CN116478377A - Polymer, anion exchange membrane and preparation method and application thereof - Google Patents
Polymer, anion exchange membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN116478377A CN116478377A CN202310395102.7A CN202310395102A CN116478377A CN 116478377 A CN116478377 A CN 116478377A CN 202310395102 A CN202310395102 A CN 202310395102A CN 116478377 A CN116478377 A CN 116478377A
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- China
- Prior art keywords
- polymer
- anion exchange
- solvent
- exchange membrane
- trifluoromethyl
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 135
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 32
- 238000005342 ion exchange Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims description 52
- -1 ketone compounds Chemical class 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 36
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 12
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NHFRGTVSKOPUBK-UHFFFAOYSA-N 4-phenylbutanal Chemical compound O=CCCCC1=CC=CC=C1 NHFRGTVSKOPUBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 7
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 150000001450 anions Chemical group 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- WLUJHMKCLOIRSK-UHFFFAOYSA-N 1,2,4,5-tetramethylimidazole Chemical compound CC=1N=C(C)N(C)C=1C WLUJHMKCLOIRSK-UHFFFAOYSA-N 0.000 claims description 4
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 4
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 4
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims description 4
- BDVKAMAALQXGLM-UHFFFAOYSA-N 1-ethylpiperidin-4-one Chemical compound CCN1CCC(=O)CC1 BDVKAMAALQXGLM-UHFFFAOYSA-N 0.000 claims description 4
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 claims description 4
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- YGDZKYYCJUNORF-UHFFFAOYSA-N 1-propylpiperidin-4-one Chemical compound CCCN1CCC(=O)CC1 YGDZKYYCJUNORF-UHFFFAOYSA-N 0.000 claims description 4
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- ZLSDEVRDASOICE-UHFFFAOYSA-N 2-azaadamantane Chemical compound C1C(N2)CC3CC1CC2C3 ZLSDEVRDASOICE-UHFFFAOYSA-N 0.000 claims description 4
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 4
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 4
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 4
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- XKGLSKVNOSHTAD-UHFFFAOYSA-N valerophenone Chemical compound CCCCC(=O)C1=CC=CC=C1 XKGLSKVNOSHTAD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 19
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract description 14
- 125000002091 cationic group Chemical group 0.000 abstract description 12
- 229920006037 cross link polymer Polymers 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 37
- 239000002244 precipitate Substances 0.000 description 12
- 238000005349 anion exchange Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 229930184652 p-Terphenyl Natural products 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012722 thermally initiated polymerization Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- 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
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
-
- 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
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- 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
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1414—Unsaturated aliphatic units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/148—Side-chains having aromatic units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
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Abstract
The invention discloses a polymer, an anion exchange membrane, a preparation method and application thereof, wherein the polymer is a cross-linked polymer, the main chain of the cross-linked polymer contains aryl and piperidine cation structure, and contains-CF 3 C-Structure, backbone-CF 3 The C-side chain containing cationic groups is crosslinked to form a crosslinked network structure, so that the ion exchange capacity and ion conductivity of the anion exchange membrane are improved, and the mechanical strength of the anion exchange membrane is improvedAnd dimensional stability.
Description
Technical Field
The invention belongs to the technical field of ion exchange polymers, and particularly relates to a polymer, an anion exchange membrane, a preparation method and application thereof.
Background
The anion exchange membrane can conduct anions and can be used in devices such as alkaline fuel cells, water separators and the like. Ionic conductivity, chemical stability and mechanical properties are important properties of anion exchange membranes. At present, on the basis of high ionic conductivity, anion exchange membranes having both excellent chemical stability and mechanical properties are still relatively few, which limits the development of practical applications. In recent years, attention has been paid to anion exchange polymers containing biphenyl and piperidine quaternary ammonium cationic structural units, which have excellent chemical stability, however, ion exchange capacity is still low, ion conductivity is limited, and mechanical strength and dimensional stability are also required to be improved. Therefore, there is a need to develop an anion exchange polymer with excellent properties such as ion exchange capacity, ion conductivity, mechanical strength, dimensional stability, etc., to meet the material requirements under different application conditions.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: the ion exchange capacity, ion conductivity, mechanical strength, dimensional stability and other properties of the existing anion exchange polymers are to be improved.
The present invention aims to solve at least one of the technical problems in the related art to some extent. For this purpose, the embodiment of the invention provides a polymer, an anion exchange membrane, a preparation method and application thereof, wherein the polymer is a crosslinked polymer, and the main chain of the crosslinked polymer contains aryl and piperidine cation structure and contains-CF 3 C-Structure, backbone-CF 3 C-has a positive component thereonThe side chain of the ionic group forms a cross-linked network structure through cross-linking, so that the ion exchange capacity and the ion conductivity of the anion exchange membrane are improved, and the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
The polymer of the embodiment of the invention has a structure shown in a formula (1):
wherein Ar is 1 、Ar 2 Each independently selected from substituted or unsubstituted aryl;
R 1 one selected from the hydrocarbon groups of C4-C100;
R 2 selected from any one of the following structural formulas:
R 3 、R 4 each independently selected from any one of C1-C10 chain alkyl or C3-C10 cycloalkyl;
x is an anion;
0< y <1; n is an integer between 20 and 20000; m is an integer between 5 and 500.
