDs to prepare the aliphatic chain homopolymer poly (2-chloroethyl vinyl ether) (PClEVE).
Specifically, the 2-chloroethyl vinyl ether is subjected to reduced pressure distillation treatment to remove a polymerization inhibitor;
the synthesis of the S-1-isobutoxyethyl S' -ethyl trithiocarbonate comprises the following steps:
(1) adding sodium hydride into a dry first flask under the protection of nitrogen, adding anhydrous ether into the first flask to form a first mixed solution, and cooling the first mixed solution to 0 ℃; dropwise adding freshly distilled ethanethiol into the first mixed solution to form a suspension, stirring the suspension at room temperature for 10min, and cooling to 0 ℃; adding newly steamed carbon disulfide into the suspension drop by drop to form a dark yellow suspension, and stirring the dark yellow suspension at room temperature for 2 hours to prepare a sodium ethyl trithionate suspension;
(2) adding an ether hydrochloride solution into a dry second flask, cooling liquid nitrogen of the ether hydrochloride solution to-78 ℃, dropwise adding distilled isobutyl vinyl ether into the second flask to obtain a light yellow solution, stirring the light yellow solution at-78 ℃ for 1 hour, and then heating to 0 ℃;
(3) and (3) dropwise adding the cooling solution obtained in the step (2) into the sodium ethyl trithiocarbonate suspension in the first flask to obtain a second mixed solution, stirring the second mixed solution at room temperature for 2 hours, diluting the second mixed solution with 10mL of ether, quenching the diluted solution with 10mL of saturated sodium bicarbonate solution, separating the solution and extracting the solution with ether, collecting the organic phase, washing the organic phase with water and brine respectively, diluting the organic phase with n-hexane, drying the organic phase with anhydrous sodium sulfate and drying the organic phase in a vacuum drying box to obtain a crude product, and purifying a chromatographic column of the crude product to obtain a pure chain transfer reagent, namely the S-1-isobutoxyethyl S' -ethyl trithiocarbonate, wherein the specific synthetic process is shown as a formula (1).
The synthesis process of the 2,4, 6-tri (p-methoxyphenyl) pyran boron tetrafluoride salt is as follows: adding 3.4g of p-methoxybenzaldehyde and 7.5g of p-methoxybenzophenone into 7.5g of boron trifluoride diethyl etherate solution, reacting for 2h at 100 ℃ to obtain brick red solid precipitate, filtering, washing with diethyl ether for 3 times, and drying in a vacuum oven at 60 ℃ to obtain brick red solid powder, namely the 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride pyran salt, wherein the specific synthetic process is shown in formula (2).
The light-controlled cationic polymerization reaction specifically comprises the following steps: adding the C1 into a schlenk reaction bottle, vacuumizing and introducing nitrogen for 3 times to remove oxygen in the reaction bottle, then adding corresponding amounts of the CTA1, the ClEVE and a solvent Dichloromethane (DCM) under the nitrogen atmosphere, sealing the bottle mouth, placing the reaction bottle under the irradiation of Blue LEDs to perform controllable cationic polymerization reaction of the ClEVE to obtain a first reaction liquid, performing the reaction at room temperature for 18-48 h, performing rotary evaporation treatment on the first reaction liquid to remove the solvent to obtain the polymer PClEVE, wherein the specific synthetic process is shown as formula (3). Wherein the molar ratio of the ClEVE, the CTA1 and the C1 is 100-1000: 1: 0.02-0.08, and is more preferably set to be 400: 1: 0.04.
the polymerization process of the PClEVE is controllable, and the polymerization degree of the PClEVE can be controlled by adjusting the feeding ratio of the chain transfer reagent and the monomer and the reaction time. The polymerization degree of the PClEVE is 97-600.
