CN112708157A - Alkaline anion exchange membrane for fuel cell and preparation method thereof - Google Patents
Alkaline anion exchange membrane for fuel cell and preparation method thereof Download PDFInfo
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- CN112708157A CN112708157A CN202110133147.8A CN202110133147A CN112708157A CN 112708157 A CN112708157 A CN 112708157A CN 202110133147 A CN202110133147 A CN 202110133147A CN 112708157 A CN112708157 A CN 112708157A
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000446 fuel Substances 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 10
- 230000031709 bromination Effects 0.000 claims abstract description 9
- 238000005893 bromination reaction Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Substances BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 20
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- -1 diethylene glycol monovinyl ether sodium Chemical compound 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- MICMHFIQSAMEJG-UHFFFAOYSA-N 1-bromopyrrolidine-2,5-dione Chemical compound BrN1C(=O)CCC1=O.BrN1C(=O)CCC1=O MICMHFIQSAMEJG-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012434 nucleophilic reagent Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- FGYADSCZTQOAFK-UHFFFAOYSA-N 1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C=NC2=C1 FGYADSCZTQOAFK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 229960001701 chloroform Drugs 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- MHFGGKKVDZSTKK-UHFFFAOYSA-N 4-methylphenol;sodium Chemical compound [Na].CC1=CC=C(O)C=C1 MHFGGKKVDZSTKK-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 239000012038 nucleophile Substances 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- ZECBPBHBGNLLMU-UHFFFAOYSA-M sodium;4-methylphenolate Chemical compound [Na+].CC1=CC=C([O-])C=C1 ZECBPBHBGNLLMU-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- NAVDBUWCGQBJMO-UHFFFAOYSA-N 1,2-dimethylimidazo[4,5-b]pyridine Chemical compound C1=CC=C2N(C)C(C)=NC2=N1 NAVDBUWCGQBJMO-UHFFFAOYSA-N 0.000 description 1
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers
- C08J2343/02—Homopolymers or copolymers of monomers containing phosphorus
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- 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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Abstract
The invention relates to an alkaline anion exchange membrane for a fuel cell and a preparation method thereof, wherein the membrane is prepared by the following steps: 1) reacting p-methyl phenol and diethylene glycol monovinyl ether with hexachlorocyclotriphosphazene HCCP according to a certain proportion; 2) copolymerizing the product obtained in the step 1) and styrene according to different feeding ratios; 3) NBS methyl bromination of the polymer of step 2) above; 4) quaternizing the polymer obtained in the step 3) by using tertiary amine, and then putting the polymer into a dilute sodium hydroxide solution for alkalization to obtain the alkaline anion exchange membrane. The method has the advantages that the main chain does not contain heteroatoms, the cyclotriphosphazene is grafted with high-density conduction sites, the alkali resistance and the conductivity are improved to a certain degree, the thermal stability is high, and the used raw materials are simple and easy to obtain and convenient to operate.
Description
Technical Field
The invention belongs to the field of alkaline anion exchange membranes, and relates to a method for preparing an anion exchange membrane by using hexachlorocyclotriphosphazene as a carrier, generating carbon-carbon double bond straight-chain alcohol and p-methylphenol co-substituted phosphazene through nucleophilic substitution reaction, polymerizing phosphazene containing carbon-carbon double bonds and styrene, and sequentially carrying out NBS bromination, tertiary amine quaternization and alkalization.
Background
Alkaline anion exchange membrane fuel cells, which are currently a device of general interest in countries around the world to convert chemical energy stored in a fuel such as hydrogen into electrical energy, are considered to be one of the most promising environmentally friendly chemical power sources to replace traditional energy sources. The alkaline anion exchange membrane is a key component of the fuel cell and plays a role in dividing a cathode electrode and an anode electrode and conducting hydroxide ions. The performance of the alkaline anion exchange membrane is therefore decisive for the performance of the fuel cell. The basic anion exchange membrane should have the following characteristics: high OH-Ion conductivity, excellent alkali resistance stability, mechanical property, good thermal stability and low cost, and can prevent fuel permeation. The alkaline anion exchange membrane is composed of a polymer main chain and OH-The conduction active point is formed, the commonly used main chain is polysulfone, polyethersulfone, polyetherketone and polyphenylether, and the main chain structure contains hetero atoms and is easy to be subjected to OH-Resulting in poor backbone stability, commonly used OH-The conductive active site is a cationic functional group such as quaternary ammonium salt, quaternary phosphonium salt and the like.