The polymer of the embodiment of the invention has the advantages and technical effects that the polymer is a cross-linked polymer, the main chain of the cross-linked polymer contains aryl and piperidine cation structure and contains-CF 3 C-Structure, backbone-CF 3 The side chain containing the cationic groups is arranged on the C-and improves the proportion of the cationic groups in the polymer, and the side chain forms a cross-linked network structure through cross-linking, so that the ion exchange capacity and the ion conductivity of the anion exchange membrane are improved, and meanwhile, the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
In some embodiments, ar 1 、Ar 2 Each independently selected from one of the following structural formulas:
R 1 selected from one of the following structural formulas:
q is an integer of 1 to 20.
In some embodiments, 0.6.ltoreq.y <1.
In some embodiments, the polymer comprises at least one of formulas (2) - (4):
the preparation method of the polymer provided by the embodiment of the invention comprises the following steps:
(1) Carrying out polymerization reaction on ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers under the action of a first solvent and a catalyst to obtain a first polymer;
(2) The first polymer reacts with an amine compound in a second solvent to obtain a second polymer;
(3) The second polymer reacts with a quaternizing agent in a third solvent to obtain a third polymer;
(4) And dissolving the third polymer in a fourth solvent to obtain a solution, and performing a crosslinking reaction to obtain the polymer.
The preparation method of the polymer of the embodiment of the invention comprises the steps of polymerizing ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers to obtain the polymer containing aryl, piperidine cation structure and-CF 3 Backbone of C-structure, -CF of backbone 3 Having cationic groups on CThe side chain of the third polymer contains an unsaturated carbon-carbon double bond structure, and the side chain forms a cross-linked network through cross-linking, so that the ion exchange capacity and the ion conductivity of the anion exchange membrane are improved, and the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
The anion exchange membrane of the embodiment of the invention comprises the polymer of the embodiment of the invention or the polymer prepared by the preparation method of the embodiment of the invention. The anion exchange membrane of the embodiment of the invention comprises a cross-linked polymer, wherein the main chain of the cross-linked polymer contains aryl and piperidine cation structure and contains-CF 3 C-Structure, backbone-CF 3 The side chain containing the cationic group is arranged on the C-and forms a cross-linked network structure through cross-linking, so that the ion exchange capacity and the ion conductivity of the anion exchange membrane are improved, and the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
The preparation method of the anion exchange membrane provided by the embodiment of the invention comprises the following steps:
(1) Carrying out polymerization reaction on ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers under the action of a first solvent and a catalyst to obtain a first polymer;
(2) The first polymer reacts with an amine compound in a second solvent to obtain a second polymer;
(3) The second polymer reacts with a quaternizing agent in a third solvent to obtain a third polymer;
(4) And dissolving the third polymer in a fourth solvent to obtain a solution, spreading the solution on a plane, and heating to form a film to obtain the anion exchange membrane.
The preparation method of the anion exchange membrane of the embodiment of the invention comprises the steps of polymerizing ketone compounds, aryl monomers and piperidone monomers containing trifluoromethyl, carbon-carbon double bonds and halogen to obtain the anion exchange membrane containing aryl, piperidone cationic structures and-CF 3 Backbone of C-structure, -CF of backbone 3 Having side chains containing cationic groups and carbon-carbon double bonds on C-, which side chains are formed during the film formation by heatingThe cross-linked network structure is formed by in-situ cross-linking through thermal polymerization, so that the ion exchange capacity and ion conductivity of the anion exchange membrane are improved, and the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
In some embodiments, the ketone compound containing trifluoromethyl, carbon-carbon double bond, and halogen includes at least one of trifluoromethyl p- (2-p-bromomethylphenyl vinyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromomethylphenyl-2-butenyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromoethylphenyl-2-butenyl) phenylbutyl ketone, trifluoromethyl-7-dodecenyl ketone;
the amine compound comprises at least one of trimethylamine, N-methylpiperidine, 4-azaadamantane, N-methylimidazole and N,2,4, 5-tetramethylimidazole;
the aryl monomer comprises at least one of biphenyl, para-terphenyl, meta-terphenyl, para-terphenyl, diphenylmethane, 1, 2-diphenylethane and 9,9' -dimethylfluorene;
the piperidone monomer comprises at least one of N-methyl-4-piperidone, N-ethyl-4-piperidone and N-propyl-4-piperidone;
the quaternizing agent comprises at least one of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide or butyl bromide;
the molar ratio of the trifluoromethyl, carbon-carbon double bond and halogen-containing ketone compound to aryl monomer to piperidone monomer is 0-0.5: 1:0.7 to 1.2;
the molar ratio of the structural unit containing trifluoromethyl and halogen in the first polymer to the amine compound is 1:1-20;
the molar ratio of the second polymer to the quaternizing agent is 1:1-50.