And performing nuclear magnetic resonance hydrogen spectrum tests on the photocatalyst, the chain transfer reagent and the PClEVE respectively, wherein the test results are shown in figures 1-3. The catalyst C1 takes deuterium dimethyl sulfoxide (2.50ppm) as a solvent, and as can be seen from figure 1, the chemical shift of the measured nuclear magnetic resonance hydrogen spectrum has a good corresponding relationship with the actual structure, wherein peaks 1,2,3,4(7.0-9.0ppm) correspond to protons on a benzene ring, peaks 5,6(3.97ppm, 3.94ppm) correspond to protons on a methoxyl group, and the integral area ratio of each peak also corresponds to the actual number of protons one to one, so that the successful preparation of the catalyst C1 is proved. The chain transfer reagent CTA1 uses deuterated chloroform as a solvent, and as can be seen from FIG. 2, the peak shifts of the respective protons are correctly assigned, and the integral area ratio is also correct, thus confirming the successful preparation of the chain transfer reagent CTA 1. The PClEVE uses deuterated chloroform as a solvent to carry out nuclear magnetic resonance hydrogen spectrum characterization, and as can be seen from figure 3, the displacement and integral area ratios of all peaks correspond to protons in an actual structure one by one, so that the successful polymerization of the monomer is verified, wherein a corresponding solvent peak appears at 5.30ppm of a synthetic resonance hydrogen spectrum due to the residual solvent dichloromethane used in the polymerization reaction.
The prepared polymer was subjected to gel permeation chromatography test using the PClEVE, the test result is shown in FIG. 4, the retention time of the polymer is about 7.8min according to FIG. 4, and the number average molecular weight of the polymer is 10274g/mol, the weight average molecular weight is 14264g/mol and the molecular weight distribution is 1.39, which are measured by using polystyrene as a reference standard, and the high controllability of the photo-controlled polymerization process is confirmed.
And secondly, using polyamine compounds as a quaternizing agent and a cross-linking agent, carrying out quaternization reaction on the aliphatic chain polymer and the amine compounds, and preparing the photocatalytic anion exchange membrane PQEVE by adopting a tape casting film forming method.
Specifically, dissolving the PClEVE in an organic solvent, heating the organic solution of the PClEVE to 150-170 ℃, and carrying out heat treatment for 10-60 min to obtain a second reaction solution; and then adding the polyamine compound into the second reaction solution, stirring at room temperature for 5-30 min, raising the reaction temperature to 60-90 ℃ for quaternization reaction to obtain a third reaction solution, monitoring the change of the viscosity of the third reaction solution along with time, supplementing a solvent to dilute the viscosity of the third reaction solution when the viscosity of the third reaction solution is higher, coating the third reaction solution on a substrate, and drying to obtain the photocatalytic anion exchange membrane, wherein the specific synthetic process is shown as formula (4). Wherein, the heat treatment temperature is preferably 160 ℃, and the drying temperature is preferably 60-90 ℃.
The polyamine compound comprises triethylene Diamine (DABCO), pentamethyl diethylenetriamine or N, N, N ', N' -tetramethyl p-phenylenediamine, and the organic solvent comprises N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) or N, N-Dimethylformamide (DMF); the molar ratio of the PClEVE to the polyamine compound is 5-15: 1, more preferably 10:1, and the PClEVE is dissolved in the organic solvent to obtain a solution with the mass ratio of 10 wt%.
Fourier infrared spectrum test is carried out on the prepared photocatalytic anion exchange membrane, and the test result is shown in figure 55, the existence of the quaternary amination group leads the prepared anion-exchange membrane to have stronger water absorption, and the absorbed water is 3400cm-1Has a stretching vibration peak of absorbed water, and indicates the success of the quaternization reaction of the polymer in the invention.
The Ion Exchange Capacity (IEC) of the photocatalytic anion exchange membrane prepared by the invention is 1.24 mmol/g-1.94 mmol/g; the Ion Exchange Capacity (IEC) of the photocatalytic anion exchange membrane can be controlled by controlling the feeding and reaction time of the quaternization agent, and the method is high in controllability and simple to operate.
The prepared photocatalytic anion exchange membrane is subjected to chloride ion conductivity, water content and linear swelling rate tests, and the test results are shown in the following table:
as can be seen from the table above, the photocatalytic anion exchange membrane has high ionic conductivity, and simultaneously has low water content and linear swelling rate, so that high water-resistant swelling property is ensured.