The phosphonitrile compound refers to various compounds containing phosphorus-nitrogen unsaturated bonds, Hexachlorocyclotriphosphazene (HCCP) is a common compound, and due to the fact that P-Cl chemical bonds of the phosphonitrile compound are very active, hexachlorocyclotriphosphazene is used as a raw material to react with a nucleophilic reagent, a plurality of cyclic phosphazene derivatives with different functions can be prepared, and the cyclic phosphazene derivatives can also be subjected to ring-opening polymerization to prepare linear polyphosphazene. Allcock has long proposed polyphosphazene backbones for use in polymer electrolytes. The main chain load of the polymer has high flexibility oligomeric ethylene oxide side group, is an amorphous polymer, and each repeating unit contains six oxygen atoms, so that the polymer is a good polymer electrolyte. By utilizing the hexachlorocyclotriphosphazene structure, functional sites with high substitution density for conducting ions can be synthesized, and the ionic conductivity can be improved.
Disclosure of Invention
The invention aims to provide a basic anion-exchange membrane and a preparation method thereof, and the preparation of the basic anion-exchange membrane relates to a method for preparing the anion-exchange membrane by taking hexachlorocyclotriphosphazene as a carrier, generating carbon-carbon double bond straight-chain alcohol and p-methylphenol co-substituted phosphazene through nucleophilic substitution reaction, polymerizing the phosphazene with the carbon-carbon double bond and styrene, and sequentially carrying out NBS (N-bromosuccinimide) bromination, tertiary amine quaternization and alkalization.
In order to achieve the purpose, the invention adopts the following scheme to realize the purpose:
an alkaline anion exchange membrane for a fuel cell and a preparation method thereof can be prepared according to the following processes:
1) phosphazene substitution reaction: and (2) putting the sodium metal oxide with the surface removed into 2 flasks, adding anhydrous tetrahydrofuran THF, introducing nitrogen, slowly dripping an anhydrous THF solution of p-methylphenol and diethylene glycol monovinyl ether into the 2 flasks, carrying out reflux reaction for 8 hours, and obtaining the nucleophilic reagent of the p-methylphenol sodium and the diethylene glycol monovinyl ether sodium after the reaction is finished. Weighing hexachlorocyclotriphosphazene HCCP (hydrochloric acid phosphate) which is one fifth of the molar weight of p-methylphenol sodium, putting the hexachlorocyclotriphosphazene HCCP into a flask, adding anhydrous THF (tetrahydrofuran) to dissolve the HCCP, slowly dripping the p-methylphenol sodium reagent into the flask under the condition of nitrogen, and reacting for 12 hours after dripping. And slowly dropping a diethylene glycol monovinyl ether sodium reagent into the flask to replace the residual P-Cl, and reacting for 16 hours after the dropping is finished. After the reaction is finished, filtering, carrying out rotary evaporation to remove THF, dissolving the product in chloroform, washing with a large amount of deionized water, drying with anhydrous sodium sulfate, and carrying out rotary evaporation to remove chloroform to obtain a product I;
2) polymer preparation: under the protection of nitrogen, dissolving styrene and a product I in anhydrous chlorobenzene, adding an initiator AIBN with the weight ratio of 2%, magnetically stirring, carrying out reflux reaction at 70 ℃ for 24 hours, cooling, pouring a reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer again with ethanol, separating out the polymer with the petroleum ether, repeating the reaction for 2 times, and drying in vacuum to obtain a copolymer II;
3) NBS bromination: under the protection of nitrogen, adding AIBN and N-bromosuccinimide NBS into an anhydrous chlorobenzene solvent containing a copolymer II, heating and refluxing for 12 hours, concentrating, washing with a large amount of ethanol, filtering, and drying to obtain a brominated polymer III;
4) quaternization of the polymer: under the protection of nitrogen, dissolving the polymer III in a solvent DMF, adding a certain amount of tertiary amine, magnetically stirring, refluxing at 30-65 ℃, reacting for 24 hours, then paving the mixed solution on a glass plate, putting the glass plate into a vacuum oven to dry the solvent to obtain an anion exchange membrane, stripping the anion exchange membrane, and soaking in 1M sodium hydroxide solution at room temperature for 48 hours to obtain the alkaline anion exchange membrane.