In some embodiments, in step (1), the polymerization reaction temperature is from-5 ℃ to 5 ℃; the polymerization reaction time is 6-72 h; the first solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene; the catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid and methanesulfonic acid; after the polymerization reaction, adding the product into an alkali solution, soaking and washing; the alkali solution is at least one of sodium carbonate solution, potassium bicarbonate solution, sodium hydroxide solution or potassium hydroxide solution; the concentration of the alkali solution is 0.1-10 mol/L; the soaking time is 1-48 h;
in the step (2), the temperature of the reaction is 10-40 ℃; the reaction time is 3-24h; the second solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene;
in the step (3), the temperature of the reaction is 10-40 ℃; the reaction time is 6-72 h; the third solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; after the reaction, adding the product into a poor solvent to precipitate a polymer, and then washing and drying to obtain a third polymer; the poor solvent comprises at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, propyl propionate, butyl propionate and propyl butyrate;
in the step (4), the fourth solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; the mass ratio of the third polymer to the fourth solvent is 1-20:100; the heating temperature is 60-120 ℃, and the heating time is 1-72 h; the alkali liquor comprises at least one of 0.1-10M KOH solution and 0.1-10M NaOH solution; the ion exchange time is 12-72 h.
The anion exchange membrane of the embodiment of the invention or the anion exchange membrane prepared by the preparation method of the embodiment of the invention is used for an alkaline fuel cell or a water electrolyzer. The application of the anion exchange membrane in the embodiment of the present invention has all advantages and technical effects brought by the anion exchange membrane, and is not described herein.
Drawings
FIG. 1 is a schematic illustration of an embodiment and pair of the present inventionOH at 80℃for a proportional anion exchange membrane - Ion conductivity.
Fig. 2 is a graph showing the tensile strength of the anion exchange membranes of the examples and comparative examples of the present invention.
FIG. 3 shows the swelling ratios at 80℃of the anion exchange membranes of examples and comparative examples of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The polymer of the embodiment of the invention has a structure shown in a formula (1):
wherein Ar is 1 、Ar 2 Each independently selected from substituted or unsubstituted aryl;
R 1 one selected from the hydrocarbon groups of C4-C100; preferably, one selected from the group consisting of C8-C50 hydrocarbon groups containing a carbon-carbon double bond;
R 2 selected from any one of the following structural formulas:
R 3 、R 4 each independently selected from any one of C1-C10 chain alkyl or C3-C10 cycloalkyl;
x is an anion; preferably, X is selected from OH - 、Cl-、Br-、I-、F-、NO 3 - 、HCO 3 -at least one of;
0< y <1, optionally, e.g., 0.1,0.2,0.4,0.5,0.6,0.7,0.9; n is an integer between 20 and 20000, optionally, for example, 20, 50, 100, 500, 1000, 2000, 10000, 20000; m is an integer between 5 and 500, alternatively, for example, 5, 10, 50, 100, 200, 500.
The polymer of the embodiment of the invention has the advantages and technical effects that the polymer is a cross-linked polymer, the main chain of the cross-linked polymer contains aryl and piperidine cation structure and contains-CF 3 C-Structure, backbone-CF 3 The side chain containing the cationic groups is arranged on the C-and improves the proportion of the cationic groups in the polymer, and the side chain forms a cross-linked network structure through cross-linking, so that the ion exchange capacity and the ion conductivity of the anion exchange membrane are improved, and meanwhile, the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
In some embodiments, ar 1 、Ar 2 Each independently selected from one of the following structural formulas:
in the embodiment of the invention, aryl in the main chain of the polymer can be selected from biphenyl, terphenyl and the like, and the obtained polymer can improve the ion exchange capacity and ion conductivity of the anion exchange membrane and improve the mechanical strength and the dimensional stability.
In some embodiments, R 1 Selected from one of the following structural formulas:
q is an integer between 1 and 20, specifically, for example, 1,2,3,4,5,8, 10, 13, 15, 20.
In embodiments of the invention, R in the side chain of the polymer is preferred 1 The obtained polymer has the structural formula shown above, and is beneficial to further improving the ion exchange capacity and ion conductivity of the anion exchange membrane, and improving the mechanical strength and the dimensional stability.
In some embodiments, 0.6+.y <1, specifically, for example, 0.6,0.7,0.75,0.8,0.85,0.9,0.95. In the embodiment of the invention, the value of y in the polymer is optimized, so that the construction of a cross-linked network structure and the subsequent preparation of the anion exchange membrane can be ensured, and the ion exchange capacity, the ion conductivity, the mechanical strength and the dimensional stability of the anion exchange membrane can be improved.
In some embodiments, the polymer comprises at least one of formulas (2) - (4):
q is an integer between 1 and 20, specifically, for example, 1,2,3,4,5,8, 10, 13, 15, 20.
In the embodiment of the invention, the type of the polymer is further optimized, which is beneficial to further improving the ion exchange capacity and ion conductivity of the anion exchange membrane and improving the mechanical strength and the dimensional stability.