The invention selects the aliphatic chain polymer as the main chain of the membrane material based on the poor chain mobility of the aromatic polymer which is not beneficial to the microphase separation, aiming at the problem that the fatty chain can not form a film due to too high softness and too strong viscoelasticity, the tertiary amine compound is designed and used as a quaternizing agent, the fatty chain polymer is crosslinked while quaternization is carried out, a space network structure is formed, to some extent limiting the mobility of the flexible chains, and, in addition, the present invention, when selecting a quaternizing agent, the tertiary amine molecules with stronger self-rigidity of the molecules are used as a bridge for connecting the polymer chains, the movement of the flexible polymer chains can be further limited, the invention solves the technical problem that the aliphatic chain polymer cannot form a film due to high flexibility and strong viscoelasticity, and opens up a new way for preparing the anion exchange membrane;
according to the invention, the PClEVE of the flexible aliphatic chain is introduced into the main chain of the anion exchange membrane, so that the mobility of chain segments in the film forming process of a tape casting method is greatly increased, the PQEVE of the ionic polymer is easy to generate hydrophilic-hydrophobic nano microphase separation, a through ion channel is self-assembled, the transmission of anions is promoted, and the higher ionic conductivity is realized. In addition, because the IEC of the photocatalytic anion exchange membrane is low, and the photocatalytic anion exchange membrane has a cross-linked net structure, the free volume of the membrane is small, so that the membrane can be inhibited from absorbing excessive water, the water content of the membrane is low, and the corresponding water swelling is low.
In addition, the invention adopts the light-controlled cationic polymerization technology to realize the light-controlled active polymerization of the functional monomer at room temperature to prepare the aliphatic chain homopolymer, compared with the traditional heat-initiated active polymerization technology, the preparation method has the advantages of mild conditions, high reaction rate controllability, wide source and environmental protection due to the adoption of visible light.
The photocatalytic anion exchange membrane prepared based on the aliphatic chain homopolymer has higher ionic conductivity and higher swelling resistance, realizes double promotion of ionic conductivity and water-resistant swelling performance, and can improve the working performance of an anion exchange membrane fuel cell by taking the anion exchange membrane as an electrolyte of the fuel cell.
Example one
1.1, preparing raw materials; carrying out reduced pressure distillation treatment on 2-chloroethyl vinyl ether (ClEVE) and respectively synthesizing S-1-isobutoxyethyl S' -ethyl trithiocarbonate (CTA1) and 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride pyran salt (C1);
1.2 Synthesis of poly-2-chloroethyl vinyl ether (PClEVE); adding 0.04mmol of C1 into a schlenk reaction bottle, vacuumizing and introducing nitrogen for 3 times, respectively adding 1mmol of CTA1 and 400mmol of ClEVE and solvent Dichloromethane (DCM) under the nitrogen atmosphere, sealing the bottle mouth, placing the reaction bottle under the irradiation of Blue LEDs and reacting for 24 hours at room temperature to obtain a first reaction solution, performing rotary evaporation treatment on the first reaction solution to remove the solvent and residual monomers to obtain the polymer PClEVE, and testing that the polymerization degree of the PClEVE is 350;
1.3 preparing the photocatalytic anion exchange membrane; dissolving the PClEVE in the N-methylpyrrolidone (NMP) to obtain a first solution with the mass ratio of 10 wt%, and placing the first solution in a 160 ℃ oil bath pan for heat treatment for 25min to obtain a second reaction solution; adding the triethylene Diamine (DABCO) into a second reaction solution, wherein the molar ratio of the PClEVE to the DABCO is 10:1, stirring for 30min at room temperature, then raising the reaction temperature to 75 ℃ for carrying out quaternization reaction to obtain a third reaction solution, monitoring the change of the viscosity of the third reaction solution along with time, supplementing a solvent to dilute the viscosity of the third reaction solution when the viscosity of the third reaction solution is higher, then coating the third reaction solution on the substrate, and drying at 75 ℃ to obtain the photocatalytic anion exchange membrane.
The IEC of the photocatalytic anion exchange membrane prepared in this example was 1.75 mmol/g. The ion conductivity of the photocatalytic anion exchange membrane at different temperatures is tested, the test result is shown in figure 6, and as can be seen from figure 6, the chloride ion conductivity of the photocatalytic anion exchange membrane is as high as 83.60mS/cm at 30 ℃ and higher than the proton conductivity (about 80 mS/cm) of a commercial standard Nafion membrane; and the ion conductivity of the photocatalytic anion exchange membrane is continuously improved along with the continuous increase of the temperature, and the ion conductivity of the photocatalytic anion exchange membrane is hardly changed after 70 ℃.
