CN105542148A - A polyethersulfone anion-exchange membrane capable of being used for alkaline polymer electrolyte fuel cells, a preparing method thereof and applications of the membrane - Google Patents
A polyethersulfone anion-exchange membrane capable of being used for alkaline polymer electrolyte fuel cells, a preparing method thereof and applications of the membrane Download PDFInfo
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- CN105542148A CN105542148A CN201510976625.6A CN201510976625A CN105542148A CN 105542148 A CN105542148 A CN 105542148A CN 201510976625 A CN201510976625 A CN 201510976625A CN 105542148 A CN105542148 A CN 105542148A
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- polymer electrolyte
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 71
- 239000000446 fuel Substances 0.000 title claims abstract description 44
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 34
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 19
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 5
- 239000012528 membrane Substances 0.000 title abstract description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 60
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 125000005843 halogen group Chemical group 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229920000570 polyether Polymers 0.000 claims description 22
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005893 bromination reaction Methods 0.000 claims description 16
- 239000005357 flat glass Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000003880 polar aprotic solvent Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 229920001643 poly(ether ketone) Polymers 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 22
- 230000003252 repetitive effect Effects 0.000 description 20
- 238000005201 scrubbing Methods 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 230000002596 correlated effect Effects 0.000 description 12
- 230000008676 import Effects 0.000 description 9
- 239000002952 polymeric resin Substances 0.000 description 9
- 229920003002 synthetic resin Polymers 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000090 poly(aryl ether) Polymers 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 benzyl methyl Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- YGYPMFPGZQPETF-UHFFFAOYSA-N Cc1cc(-c(cc2C)cc(C)c2O)cc(C)c1O Chemical compound Cc1cc(-c(cc2C)cc(C)c2O)cc(C)c1O YGYPMFPGZQPETF-UHFFFAOYSA-N 0.000 description 1
- PJYUAQFKSFWWAH-UHFFFAOYSA-N Cc1cc(C2(CCCCC2)c(cc2)ccc2O)ccc1O Chemical compound Cc1cc(C2(CCCCC2)c(cc2)ccc2O)ccc1O PJYUAQFKSFWWAH-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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
-
- 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
-
- 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
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a polyethersulfone anion-exchange membrane capable of being used for alkaline polymer electrolyte fuel cells, a preparing method thereof and applications of the membrane. The membrane has a structure shown as a formula (I). The membrane is prepared from polyethersulfone or polyether ketone containing a quaternary ammonium salt ion exchange group. The main chain of the polyethersulfone or the polyether ketone has good mechanical properties and thermal stability. The quaternary ammonium salt ion exchange group is controllable in content and good in chemical stability and ion exchange performance. The prepared membrane is high in ion conductivity and good in thermal stability and alkaline stability, can meet using requirements of the alkaline polymer electrolyte fuel cells on the anion-exchange membrane, and has a good application prospect in the field of alkaline fuel cells.
Description
Technical field
The invention belongs to ion exchange membrane material field, be specifically related to a kind of polyether compound, its anion-exchange membrane and its preparation method and application that contain hexanaphthene group and quaternary ammonium salt side.
Background technology
In the past few decades, polymer electrolyte fuel cells (PEFCs) is considered to one of generating set most with prospects because of the feature such as efficient, clean.Proton Exchange Membrane Fuel Cells (PEMFCs), owing to there is fuel infiltration, noble metal catalyst and intermediate product need being used to cause the defects such as poison electrode catalysts, hinders it and further develops and marketization application.
Alkaline polymer electrolyte fuel cell (AEMFCs), as a kind of fuel cell technology worked under alkaline environment, compared with Proton Exchange Membrane Fuel Cells, has following obvious advantage:
(1) effectively can intercept fuel and the oxygenant at negative and positive the two poles of the earth, methanol permeability is low; (2) have than speed of response faster in Proton Exchange Membrane Fuel Cells; (3) poison electrode catalysts can not be caused; (4) avoid the situation that must use noble metal catalyst, can silver be selected, cobalt, the non-precious metal catalysts such as nickel, greatly reduce production cost.