The preparation method of the polymer provided by the embodiment of the invention comprises the following steps:
(1) Carrying out polymerization reaction on ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers under the action of a first solvent and a catalyst to obtain a first polymer;
(2) The first polymer reacts with an amine compound in a second solvent to obtain a second polymer;
(3) The second polymer reacts with a quaternizing agent in a third solvent to obtain a third polymer;
(4) And dissolving the third polymer in a fourth solvent to obtain a solution, and performing a crosslinking reaction to obtain the polymer.
The preparation method of the polymer of the embodiment of the invention comprises the steps of polymerizing ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers to obtain the polymer containing aryl, piperidine cation structure and-CF 3 Backbone of C-structure, -CF of backbone 3 C-has a side chain containing a cationic group, the second polymer undergoes quaternization reaction with a quaternizing agent to obtain a third polymer, and the side chain of the third polymer contains an unsaturated carbon-carbon double bondThe side chains form a cross-linked network through cross-linking, so that the ion exchange capacity and ion conductivity of the anion exchange membrane are improved, and the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
In some embodiments, the ketone compound containing trifluoromethyl, carbon-carbon double bond, and halogen includes at least one of trifluoromethyl p- (2-p-bromomethylphenyl vinyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromomethylphenyl-2-butenyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromoethylphenyl-2-butenyl) phenylbutyl ketone, trifluoromethyl-7-dodecenyl ketone;
the amine compound comprises at least one of trimethylamine, N-methylpiperidine, 4-azaadamantane, N-methylimidazole and N,2,4, 5-tetramethylimidazole;
the aryl monomer comprises at least one of biphenyl, para-terphenyl, meta-terphenyl, para-terphenyl, diphenylmethane, 1, 2-diphenylethane and 9,9' -dimethylfluorene;
the piperidone monomer comprises at least one of N-methyl-4-piperidone, N-ethyl-4-piperidone and N-propyl-4-piperidone;
the quaternizing agent comprises at least one of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide or butyl bromide;
the molar ratio of the trifluoromethyl, carbon-carbon double bond and halogen-containing ketone compound to aryl monomer to piperidone monomer is 0-0.5: 1:0.7 to 1.2, specifically, for example, 0.1:1:0.7,0.2:1:0.8,0.3:1:1.2;
the molar ratio of the structural units containing trifluoromethyl and halogen to the amine compound in the first polymer is 1:1-20, specifically, for example, 1:1,1:3,1:5,1:10,1:15,1:20;
the molar ratio of the second polymer to the quaternizing agent is from 1:1 to 50, specifically, for example, 1:1,1:5,1:10,1:20,1:30,1:40,1:50.
In some embodiments, in step (1), the polymerization reaction temperature is from-5 ℃ to 5 ℃, optionally, 0 ℃; the polymerization reaction time is 6h to 72h, specifically, for example, 6h,12h,24h,36h,72h; the first solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene; the catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid and methanesulfonic acid, preferably, the volume ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid is 12:1; after the polymerization reaction, adding the product into an alkali solution, soaking and washing; the alkali solution is at least one of sodium carbonate solution, potassium bicarbonate solution, sodium hydroxide solution or potassium hydroxide solution; the concentration of the alkali solution is 0.1 to 10mol/L, specifically, for example, 0.1mol/L,1mol/L,5mol/L,10mol/L; the soaking time is 1-48 hours, specifically, for example, 1 hour, 12 hours, 24 hours, 36 hours, 48 hours;
in the step (2), the temperature of the reaction is 10 to 40 ℃, specifically, for example, 10 ℃,20 ℃,25 ℃,30 ℃,40 ℃; the reaction time is 3 to 24 hours, specifically, for example, 3 hours, 6 hours, 9 hours, 12 hours, 24 hours; the second solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene;
in the step (3), the temperature of the reaction is 10 to 40 ℃, specifically, for example, 10 ℃,20 ℃,25 ℃,30 ℃,40 ℃; the reaction time is 6 to 72 hours, specifically, for example, 6 hours, 12 hours, 24 hours, 36 hours, 72 hours; the third solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; after the reaction, adding the product into a poor solvent to precipitate a polymer, and then washing and drying to obtain a third polymer; the poor solvent comprises at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, propyl propionate, butyl propionate and propyl butyrate;
in the step (4), the fourth solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; the mass ratio of the third polymer to the fourth solvent is 1-20:100, specifically, for example, 1:100,5:100, 10:100, 20:100;
in the step (4), the crosslinking reaction includes at least one of a photoinitiated polymerization crosslinking reaction or a thermally initiated polymerization crosslinking reaction;
the photoinitiated polymerization crosslinking reaction comprises the steps of adding a photoinitiator into the solution, and carrying out photopolymerization crosslinking reaction under the irradiation of ultraviolet rays; the photoinitiator comprises at least one of Irgacure2959, irgacure500, irgacure127, TPO, ultraviolet light initiator 184, ultraviolet light initiator 1173 and ultraviolet light initiator 907; the mass ratio of the photoinitiator to the third polymer is 0.2-0.8:100, specifically, for example, 0.2:100,0.4:100,0.5:100,0.6:100,0.8:100; the photopolymerization reaction time is 1 to 60 minutes, specifically, for example, 1min,5min,10min,20min,40min,60min;
the thermally initiated polymeric crosslinking reaction includes heating the solution; the heating temperature is 60 to 120 ℃, specifically, for example, 60 ℃,80 ℃,100 ℃,120 ℃, and the heating time is 1 to 72 hours, specifically, for example, 1 hour, 6 hours, 12 hours, 24 hours, 36 hours, 48 hours, 72 hours.