Testing the water content and the linear swelling rate of the photocatalytic anion exchange membrane, wherein the water content of the photocatalytic anion exchange membrane at 60 ℃ is 19.61 wt%, the linear swelling rate is 2.22%, the photocatalytic anion exchange membrane has high water swelling resistance, the ionic conductivity of the photocatalytic anion exchange membrane at 60 ℃ is up to 180.31mS/cm, and the photocatalytic anion exchange membrane shows ultrahigh ionic conductivity; in addition, the water content of the photocatalytic anion exchange membrane at 30 ℃ is 11.76 wt%, and the linear swelling rate is 1.13%. The flexible aliphatic chain is introduced as the main chain of the membrane, so that compared with an aromatic chain adopted in the prior art, the mobility of a chain segment in the process of film formation by a tape casting method is greatly increased, the ionic polymer is easy to generate micro-phase separation to form a through ion channel, the transmission of anions is promoted, and the ionic conductivity is improved; in addition, in order to reduce the stronger viscoelasticity of the membrane caused by excessive movement of a flexible polymer chain, the invention adopts tertiary amine molecules with stronger rigidity as a quaternizing agent to improve the rigidity of the ionic polymer, and simultaneously, the prepared membrane has a cross-linked network structure, so that the membrane can be inhibited from absorbing excessive moisture, and the membrane has good water-resistant swelling performance.
Example two
2.1, preparing raw materials; carrying out reduced pressure distillation treatment on 2-chloroethyl vinyl ether (ClEVE) and respectively synthesizing S-1-isobutoxyethyl S' -ethyl trithiocarbonate (CTA1) and 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride pyran salt (C1);
2.2 Synthesis of poly-2-chloroethyl vinyl ether (PClEVE); adding 0.02mmol of C1 into a schlenk reaction bottle, vacuumizing and introducing nitrogen for 3 times, respectively adding 1mmol of CTA1, 100mmol of ClEVE and solvent Dichloromethane (DCM) under the nitrogen atmosphere, sealing the bottle mouth, placing the reaction bottle under the irradiation of Blue LEDs and reacting for 18 hours at room temperature to obtain a first reaction solution, performing rotary evaporation treatment on the first reaction solution to remove the solvent and residual monomers to obtain the polymer PClEVE, and testing that the polymerization degree of the PClEVE is 97;
2.3 preparing the photocatalytic anion exchange membrane; dissolving the PClEVE in the dimethyl sulfoxide (DMSO) to obtain a first solution with the mass ratio of 10 wt%, and placing the first solution in a 150 ℃ oil bath pot for heat treatment for 60min to obtain a second reaction solution; adding the pentamethyl diethylenetriamine into a second reaction solution, wherein the molar ratio of the PClEVE to the pentamethyl diethylenetriamine is 15:1, stirring for 5min at room temperature, then raising the reaction temperature to 60 ℃, carrying out quaternization reaction to obtain a third reaction solution, monitoring the change of the viscosity of the third reaction solution along with time, supplementing a solvent to dilute the viscosity of the third reaction solution when the viscosity of the third reaction solution is higher, then coating the third reaction solution on the substrate, and drying at 60 ℃ to obtain the photocatalytic anion-exchange membrane.
The IEC of the photocatalytic anion exchange membrane prepared in this example was 1.24 mmol/g. Respectively testing the conductivity, the water content and the linear swelling rate of the chloride ions of the photocatalytic anion exchange membrane, wherein the conductivity of the chloride ions at 30 ℃ is 31.21mS/cm, the water content is 6.11 wt%, and the linear swelling rate is 0.42%; the chloride ion conductivity at 60 ℃ was 50.08mS/cm, the water content was 11.0 wt%, and the linear swelling ratio was 1.1%.
EXAMPLE III
3.1 preparing raw materials; carrying out reduced pressure distillation treatment on 2-chloroethyl vinyl ether (ClEVE) and respectively synthesizing S-1-isobutoxyethyl S' -ethyl trithiocarbonate (CTA1) and 2,4, 6-tri (p-methoxyphenyl) boron tetrafluoride pyran salt (C1);
3.2 Synthesis of poly-2-chloroethyl vinyl ether (PClEVE); adding 0.08mmol of C1 into a schlenk reaction bottle, vacuumizing and introducing nitrogen for 3 times, respectively adding 1mmol of CTA1, 1000mmol of ClEVE and solvent Dichloromethane (DCM) under the nitrogen atmosphere, sealing the bottle mouth, placing the reaction bottle under the irradiation of Blue LEDs and reacting for 48 hours at room temperature to obtain a first reaction solution, performing rotary evaporation treatment on the first reaction solution to remove the solvent and residual monomers to obtain the polymer PClEVE, and testing that the polymerization degree of the PClEVE is 600;
3.3 preparing the photocatalytic anion exchange membrane; dissolving the PClEVE in the N, N-Dimethylformamide (DMF) to obtain a first solution with the mass ratio of 10 wt%, and placing the first solution in an oil bath kettle at 170 ℃ for heat treatment for 10min to obtain a second reaction solution; adding the N, N, N ', N' -tetramethyl-p-phenylenediamine into a second reaction solution, wherein the molar ratio of the PClEVE to the N, N, N ', N' -tetramethyl-p-phenylenediamine is 5:1, stirring for 15min at room temperature, raising the reaction temperature to 90 ℃, conducting quaternization reaction to obtain a third reaction solution, monitoring the change of the viscosity of the third reaction solution along with time, supplementing a solvent to dilute the viscosity of the third reaction solution when the viscosity of the third reaction solution is higher, coating the third reaction solution on the substrate, and drying at 90 ℃ to obtain the photocatalytic anion-exchange membrane.