As the important component part of alkaline polymer electrolyte fuel cell, the performance of performance to alkaline fuel cell of anion-exchange membrane has material impact.Anion-exchange membrane in alkaline polymer electrolyte fuel cell, needs to have higher ionic conductivity, high chemical stability and thermostability and good mechanical property etc.The main chain of anion-exchange membrane is generally made up of polyarylether compounds or fatty-chain polymers, and side base is made up of charged quaternary ammonium salt group.Polyether compound has remarkable thermostability, mechanical property and corrosion resistance nature, is applied widely at fuel cell ion exchange membrane Material Field.Ionic conductivity and chemical stability are the bottlenecks of current anion-exchange membrane technical development.(the JournaloftheAmericanChemicalSociety such as M.Tanaka, 2011,133,10646 – 10654) report adopt this group containing large steric hindrance of fluorenyl to prepare quaternary ammonium salt polyether compound that hydrophobe is separated to improve ionic conductivity and the chemical stability of anion-exchange membrane.(the ACSAppliedMaterials & Interfaces such as QingLinLiu, 2015,7, ionic conductivity 8284-8292) by introducing anion-exchange membrane prepared by this large steric hindrance of phenolphthalein and nonplanar aromatic group on main polymer chain reaches 146mS/cm 80 DEG C time, and at 2MKOH, place in 60 DEG C after 25 days and ionic conductivity still can be made to remain on about 70mS/cm.Document (K.Miyatake, PolymerChemistry, 2011,2,1919-1929) report, the molecular radical of this large steric hindrance of fluorenes, phenolphthalein and hexanaphthene is conducive to improving the free volume in the thermostability of anion-exchange membrane and chemical stability and film, is conducive to improving ionic conductance.Present specification has larger steric hindrance and nonplanar group equally and introduces polyarylether polymer main chain by this for hexanaphthene and be conducive to improving the ionic conductance of its anion-exchange membrane, chemical stability and thermal stability, can be applied in alkaline polymer fuel cell as anion-exchange membrane.
Summary of the invention
An object of the present invention is to be for the deficiencies in the prior art, there is provided a kind of polyethersulfone anion-exchange membrane that can be used for alkaline polymer electrolyte fuel cell, this anion-exchange membrane has higher ionic conductivity, chemical stability, thermostability and mechanical property.Anion-exchange membrane main chain of the present invention is polyethersulfone or polyether ketone polymer, there is good mechanical property and thermal stability, side base is for containing Trimethylamine 99, N-Methylimidazole, 1, any one in 2-methylimidazole, pyridine, guanidine, has good ion exchanging function and chemical stability.
Technical scheme of the present invention is as follows:
Can be used for a polyethersulfone anion-exchange membrane for alkaline polymer electrolyte fuel cell, the polyether compound containing hexanaphthene group and quaternary ammonium salt side for such as shown in formula I:
Wherein m and n represents the polymerization degree, m=1 ~ 200 and n=0 ~ 200,0<m/ (m+n)≤1, and the relative molecular weight of polymkeric substance is 10000 ~ 100000; R
1, R
2respective is independently hydrogen atom, methyl or quaternary ammonium salt group.
Preferably,
the respective one be independently selected from formula (1) ~ formula (3):
Work as R
1=R
2during=H, preferably
be selected from formula (4) ~ formula (6) any one:
Work as R
1=Q, R
2=H or R
1=H, R
2=Q or R
1=R
2during=Q, preferably
be selected from formula (7) ~ formula (9) any one:
Wherein Q can be any one in several substituting group below:
Wherein, X is the negatively charged ion of the negative valence charge of band, can be Br
-, Cl
-or OH
-.
According to the present invention, described formula I is random copolymers.
By controlling the ratio that feeds intake, can the ratio of control m and n component, the numerical value of m and n reflects molecular weight and the range of molecular weight distributions of polyether compound.
Another object of the present invention is to provide the above-mentioned preparation method containing the polyether compound of hexanaphthene group and quaternary ammonium salt side.
The inventive method comprises the following steps:
Step (1), by bisphenol cyclohexane monomer, biphenol monomer B, fragrant monomer A containing halogen atom, fragrant monomer C containing halogen atom and catalyzer are according to mol ratio 1:(0 ~ 199): 1:(0 ~ 199): (2.5 ~ 500) join reaction vessel, then water entrainer and polar aprotic solvent p is added, after reacting 3h at 140 DEG C, be warming up to 150 ~ 210 DEG C of reaction 3 ~ 16h, reactant is poured in ethanol and separates out, and with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 24h at 80 DEG C, obtains polyether compound CHPES; The volume ratio of described water entrainer and polar aprotic solvent p is (0.2 ~ 0.4): 1;
Described biphenol monomer B need add with the fragrant monomer C containing halogen atom simultaneously, or does not add simultaneously.