The anion exchange membrane of the embodiment of the invention comprises the polymer of the embodiment of the invention or the polymer prepared by the preparation method of the embodiment of the invention. The anion exchange membrane of the embodiment of the invention comprises a cross-linked polymer, wherein the main chain of the cross-linked polymer contains aryl and piperidine cation structure and contains-CF 3 C-Structure, backbone-CF 3 The side chain containing the cationic group is arranged on the C-and forms a cross-linked network structure through cross-linking, so that the ion exchange capacity and the ion conductivity of the anion exchange membrane are improved, and the mechanical strength and the dimensional stability of the anion exchange membrane are improved.
The preparation method of the anion exchange membrane provided by the embodiment of the invention comprises the following steps:
(1) Carrying out polymerization reaction on ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers under the action of a first solvent and a catalyst to obtain a first polymer;
(2) The first polymer reacts with an amine compound in a second solvent to obtain a second polymer;
(3) The second polymer reacts with a quaternizing agent in a third solvent to obtain a third polymer;
(4) And dissolving the third polymer in a fourth solvent to obtain a solution, spreading the solution on a plane, and heating to form a film to obtain the anion exchange membrane.
The preparation method of the anion exchange membrane of the embodiment of the invention comprises the steps of polymerizing ketone compounds, aryl monomers and piperidone monomers containing trifluoromethyl, carbon-carbon double bonds and halogen to obtain the anion exchange membrane containing aryl, piperidone cationic structures and-CF 3 Backbone of C-structure, -CF of backbone 3 The side chain containing the cationic group and the carbon-carbon double bond is arranged on the C-and is in situ crosslinked to form a crosslinked network structure through thermal polymerization in the heating film forming process, so that the ion exchange capacity and the ion conductivity of the anion exchange film are improved, and the mechanical strength and the dimensional stability of the anion exchange film are improved.
In the embodiment of the invention, the heat-initiated cross-linked polymerization enables the cross-linked network structure to be in situ performed in the film heating and forming process, the uncrosslinked third polymer solution is thermally initiated to obtain the cross-linked film, and a larger cross-linking degree can be obtained.
In some embodiments, the ketone compound containing trifluoromethyl, carbon-carbon double bond, and halogen includes at least one of trifluoromethyl p- (2-p-bromomethylphenyl vinyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromomethylphenyl-2-butenyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromoethylphenyl-2-butenyl) phenylbutyl ketone, trifluoromethyl-7-dodecenyl ketone;
the amine compound comprises at least one of trimethylamine, N-methylpiperidine, 4-azaadamantane, N-methylimidazole and N,2,4, 5-tetramethylimidazole;
the aryl monomer comprises at least one of biphenyl, para-terphenyl, meta-terphenyl, para-terphenyl, diphenylmethane, 1, 2-diphenylethane and 9,9' -dimethylfluorene;
the piperidone monomer comprises at least one of N-methyl-4-piperidone, N-ethyl-4-piperidone and N-propyl-4-piperidone;
the quaternizing agent comprises at least one of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide or butyl bromide;
the molar ratio of the trifluoromethyl, carbon-carbon double bond and halogen-containing ketone compound to aryl monomer to piperidone monomer is 0-0.5: 1:0.7 to 1.2, specifically, for example, 0.1:1:0.7,0.2:1:0.8,0.3:1:1.2;
the molar ratio of the structural units containing trifluoromethyl and halogen to the amine compound in the first polymer is 1:1-20, specifically, for example, 1:1,1:3,1:5,1:10,1:15,1:20;
the molar ratio of the second polymer to the quaternizing agent is from 1:1 to 50, specifically, for example, 1:1,1:5,1:10,1:20,1:30,1:40,1:50.
In some embodiments, in step (1), the polymerization reaction temperature is from-5 ℃ to 5 ℃, optionally, 0 ℃; the polymerization reaction time is 6h to 72h, specifically, for example, 6h,12h,24h,36h,72h; the first solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene; the catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid and methanesulfonic acid, preferably, the volume ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid is 12:1; after the polymerization reaction, adding the product into an alkali solution, soaking and washing; the alkali solution is at least one of sodium carbonate solution, potassium bicarbonate solution, sodium hydroxide solution or potassium hydroxide solution; the concentration of the alkali solution is 0.1 to 10mol/L, specifically, for example, 0.1mol/L,1mol/L,5mol/L,10mol/L; the soaking time is 1-48 hours, specifically, for example, 1 hour, 12 hours, 24 hours, 36 hours, 48 hours;
in the step (2), the temperature of the reaction is 10 to 40 ℃, specifically, for example, 10 ℃,20 ℃,25 ℃,30 ℃,40 ℃; the reaction time is 3 to 24 hours, specifically, for example, 3 hours, 6 hours, 9 hours, 12 hours, 24 hours; the second solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene;
in the step (3), the temperature of the reaction is 10 to 40 ℃, specifically, for example, 10 ℃,20 ℃,25 ℃,30 ℃,40 ℃; the reaction time is 6 to 72 hours, specifically, for example, 6 hours, 12 hours, 24 hours, 36 hours, 72 hours; the third solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; after the reaction, adding the product into a poor solvent to precipitate a polymer, and then washing and drying to obtain a third polymer; the poor solvent comprises at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, propyl propionate, butyl propionate and propyl butyrate;
in the step (4), the fourth solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; the mass ratio of the third polymer to the fourth solvent is 1-20:100, specifically, for example, 1:100,5:100, 10:100, 20:100; the temperature of the heating is 60 to 120 ℃, specifically, for example, 60 ℃,80 ℃,100 ℃,120 ℃, and the time of the heating is 1 to 72 hours, specifically, for example, 1 hour, 6 hours, 12 hours, 24 hours, 36 hours, 48 hours, 72 hours; optionally, the flat surface is a groove of a flat glass plate.