Preferably, the molar ratio of the p-methylphenol, the hexachlorocyclotriphosphazene and the diethylene glycol monovinyl ether in the step 1) is 1:0.2 (0.2-0.3).
Preferably, the molar ratio of the p-methylphenol to the sodium in the step 1) is 1 (1.01-1.2), and the molar ratio of the diethylene glycol monovinyl ether to the sodium is 1 (1.01-1.2).
Preferably, the molar ratio of the styrene to the product I in the step 2) is 1 (0.1-3).
Preferably, the molar ratio of the copolymer II, NBS and AIBN in the step 3) is 1 (0.1-4) to (0.03-0.2).
Preferably, the molar ratio of the copolymer III to the tertiary amine in the step 4) is 1 (0.1-4).
Preferably, the tertiary amine in step 4) is trimethylamine, triethylamine, 1-methylimidazole, 1, 2-dimethylimidazopyridine, N-methylpiperidine, N-methylbenzimidazole.
Due to the application of the technical scheme, the invention has the following beneficial effects:
the invention provides a preparation method of an alkaline anion exchange membrane, which relates to a preparation method of the alkaline anion exchange membrane by taking hexachlorocyclotriphosphazene as a carrier, generating carbon-carbon double bond straight-chain alcohol and p-methylphenol co-substituted phosphazene through nucleophilic substitution reaction, polymerizing the phosphazene with the carbon-carbon double bond and styrene, and carrying out NBS bromination, tertiary amine quaternization and alkalization in sequence. The main chain of the method does not contain heteroatoms such as polysulfone, polyethersulfone, polyetherketone, polyphenylene ether chain and the like, and is not easy to be subjected to OH-The alkali resistance is improved to a certain extent, and the cyclotriphosphazene can be grafted with high-density conductive OH-The site and the conductivity are correspondingly improved, the thermal stability is high, and the used raw materials are simple and easy to obtain and convenient to operate.
Drawings
FIG. 1 is a graph of performance data for anion exchange membranes obtained in examples 1-3 of the present invention.
Detailed Description
Example 1
1) Phosphazene substitution reaction: and (3) placing 12.6g of sodium metal oxide with the surface removed into a flask, adding anhydrous Tetrahydrofuran (THF), introducing nitrogen, slowly dripping 54g of anhydrous THF solution of p-methylphenol into the flask, carrying out reflux reaction for 8 hours, and obtaining the p-methylphenol sodium nucleophile after the reaction is finished. And 3.04g of metal sodium is put into a flask, anhydrous tetrahydrofuran THF is added, nitrogen is introduced, 15.8g of anhydrous THF solution of diethylene glycol monovinyl ether is slowly dripped into the flask, reflux reaction is carried out for 8 hours, and the diethylene glycol monovinyl ether sodium nucleophile is obtained after the reaction is finished. 34.76g of hexachlorocyclotriphosphazene HCCP is weighed and placed into a flask, anhydrous THF is added to dissolve the hexachlorocyclotriphosphazene HCCP, a sodium p-methylphenolate reagent is slowly dripped into the flask under the condition of nitrogen, and the reaction lasts for 12 hours after the dripping. And slowly dropping a diethylene glycol monovinyl ether sodium reagent into the flask to replace the residual P-Cl, and reacting for 16 hours after the dropping is finished. After the reaction is finished, filtering, carrying out rotary evaporation to remove THF, dissolving the product in chloroform, washing with a large amount of deionized water, drying with anhydrous sodium sulfate, and carrying out rotary evaporation to remove chloroform to obtain a product I;