1. R is worked as
1=R
2during=H:
The described biphenol monomer containing hexanaphthene has following structure:
Described have following structure containing biphenol monomer B:
wherein
be selected from formula (11) ~ formula (13) any one:
Described fragrant monomer A and C containing halogen atom has following structure:
Wherein
respective be independently selected from formula (14) ~ (16) any one:
2. R is worked as
1=Q, R
2=H or R
1=H, R
2=Q or R
1=R
2during=Q:
Described cyclohexane monomer has as shown in the formula any one in (17) ~ formula (19) structure:
Described biphenol monomer B has following structure:
wherein
be selected from formula (20) ~ formula (22) any one:
The described fragrant monomer containing halogen atom
there is same above formula (14) ~ formula (16) structure.
Step (2), the polyether compound CHPES of preparation in step (1) is dissolved in the enpara kind solvent of certain volume, then appropriate bromizating agent and initiator is added, carry out bromination reaction 5 ~ 8h at a certain temperature, pour in ethanol and precipitate, then use ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain brominated product BCHPES; The mass ratio of described polyether compound CHPES, alkyl halide varsol, bromizating agent and initiator is 1:(24.70 ~ 31.90): (1.27 ~ 2.0304): (0.0583 ~ 0.086).
Step (3), brominated product BCHPES described in step (2) is dissolved in polar aprotic solvent q after, add quaternizing agent, reaction overnight 24h at 50 DEG C, obtains quaternized products QCHPES; The mass ratio of described brominated product BCHPES, polar aprotic solvent q and quaternizing agent is 1:9:(0.32 ~ 10).
Step (4), the quaternized products QCHPES obtained is coated in prior level-off clean sheet glass above, at 50 DEG C, dry 24h is to make solvent evaporates complete, film is taken off above sheet glass, obtain described anion-exchange membrane, prepared anion-exchange membrane is assembled in alkaline polymer electrolyte fuel cell and all-vanadium flow battery respectively and tests correlated performance.
Preferably, the polar aprotic solvent q in the polar aprotic solvent p described in step (1), step (3) is independently N,N-dimethylacetamide separately, DMF, tetramethylene sulfone, N-Methyl pyrrolidone, the one in dimethyl sulfoxide (DMSO).
Preferably, the water entrainer described in step (1) is toluene.
Preferably, the catalyzer described in step (1) is salt of wormwood, any one in sodium carbonate or cesium carbonate.
Preferably, the polymeric reaction temperature described in step (1) is 150 ~ 210 DEG C.
Preferably, described in step (2), enpara kind solvent is sym.-tetrachloroethane, 1,2-ethylene dichloride, any one in tetracol phenixin.
Preferably, initiator described in step (2) is any one in benzoyl peroxide or Diisopropyl azodicarboxylate.
Preferably, bromizating agent described in step (2) is any one in N-bromo-succinimide or C5H6Br2N2O2.
Preferably, the bromination reaction temperature described in step (2) is 75 ~ 85 DEG C.
Preferably, described in step (3), quaternizing agent is Trimethylamine 99, N-Methylimidazole, 1,2 dimethylimidazole, any one in pyridine and guanidine.
Another object of the present invention is to provide the above-mentioned polyarylether anion-exchange membrane containing hexanaphthene group and quaternary ammonium salt side, can apply in alkaline polymer electrolyte fuel cell and all-vanadium flow battery.
Preparation method and application described in the inventive method are the scheme optimized, and reaction monomers of the present invention, temperature, time and other correlated response conditions are the claimed content of this patent, and this patent is claimed is not limited only to this.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention is from Molecular Structure Design and polymer performance angle, and prepare polyether compound and the anion-exchange membrane thereof of a series of excellent performance, raw material is easy to get, and preparation technology is simple, and cost is low.
(2) polyether compound main chain of the present invention contains the nonplanar hexanaphthene group of large steric hindrance, and contain more fragrant phenyl ring and ehter bond in molecule, the intensity that both improve polymkeric substance turn increases the flexibility of molecule simultaneously.
(3) the present invention it also avoid the use of cancer causing agents chloromethyl ether in conventional ion exchange membrane preparation process simultaneously.
(4) anion-exchange membrane that prepared by the present invention has higher ionic conductivity, good thermostability, mechanical property and chemical stability, there is lower electrolyte permeability performance simultaneously, can be applied in alkaline polymer electrolyte fuel cell and all-vanadium flow battery as proton exchange membrane, effectively can reduce the self-discharge performance of battery.
Accompanying drawing explanation
Fig. 1 is containing hexanaphthene polyether compound resin CHPES, the hexanaphthene polyether compound BCHPES of bromination and the nuclear-magnetism figure of quaternized anion-exchange membrane QCHPES;
Fig. 2 is hexanaphthene polyether compound resin, bromination cyclohexane product and the infrared spectra containing quaternized anion-exchange membrane;
Fig. 3 is the specific conductivity of the hydroxyl form anion-exchange membrane containing hexanaphthene group and quaternary ammonium salt side;
Fig. 4 is the thermostability curve of the anion-exchange membrane containing hexanaphthene and quaternary ammonium salt side.