In some embodiments, the resulting anion exchange membrane is immersed in an alkaline solution for ion exchange; the alkali liquor comprises at least one of 0.1-10M KOH solution and 0.1-10M NaOH solution, and specifically, for example, 0.1M,1M,5M and 10M; the ion exchange time is 12 to 72 hours, specifically, for example, 12 hours, 24 hours, 36 hours, 48 hours, 72 hours.
In a preferred embodiment, the process for preparing a polymer comprising the formulae (2) to (4) comprises the following steps:
(1) The mole ratio of biphenyl or terphenyl, N-methyl-4-piperidone and trifluoromethyl to (2-p-bromomethylphenyl vinyl) phenylpropyl ketone is 10:8:2, adding dichloromethane for dissolution, adding trifluoromethanesulfonic acid and trifluoroacetic acid at the temperature of-5 ℃, wherein the volume ratio of the trifluoromethanesulfonic acid to the trifluoroacetic acid is 12:1, and carrying out mechanical stirring reaction for 6-24 hours;
pouring the product into 0.5-3M K 2 CO 3 Soaking in the solution for 1-24 hours at room temperature, filtering to obtain a white solid product, washing with water, and drying to obtain a polymer containing piperidine tertiary amine groups;
(2) The mass ratio of the polymer containing the piperidine tertiary amine group to trimethylamine or N-methylpiperidine is 2:1, dissolving in chloroform, stirring at room temperature for 3-24h to obtain a cation substituted polymer;
(3) Adding a cation substituted polymer into dimethyl sulfoxide, adding trifluoroacetic acid to promote polymer dissolution, adding potassium carbonate and methyl iodide after dissolution, and reacting for 6-72 h at room temperature; pouring the product into ethyl acetate to obtain a precipitate, washing the precipitate with ethyl acetate, washing the precipitate with water, and drying the precipitate to obtain the piperidinium functionalized polymer;
(4) Adding dimethyl sulfoxide into the piperidinium functionalized polymer, fully dissolving, pouring into a groove of a flat glass plate, and heating at 60-120 ℃ for 1-72 hours to form a film; and soaking the membrane in KOH solution for ion exchange to obtain the anion exchange membrane.
The anion exchange membrane of the embodiment of the invention or the anion exchange membrane prepared by the preparation method of the embodiment of the invention is used for an alkaline fuel cell or a water electrolyzer. The application of the anion exchange membrane in the embodiment of the present invention has all advantages and technical effects brought by the anion exchange membrane, and is not described herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1:
(y＝0.80)
(1) 10.0mmol of p-terphenyl was weighed into a 100mL three-necked flask, 8.0mmol of N-methyl-4-piperidone and 2.0mmol of trifluoromethyl p- (2-p-bromomethylphenyl vinyl) phenylpropyl ketone were added, and 10mL of methylene chloride was added to dissolve the reaction product. 12mL of trifluoromethanesulfonic acid and 1mL of trifluoroacetic acid were added at 0deg.C and reacted with mechanical stirring for 12 hours. Pouring the viscous purple product into 1M K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a polymer containing piperidine tertiary amine groups;
(2) 1.2g of the above polymer containing a piperidine tertiary amine group was weighed, dissolved in 10mL of chloroform together with 0.6g (10 mmol) of N-methylpiperidine, and stirred at room temperature for 12 hours to obtain a cation-substituted polymer.
(3) 1.2g of the cation-substituted polymer was weighed into a 100mL single-necked flask, 15mL of dimethyl sulfoxide was added, 150. Mu.L of trifluoroacetic acid was added to promote dissolution of the polymer, and after complete dissolution, 0.36g of potassium carbonate and 300. Mu.L of methyl iodide were added to react at room temperature for 24 hours. Pouring the reaction product into ethyl acetate to precipitate to obtain yellow precipitate, washing the yellow precipitate with ethyl acetate for several times, washing the yellow precipitate with water instead, and drying the yellow precipitate to obtain the piperidinium functionalized polymer with the anion of I-.