The IEC of the photocatalytic anion exchange membrane prepared in this example was 1.94 mmol/g. Respectively testing the conductivity, the water content and the linear swelling rate of the chloride ions of the photocatalytic anion exchange membrane, wherein the conductivity of the chloride ions at 30 ℃ is 100.17mS/cm, the water content is 15.2 wt%, and the linear swelling rate is 1.8%; the chloride ion conductivity at 60 ℃ was 240.15mS/cm, the water content was 24% by weight, and the linear swelling ratio was 3.2%.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a photocatalytic anion exchange membrane is characterized by comprising the following steps:
step S1, preparing an aliphatic chain polymer by using 2-chloroethyl vinyl ether as a reaction monomer and adopting a light-operated cationic polymerization technology, wherein the aliphatic chain polymer is used as a main chain of a membrane material;
and step S2, using polyamine compounds as quaternizing agents and crosslinking agents, and carrying out quaternization reaction on the aliphatic chain polymer and the amine compounds to obtain the photocatalytic anion exchange membrane.
2. The method for preparing a photocatalytic anion exchange membrane according to claim 1, wherein the specific synthetic steps of the aliphatic chain polymer in step S1 are as follows:
s1-1, carrying out light-controlled cationic polymerization reaction on the 2-chloroethyl vinyl ether, a chain transfer reagent and a photocatalyst under the irradiation of Blue LEDs to obtain a first reaction solution;
and S1-2, performing rotary evaporation treatment on the first reaction liquid to remove the solvent and the residual monomers to obtain the poly-2-chloroethyl vinyl ether.
3. The method of claim 2, wherein the photocatalyst comprises 2,4, 6-tris (p-methoxyphenyl) boron tetrafluoride and the chain transfer agent comprises S-1-isobutoxyethyl S' -ethyl trithiocarbonate.
4. The method of claim 3, wherein the molar ratio of the 2-chloroethyl vinyl ether, the S-1-isobutoxyethyl S' -ethyl trithiocarbonate and the 2,4, 6-tris (p-methoxyphenyl) boron tetrafluoride is 100-1000: 1: 0.02-0.08.
5. The method for preparing the photocatalytic anion-exchange membrane according to claim 2, wherein the light-controlled cationic polymerization reaction is carried out at room temperature, and the reaction time is controlled to be 18 h-48 h.
6. The method of preparing a photocatalytic anion exchange membrane according to claim 2, wherein the polymerization degree of the poly 2-chloroethyl vinyl ether is 97 to 600.
7. The method for preparing a photocatalytic anion exchange membrane according to any one of claims 2 to 6, wherein the step S2 specifically comprises the steps of:
s2-1, dissolving the poly 2-chloroethyl vinyl ether in an organic solvent, and heating and thermally treating to obtain a second reaction solution;
s2-2, adding the polyamine compound into the second reaction liquid, and carrying out quaternization reaction to obtain a third reaction liquid;
and S2-3, coating the third reaction solution on a substrate, and drying to obtain the photocatalytic anion exchange membrane.
8. The method for preparing a photocatalytic anion exchange membrane according to claim 7, wherein the molar ratio of the poly-2-chloroethyl vinyl ether to the polyamine-based compound is 5-15: 1.
9. The method of claim 7, wherein the polyamine compound comprises triethylenediamine, pentamethyldiethylenetriamine, or N, N, N ', N' -tetramethylp-phenylenediamine.
10. The method of preparing a photocatalytic anion exchange membrane according to claim 8, wherein the mass percentage of the poly 2-chloroethyl vinyl ether dissolved in the organic solvent is 10 wt%.
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