Embodiment
For further analysis to the present invention below in conjunction with specific embodiment.
Embodiment 1
By the cyclohexane monomer (formula 10) of 10mmol, the biphenol monomer B (formula 11) of 10mmol, the fragrant monomer C (formula 14) of the fragrant monomer A (formula 14) of the halogen atom-containing of 10mmol and the halogen atom-containing of 10mmol joins and water trap is housed, in the there-necked flask of the 250ml of agitator and import and export of nitrogen, add the salt of wormwood of 50mmol as catalyzer, the toluene of 30ml is as water entrainer, add the tetramethylene sulfone of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C reaction 3h, polymers soln is poured in ethanol and precipitates, and with ethanol and deionized water repetitive scrubbing 3 times, vacuum-drying 24h at 80 DEG C, obtain white polymer resin CHPES, productive rate is 92%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (31.86g), 1,2, in 2-tetrachloroethane, the N-bromo-succinimide adding 1.27g is as the benzoyl peroxide of bromizating agent and 0.086g as initiator, and bromination reaction 5h is carried out in lower 85 DEG C of nitrogen protection, pours in ethanolic soln and precipitate after being cooled to room temperature, with ethanol repetitive scrubbing 3 times, at 60 DEG C, vacuum-drying obtains white fibrous product B CHPES, get the N,N-dimethylacetamide that 0.5gBCHPES is dissolved in 4.5g in the there-necked flask of 50ml, form 10% solution, after add 1 of 0.2g, 2-methylimidazole, reaction overnight 24h at 50 DEG C, is coated on the clean sheet glass of prior leveling, dry at 50 DEG C, obtain described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
Containing the hexanaphthene polyether compound BCHPES of hexanaphthene polyether compound resin CHPES, bromination and quaternized anion-exchange membrane QCHPES proton nuclear magnetic spectrogram as shown in Figure 1, in the proton nuclear magnetic spectrogram of CHPES resin, there is a strong fignal center at 2.0ppm place, and this is the benzyl methyl signals in formula (1); The fignal center at 1.5ppm and 2.3ppm place is methylene signals, and 8.0ppm place is the fignal center with sulfuryl adjacent protons in phenyl ring, shows the formation of sulfuryl polymkeric substance.In the nuclear-magnetism of brominated product BCHPES, 4.2ppm place is brooethyl peak, shows that brominated product is formed.In the nuclear-magnetism figure of anion-exchange membrane QCHPES, the appearance of 3.5ppm and 2.5ppm fignal center shows that 1,2 dimethylimidazole is successfully incorporated into above polymer pendant groups, and 5.3ppm place is the benzyl methyl signals peak be connected with 1,2 dimethylimidazole.
Fig. 2 is the infrared spectrogram of hexanaphthene polyether compound resin CHPES, brominated hexane product B CHPES and quaternized anion-exchange membrane QCHPES.1658cm in figure
-1absorption peak is C-N key on imidazole ring.1600cm
-1and 1488cm
-1be respectively the absorption peak of C=C and C=N on phenyl ring and imidazoles.
The ionic conductivity of quaternized anion-exchange membrane prepared by the present embodiment is as shown in QCHPES-1 in Fig. 3, and when 30 DEG C, this film ionic conductivity is in deionized water 6.2mS/cm, reaches 15.5mS/cm when 80 DEG C.
Embodiment 2
By the hexanaphthene (formula 10) of 10mmol, the biphenol monomer B (formula 12) of 10mmol, the fragrant monomer C (formula 15) of the fragrant monomer A (formula 15) of the halogen atom-containing of 10mmol and the halogen atom-containing of 10mmol joins and water trap is housed, in the 250ml there-necked flask of agitator and import and export of nitrogen, the toluene of 30ml is as water entrainer, add the sodium carbonate of 50mmol as catalyzer, add the N of 100ml, N-N,N-DIMETHYLACETAMIDE is as solvent, 140 DEG C of reaction 3h, after be warming up to 165 DEG C reaction 12h, polymers soln is poured in ethanolic soln and precipitates, with ethanol and deionized water repetitive scrubbing 3 times, at 80 DEG C, vacuum-drying 24h obtains white polymer resin CHPES, productive rate 90%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (31.86g), 1,2, in 2-tetrachloroethane, the N-bromo-succinimide adding 1.27g is as the benzoyl peroxide of bromizating agent and 0.086g as initiator, and bromination reaction 5h is carried out in lower 85 DEG C of nitrogen protection, pours in ethanolic soln and precipitate after cooling, with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, get the N-Methyl pyrrolidone that 0.5gBCHPES is dissolved in 4.5g in the there-necked flask of 50ml, form 10% solution, after add the N-Methylimidazole of 0.18mg, reaction overnight 24h at 50 DEG C, be coated on the clean sheet glass of prior leveling, dry at 50 DEG C, obtain described anion-exchange membrane, prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
The ionic conductivity of quaternized anion-exchange membrane prepared by the present embodiment is as shown in QCHPES-2 in Fig. 3, and when 30 DEG C, this film ionic conductivity is in deionized water 10.5mS/cm, reaches 26.5mS/cm when 80 DEG C.