(4) 1g of the piperidinium functionalized polymer is weighed, 50mL of dimethyl sulfoxide is added, the mixture is poured into a groove of a flat glass plate after being fully dissolved, and the mixture is heated at 80 ℃ for 48 hours to form a film, and meanwhile, a crosslinked network structure is formed in situ. The membrane was peeled off from the glass plate and immersed in a 1M KOH solution, followed by ion exchange at room temperature for 48 hours to obtain an anion exchange membrane having OH-anions.
The OH-ion conductivity of the fully wet anion exchange membrane in pure water was measured using a four electrode AC impedance method. The ion conductivity of the anion exchange membrane obtained in this example was 152mS/cm at 80 ℃.
The anion exchange membranes described in this example were subjected to swelling and tensile strength testing. After washing the OH-type anion exchange membrane with ultrapure water, the swelling of the membrane was tested with respect to the dry membrane. The anion exchange membrane obtained in this example swells to 8% at 80 ℃. The tensile strength of the anion-exchange membrane at room temperature was measured by using a tensile tester, and the tensile strength of the anion-exchange membrane obtained in this example was 89.3MPa at room temperature.
Example 2:
the same preparation method as in example 1 was used, except that in the step (2), N-methylpiperidine was replaced with trimethylamine. The anion exchange polymer contained in the obtained anion exchange membrane has the structure shown below (y=0.80):
example 3:
the same preparation method as in example 1 was used, except that in the above step (1), p-terphenyl was replaced with biphenyl. The anion exchange polymer contained in the obtained anion exchange membrane has the structure shown below (y=0.80):
comparative example 1:
(1) 10.0mmol of p-terphenyl was weighed into a 100mL three-necked flask, 8.0mmol of N-methyl-4-piperidone and 2.0mmol of 1, 1-trifluoroacetone were added, and 10mL of methylene chloride was added to dissolve the reaction product. 12mL of trifluoromethanesulfonic acid and 1mL of trifluoroacetic acid were added at 0deg.C and reacted with mechanical stirring for 12 hours. Pouring the viscous product into 1M K 2 CO 3 Soaking in the solution for 24 hours at room temperature, filtering to obtain a white solid product, fully washing with deionized water, and drying to obtain a polymer containing piperidine tertiary amine groups;
(2) 1.2g of the cation-substituted polymer was weighed into a 100mL single-necked flask, 15mL of dimethyl sulfoxide was added, 150. Mu.L of trifluoroacetic acid was added to promote dissolution of the polymer, and after complete dissolution, 0.36g of potassium carbonate and 300. Mu.L of methyl iodide were added to react at room temperature for 24 hours. Pouring the reaction product into ethyl acetate to precipitate and obtain a precipitate, washing the precipitate with ethyl acetate for a plurality of times, washing the precipitate with water instead, and drying the precipitate to obtain the piperidinium functionalized polymer with the anion of I-.
(3) 1g of the above piperidinium functionalized polymer was weighed, 50mL of dimethyl sulfoxide was added, and after sufficient dissolution, poured into a groove of a flat glass plate, and heated at 80℃for 48 hours to form a film. The membrane was peeled off from the glass plate and immersed in a 1M KOH solution, followed by ion exchange at room temperature for 48 hours to obtain an anion exchange membrane having OH-anions.
The anion exchange polymer contained in the obtained anion exchange membrane has the structure shown below (y=0.80):
comparative example 2:
the same procedure as in comparative example 1 was followed except that in step (1), p-terphenyl was exchanged for biphenyl.
The anion exchange polymer contained in the obtained anion exchange membrane has the structure shown below (y=0.80):
the anion exchange membranes prepared in examples 2-3 and comparative examples 1-2 were also subjected to performance testing, the test results are shown in FIGS. 1-3. As can be seen from FIGS. 1 to 3, the polymers in the anion exchange membranes of examples 1 to 3 have a poly (arylpiperidine) backbone containing piperidinium and containing-CF 3 C-Structure, backbone-CF 3 The side chain with the cationic group on the C-is provided with an unsaturated double bond structure, and a cross-linked network structure is formed in situ in a thermal polymerization mode in the heating film forming process, so that the ion exchange capacity and the ion conductivity of the anion exchange film are improved, and the mechanical strength and the dimensional stability of the anion exchange film are improved.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (10)
1. A polymer, characterized in that the polymer has a structure represented by formula (1):
wherein Ar is 1 、Ar 2 Each independently selected from substituted or unsubstituted aryl;
R 1 one selected from the hydrocarbon groups of C4-C100;
R 2 selected from any one of the following structural formulas:
R 3 、R 4 each independently selected from any one of C1-C10 chain alkyl or C3-C10 cycloalkyl;
x is an anion;
0< y <1; n is an integer between 20 and 20000; m is an integer between 5 and 500.
2. The polymer of claim 1, wherein Ar 1 、Ar 2 Each independently selected from one of the following structural formulas:
R 1 selected from one of the following structural formulas:
q is an integer of 1 to 20.