Embodiment 3
By the cyclohexane monomer (formula 10) of 2mmol, the fragrant monomer C (formula 15) of the fragrant monomer A (formula 15) of the biphenol monomer B (formula 13) of 18mmol and the halogen atom-containing of 2mmol and the halogen atom-containing of 18mmol joins and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 20ml is as water entrainer, add the cesium carbonate of 50mmol as catalyzer, add the N of 100ml, dinethylformamide is as solvent, , 140 DEG C of reaction 3h, after be warming up to 150 DEG C reaction 16h, polymers soln is poured in ethanolic soln and precipitates, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, vacuum-drying 24h obtains white polymer resin CHPES, productive rate 94%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (24.70g), in 2-ethylene dichloride, the N-bromo-succinimide adding 1.27g as the benzoyl peroxide of bromizating agent and 0.086g as initiator, bromination reaction 6h is carried out in lower 80 DEG C of nitrogen protection, cool to pour in ethanolic soln and precipitate, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, get the tetramethylene sulfone that 0.5gBCHPES is dissolved in 4.5g in the there-necked flask of 50ml, form 10% solution, after add reaction overnight 24h at the 1,2 dimethylimidazole 50 DEG C of 0.2g, be coated on the clean sheet glass of prior leveling, dry at 50 DEG C, obtain described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
In Fig. 3, QCHPES-3 is the ionic conductance rate curve of quaternized anion-exchange membrane prepared by the present embodiment, and as can be seen from the figure, when 30 DEG C, this film ionic conductivity is in deionized water 11.2mS/cm, reaches 37.6mS/cm when 80 DEG C.
Embodiment 4
By the cyclohexane monomer (formula 17) of 10mmol, the biphenol monomer B (formula 20) of 10mmol, the fragrant monomer C (formula 14) of the fragrant monomer A (formula 14) of the halogen atom-containing of 10mmol and the halogen atom-containing of 10mmol joins and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 30ml is as water entrainer, add the salt of wormwood of 50mmol as catalyzer, add the tetramethylene sulfone of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C reaction 3h, be cooled to room temperature polymers soln is poured in ethanolic soln to precipitate, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, vacuum-drying 24h obtains white polymer resin CHPES, productive rate 93%, the hexanaphthene resin (CHPES) of 1g is dissolved in the tetracol phenixin of 20ml (31.9g), the N-bromo-succinimide adding 1.27g as the Diisopropyl azodicarboxylate of bromizating agent and 0.0583g as initiator, bromination reaction 8h is carried out in lower 75 DEG C of nitrogen protection, cool to pour in ethanol and precipitate, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, the brominated product BCHPES getting 0.5g is dissolved in the N of 4.5g, dinethylformamide forms 10% solution in the there-necked flask of 50ml, after add 0.17g pyridine at 50 DEG C, react 24h reaction overnight, be coated on the clean sheet glass of prior leveling, dry at 50 DEG C, obtain described anion-exchange membrane, prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
In Fig. 3, QCHPES-4 is the ionic conductance rate curve of quaternized anion-exchange membrane prepared by the present embodiment, as can be seen from the figure, this anion-exchange membrane specific conductivity in deionized water presents the trend of increase along with the rising of temperature, when 30 DEG C, this film ionic conductivity is in deionized water 33.8mS/cm, reaches 42.2mS/cm when 80 DEG C.
As shown in Figure 4, as can be seen from the figure, the fracture of anion-exchange membrane QCHPES-4 side base occurs in 261 DEG C to the thermostability of the anion-exchange membrane QCHPES-4 prepared in this embodiment, and main chain break occurs in 382 DEG C.
Embodiment 5
By the cyclohexane monomer (formula 18) of 15mmol, the biphenol monomer B (formula 21) of 5mmol, the fragrant monomer C (formula 15) of the fragrant monomer A (formula 15) of the halogen atom-containing of 15mmol and the halogen atom-containing of 5mmol joins and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 40ml is as water entrainer, add the sodium carbonate of 50mmol as catalyzer, add the N-Methyl pyrrolidone of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 200 DEG C reaction 5h, polymers soln is poured in ethanolic soln and precipitates, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, vacuum-drying 24h obtains white polymer resin CHPES, productive rate 95%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (31.86g), 1,2, in 2-tetrachloroethane, the N-bromo-succinimide adding 1.27g is as the benzoyl peroxide of bromizating agent and 0.086g as initiator, and bromination reaction 5h is carried out in lower 85 DEG C of nitrogen protection, cools to pour in ethanol and precipitates, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, the BCHPES getting 0.5g is dissolved in the N of 4.5g, N-N,N-DIMETHYLACETAMIDE forms 10% solution in the there-necked flask of 50ml, be coated on the clean sheet glass of prior leveling, dry at 50 DEG C, being taken off from sheet glass and steep 5g massfraction by film is in the trimethylamine solution of 30%, 50 DEG C of reaction 24h, obtain described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
In Fig. 3, QCHPES-4 is the ionic conductance rate curve of quaternized anion-exchange membrane prepared by the present embodiment, as can be seen from the figure, this anion-exchange membrane specific conductivity in deionized water presents the trend of increase along with the rising of temperature, when 30 DEG C, this film ionic conductivity is in deionized water 34.5mS/cm, reaches 73.3mS/cm when 80 DEG C.
As shown in Figure 4, as can be seen from the figure, the fracture of anion-exchange membrane QCHPES-5 side base occurs in 262 DEG C to the thermostability of the anion-exchange membrane QCHPES-5 prepared in this embodiment, and main chain break occurs in 380 DEG C.
Embodiment 6
By the cyclohexane monomer (formula 19) of 10mmol, the biphenol monomer B (formula 22) of 10mmol, the fragrant monomer C (formula 16) of the fragrant monomer A (formula 16) of the halogen atom-containing of 10mmol and the halogen atom-containing of 10mmol joins and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 30ml is as water entrainer, add the sodium carbonate of 50mmol as catalyzer, add the tetramethylene sulfone of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C reaction 3h, polymers soln is poured in ethanolic soln and precipitates, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, in vacuum drying oven, dry 24h obtains white polymer resin CHPES, productive rate 95%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (24.70g), in 2-ethylene dichloride, the C5H6Br2N2O2 adding 2.0304g as the benzoyl peroxide of bromizating agent and 0.086g as initiator, bromination reaction 6h is carried out in lower 80 DEG C of nitrogen protection, cool to pour in ethanol and precipitate, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, the brominated product BCHPES getting 0.5g is dissolved in the N of 4.5g, dinethylformamide forms 10% solution in the there-necked flask of 50ml, after add the guanidine 50 DEG C of 0.16g at react 24h reaction overnight, the clean sheet glass of prior leveling applies, dry at 50 DEG C, obtain described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
Embodiment 7
By the cyclohexane monomer (formula 10) of 5mmol, the fragrant monomer C (15) of the fragrant monomer A (formula 14) of the biphenol monomer B (formula 11) of 15mmol and the halogen atom-containing of 5mmol and the halogen atom-containing of 15mmol joins and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 40ml is as water entrainer, add the cesium carbonate of 50mmol as catalyzer, add the dimethyl sulfoxide (DMSO) of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 180 DEG C reaction 10h, polymers soln is poured in ethanol and precipitates, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, in vacuum drying oven, dry 24h obtains white polymer resin CHPES, productive rate 94%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (31.86g), 1,2, in 2-tetrachloroethane, the N-bromo-succinimide adding 1.27g is as the Diisopropyl azodicarboxylate of bromizating agent and 0.0583g as initiator, and bromination reaction 5h is carried out in lower 85 DEG C of nitrogen protection, cools to pour in ethanol and precipitates, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, the dimethyl sulfoxide (DMSO) that the BCHPES getting 0.5g is dissolved in 4.5g forms 10% solution in the there-necked flask of 50ml, after add reaction overnight 24h at the 1,2 dimethylimidazole 50 DEG C of 0.2g, the clean sheet glass of prior leveling applies, dry at 50 DEG C, obtain described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