3. The polymer of claim 1, wherein 0.6.ltoreq.y <1.
4. The polymer of claim 1, wherein the polymer comprises at least one of formulas (2) - (4):
5. a process for the preparation of a polymer as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Carrying out polymerization reaction on ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers under the action of a first solvent and a catalyst to obtain a first polymer;
(2) The first polymer reacts with an amine compound in a second solvent to obtain a second polymer;
(3) The second polymer reacts with a quaternizing agent in a third solvent to obtain a third polymer;
(4) And dissolving the third polymer in a fourth solvent to obtain a solution, and performing a crosslinking reaction to obtain the polymer.
6. An anion exchange membrane comprising the polymer of any one of claims 1 to 4 or the polymer produced by the production process of claim 5.
7. A method of preparing the anion exchange membrane of claim 6, comprising the steps of:
(1) Carrying out polymerization reaction on ketone compounds containing trifluoromethyl, carbon-carbon double bonds and halogen, aryl monomers and piperidone monomers under the action of a first solvent and a catalyst to obtain a first polymer;
(2) The first polymer reacts with an amine compound in a second solvent to obtain a second polymer;
(3) The second polymer reacts with a quaternizing agent in a third solvent to obtain a third polymer;
(4) And dissolving the third polymer in a fourth solvent to obtain a solution, spreading the solution on a plane, and heating to form a film to obtain the anion exchange membrane.
8. The method for producing an anion exchange membrane according to claim 7, wherein the ketone compound containing a trifluoromethyl group, a carbon-carbon double bond and a halogen comprises at least one of trifluoromethyl p- (2-p-bromomethylphenyl vinyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromomethylphenyl-2-butenyl) phenylpropyl ketone, trifluoromethyl p- (4-p-bromoethylphenyl-2-butenyl) phenylbutyl ketone and trifluoromethyl-7-dodecenyl ketone;
the amine compound comprises at least one of trimethylamine, N-methylpiperidine, 4-azaadamantane, N-methylimidazole and N,2,4, 5-tetramethylimidazole;
the aryl monomer comprises at least one of biphenyl, para-terphenyl, meta-terphenyl, para-terphenyl, diphenylmethane, 1, 2-diphenylethane and 9,9' -dimethylfluorene;
the piperidone monomer comprises at least one of N-methyl-4-piperidone, N-ethyl-4-piperidone and N-propyl-4-piperidone;
the quaternizing agent comprises at least one of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, propyl bromide, butyl bromide or butyl bromide;
the molar ratio of the trifluoromethyl, carbon-carbon double bond and halogen-containing ketone compound to aryl monomer to piperidone monomer is 0-0.5: 1:0.7 to 1.2;
the molar ratio of the structural unit containing trifluoromethyl and halogen in the first polymer to the amine compound is 1:1-20;
the molar ratio of the second polymer to the quaternizing agent is 1:1-50.
9. The method for producing an anion exchange membrane according to claim 7, wherein in the step (1), the temperature of the polymerization reaction is-5 ℃ to 5 ℃; the polymerization reaction time is 6-72 h; the first solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene; the catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid and methanesulfonic acid; after the polymerization reaction, adding the product into an alkali solution, soaking and washing; the alkali solution is at least one of sodium carbonate solution, potassium bicarbonate solution, sodium hydroxide solution or potassium hydroxide solution; the concentration of the alkali solution is 0.1-10 mol/L; the soaking time is 1-48 h;
in the step (2), the temperature of the reaction is 10-40 ℃; the reaction time is 3-24h; the second solvent comprises at least one of dichloromethane, chloroform, tetrachloroethane and toluene;
in the step (3), the temperature of the reaction is 10-40 ℃; the reaction time is 6-72 h; the third solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; after the reaction, adding the product into a poor solvent to precipitate a polymer, and then washing and drying to obtain a third polymer; the poor solvent comprises at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl butyrate, propyl propionate, butyl propionate and propyl butyrate;
in the step (4), the fourth solvent comprises at least one of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide or dimethylacetamide; the mass ratio of the third polymer to the fourth solvent is 1-20:100; the heating temperature is 60-120 ℃, and the heating time is 1-72 h; the alkali liquor comprises at least one of 0.1-10M KOH solution and 0.1-10M NaOH solution; the ion exchange time is 12-72 h.
10. Use of an anion exchange membrane according to claim 6 or prepared by a process according to any one of claims 7 to 9, for alkaline fuel cells or water separators.
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| CN117164796A (en) * | 2023-08-10 | 2023-12-05 | 宁波中科氢易膜科技有限公司 | Cross-linked all-carbon skeleton polymer, anion exchange membrane and preparation method |
| CN117700694A (en) * | 2023-10-20 | 2024-03-15 | 宁波中科氢易膜科技有限公司 | Cross-linked polymer, binder, ionic membrane, and preparation method and application thereof |
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| CN117164796A (en) * | 2023-08-10 | 2023-12-05 | 宁波中科氢易膜科技有限公司 | Cross-linked all-carbon skeleton polymer, anion exchange membrane and preparation method |
| CN117700694A (en) * | 2023-10-20 | 2024-03-15 | 宁波中科氢易膜科技有限公司 | Cross-linked polymer, binder, ionic membrane, and preparation method and application thereof |
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