Embodiment 8
By the cyclohexane monomer (formula 10) of 0.1mmol, the fragrant monomer C (formula 15) of the fragrant monomer A (formula 14) of the biphenol monomer B (formula 11) of 19.9mmol and the halogen atom-containing of 0.1mmol and the halogen atom-containing of 19.9mmol joins and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 30ml is as water entrainer, add the sodium carbonate of 50mmol as catalyzer, add the tetramethylene sulfone of 100ml as solvent, , 140 DEG C of reaction 3h, after be warming up to 210 DEG C reaction 3h, polymers soln is poured in ethanolic soln and precipitates, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, in vacuum drying oven, dry 24h obtains white polymer resin CHPES, productive rate 94%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (31.86g), 1,2, in 2-tetrachloroethane, add 1.27g N-bromo-succinimide as the benzoyl peroxide of bromizating agent and 0.086g as initiator, bromination reaction 5h is carried out in lower 85 DEG C of nitrogen protection, cools to pour in ethanol and precipitates, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, the brominated product BCHPES getting 0.5g is dissolved in the N of 4.5g, N-N,N-DIMETHYLACETAMIDE forms 10% solution in the there-necked flask of 50ml, after add 1 of 0.2g, reaction overnight 24h at 2-methylimidazole 50 DEG C, be coated on the clean sheet glass of prior leveling, dry at 50 DEG C, obtain described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
Embodiment 9
The fragrant monomer A (formula 14) of the cyclohexane monomer (formula 10) of 20mmol and the halogen atom-containing of 20mmol is joined and water trap is housed, in the there-necked flask of the 250ml of thermometer and import and export of nitrogen, the toluene of 30ml is as water entrainer, add the salt of wormwood of 50mmol as catalyzer, add the tetramethylene sulfone of 100ml as solvent, 140 DEG C of reaction 3h, after be warming up to 210 DEG C reaction 4h, polymers soln is poured in ethanol and precipitates, with deionized water and ethanolic soln repetitive scrubbing 3 times, at 80 DEG C, in vacuum drying oven, dry 24h obtains white polymer resin CHPES, productive rate 94%, the hexanaphthene resin (CHPES) of 1g is dissolved in 1 of 20ml (31.86g), 1,2, in 2-tetrachloroethane, the N-bromo-succinimide adding 1.27g is as the benzoyl peroxide of bromizating agent and 0.086g as initiator, and bromination reaction 5h is carried out in lower 85 DEG C of nitrogen protection, pours in ethanol and precipitate after cooling, and with ethanol repetitive scrubbing 3 times, 60 DEG C of vacuum-dryings obtain white fibrous product B CHPES, the N-Methyl pyrrolidone that the brominated product BCHPES getting 0.5g is dissolved in 4.5g forms 10% solution in the there-necked flask of 50ml, after add 1 of 0.2g, reaction overnight 24h at 2-methylimidazole 50 DEG C, be coated on the clean sheet glass of prior leveling, dry at 50 DEG C and take off from sheet glass, obtaining described anion-exchange membrane.Prepared anion-exchange membrane is assembled into respectively in alkaline polymer electrolyte fuel cell and all-vanadium flow battery, test correlated performance.
A kind of correlated performance that can be used for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell and all-vanadium flow battery of preparation in table 1, embodiment 1 ~ example 9:
Claims (10)
1. can be used for a polyethersulfone anion-exchange membrane for alkaline polymer electrolyte fuel cell, it is characterized in that the polyether compound containing hexanaphthene group and quaternary ammonium salt side as shown in formula I:
Wherein m and n represents the polymerization degree, m=1 ~ 200 and n=0 ~ 200,0<m/ (m+n)≤1, and the relative molecular weight of polymkeric substance is 10000 ~ 100000;
Described
with
the respective one be independently selected from formula (1) ~ formula (3):
Work as R
1=R
2during=H, described
be selected from formula (4) ~ formula (6) any one:
2. can be used for a polyethersulfone anion-exchange membrane for alkaline polymer electrolyte fuel cell, it is characterized in that the polyether compound containing hexanaphthene group and quaternary ammonium salt side as shown in formula I:
Wherein m and n represents the polymerization degree, m=1 ~ 200 and n=0 ~ 200,0<m/ (m+n)≤1, and the relative molecular weight of polymkeric substance is 10000 ~ 100000;
Described
with
respective be independently selected from formula (1) ~ formula (3) one or both:
Work as R
1=Q, R
2=H or R
1=H, R
2=Q or R
1=R
2during=Q, wherein Q=methyl or quaternary ammonium salt group, described
be selected from formula (7) ~ formula (9) any one:
3. a kind of polyethersulfone anion-exchange membrane that can be used for alkaline polymer electrolyte fuel cell as claimed in claim 2, it is characterized in that Q can be in several substituting group below any one:
Wherein X is the negatively charged ion of the negative valence charge of band, can be Br
-, Cl
-or OH
-.
4. can be used for a preparation method for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell, it is characterized in that the method comprises the following steps:
Step (1), by bisphenol cyclohexane monomer, fragrant monomer A containing halogen atom, catalyzer according to 1:1:(2.5 ~ 500) molar ratio join reaction vessel, then water entrainer and polar aprotic solvent p is added, after reacting 3h at 140 DEG C, be warming up to 150 ~ 210 DEG C of reaction 3 ~ 16h, aftertreatment obtains polyether compound CHPES; The volume ratio of described water entrainer and polar aprotic solvent p is (0.2 ~ 0.4): 1;
Step (2), the polyether compound CHPES of preparation in step (1) is dissolved in enpara kind solvent, then appropriate bromizating agent and initiator is added, carry out bromination reaction 5 ~ 8h at a certain temperature, aftertreatment obtains brominated product BCHPES; The mass ratio of described polyether compound CHPES, alkyl halide varsol, bromizating agent and initiator is 1:(24.70 ~ 31.90): (1.27 ~ 2.0304): (0.0583 ~ 0.086).
Step (3), brominated product BCHPES described in step (2) is dissolved in polar aprotic solvent q after, add quaternizing agent, reaction overnight 24h at 50 DEG C, obtains quaternized products QCHPES; The mass ratio of described brominated product BCHPES, polar aprotic solvent q and quaternizing agent is 1:9:(0.32 ~ 10).
Step (4), the quaternized products QCHPES obtained is coated in prior level-off clean sheet glass above, at 50 DEG C, dry 24h is to make solvent evaporates complete, is taken off by film, obtain described anion-exchange membrane above sheet glass.
5. a kind of preparation method that can be used for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell as claimed in claim 4, is characterized in that step (1) can also add biphenol monomer B and the fragrant monomer C containing halogen atom.
6. a kind of preparation method that can be used for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell as claimed in claim 5, is characterized in that bisphenol cyclohexane monomer, biphenol monomer B, the mol ratio of the fragrant monomer C containing halogen atom, the fragrant monomer A containing halogen atom and catalyzer is 1:(0.01 ~ 199): (0.01 ~ 199): 1:(2.5 ~ 500).
7. a kind of preparation method that can be used for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell as claimed in claim 6, is characterized in that working as R
1=R
2during=H:
The described biphenol monomer containing hexanaphthene has following structure:
Described have following structure containing biphenol monomer B:
wherein
be selected from formula (11) ~ formula (13) any one:
Described fragrant monomer A and C containing halogen atom has following structure:
Wherein
with
respective be independently selected from formula (14) ~ (16) any one:
8. a kind of preparation method that can be used for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell as claimed in claim 6, is characterized in that working as R
1=Q, R
2=H or R
1=H, R
2=Q or R
1=R
2during=Q:
Described cyclohexane monomer has as shown in the formula any one in (17) ~ formula (19) structure:
Described biphenol monomer B has following structure:
wherein
be selected from formula (20) ~ formula (22) any one:
Described fragrant monomer A and C containing halogen atom has following structure:
Wherein
with
respective be independently selected from formula (14) ~ (16) any one:
9. a kind of preparation method that can be used for the polyethersulfone anion-exchange membrane of alkaline polymer electrolyte fuel cell as claimed in claim 4, it is characterized in that the polar aprotic solvent q in the polar aprotic solvent p described in step (1), step (3) is independently N separately, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, tetramethylene sulfone, N-Methyl pyrrolidone, the one in dimethyl sulfoxide (DMSO);
Water entrainer described in step (1) is toluene;
Catalyzer described in step (1) is salt of wormwood, any one in sodium carbonate or cesium carbonate;
Polymeric reaction temperature described in step (1) is 150 ~ 210 DEG C;
Described in step (2), enpara kind solvent is sym.-tetrachloroethane, 1,2-ethylene dichloride, any one in tetracol phenixin;
Initiator described in step (2) is any one in benzoyl peroxide or Diisopropyl azodicarboxylate;
Bromizating agent described in step (2) is any one in N-bromo-succinimide or C5H6Br2N2O2;
Bromination reaction temperature described in step (2) is 75 ~ 85 DEG C;
Described in step (3), quaternizing agent is Trimethylamine 99, N-Methylimidazole, 1,2 dimethylimidazole, any one in pyridine and guanidine.
10. a kind of polyethersulfone anion-exchange membrane that can be used for alkaline polymer electrolyte fuel cell is applied in alkaline polymer electrolyte fuel cell and all-vanadium flow battery as claimed in claim 1 or 2.
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