2) polymer preparation: under the protection of nitrogen, dissolving 10.4g of styrene and 80g of product I in anhydrous chlorobenzene, adding an initiator AIBN with the weight ratio of 2%, magnetically stirring, carrying out reflux reaction at 70 ℃ for 24 hours, cooling, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer again in ethanol, separating out the polymer by using the petroleum ether, repeating the reaction for 2 times, and drying in vacuum to obtain a copolymer II;
3) NBS bromination: under the protection of nitrogen, adding 1.64g of AIBN and 26.7g of N-bromosuccinimide NBS into an anhydrous chlorobenzene solvent containing 45.2g of copolymer II, heating and refluxing for reaction for 12 hours, concentrating, washing with a large amount of ethanol, filtering, and drying to obtain a brominated polymer III;
4) quaternization of the polymer: under the protection of nitrogen, 56g of polymer III is dissolved in a solvent DMF, 9g of trimethylamine is added, the mixture is magnetically stirred and is subjected to reflux reaction at room temperature for 24 hours, then the mixed solution is laid on a glass plate, the glass plate is placed in a vacuum oven to dry the solvent to obtain an anion exchange membrane, the anion exchange membrane is stripped out and is placed in a 1M sodium hydroxide solution at room temperature for soaking for 48 hours to obtain the alkaline anion exchange membrane.
Example 2
1) Phosphazene substitution reaction: and (3) placing 12.6g of sodium metal oxide with the surface removed into a flask, adding anhydrous Tetrahydrofuran (THF), introducing nitrogen, slowly dripping 54g of anhydrous THF solution of p-methylphenol into the flask, carrying out reflux reaction for 8 hours, and obtaining the p-methylphenol sodium nucleophile after the reaction is finished. And 3.04g of metal sodium is put into a flask, anhydrous tetrahydrofuran THF is added, nitrogen is introduced, 15.8g of anhydrous THF solution of diethylene glycol monovinyl ether is slowly dripped into the flask, reflux reaction is carried out for 8 hours, and the diethylene glycol monovinyl ether sodium nucleophile is obtained after the reaction is finished. 34.76g of hexachlorocyclotriphosphazene HCCP is weighed and placed into a flask, anhydrous THF is added to dissolve the hexachlorocyclotriphosphazene HCCP, a sodium p-methylphenolate reagent is slowly dripped into the flask under the condition of nitrogen, and the reaction lasts for 12 hours after the dripping. And slowly dropping a diethylene glycol monovinyl ether sodium reagent into the flask to replace the residual P-Cl, and reacting for 16 hours after the dropping is finished. After the reaction is finished, filtering, carrying out rotary evaporation to remove THF, dissolving the product in chloroform, washing with a large amount of deionized water, drying with anhydrous sodium sulfate, and carrying out rotary evaporation to remove chloroform to obtain a product I;
2) polymer preparation: under the protection of nitrogen, dissolving 10.4g of styrene and 80g of product I in anhydrous chlorobenzene, adding an initiator AIBN with the weight ratio of 2%, magnetically stirring, carrying out reflux reaction at 70 ℃ for 24 hours, cooling, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer again in ethanol, separating out the polymer by using the petroleum ether, repeating the reaction for 2 times, and drying in vacuum to obtain a copolymer II;
3) NBS bromination: under the protection of nitrogen, adding 1.64g of AIBN and 26.7g of N-bromosuccinimide NBS into an anhydrous chlorobenzene solvent containing 45.2g of copolymer II, heating and refluxing for reaction for 12 hours, concentrating, washing with a large amount of ethanol, filtering, and drying to obtain a brominated polymer III;
4) quaternization of the polymer: under the protection of nitrogen, 56g of polymer III is dissolved in a solvent DMF, 12.5g of 1-methylimidazole is added, magnetic stirring is carried out, reflux is carried out at 65 ℃, reaction is carried out for 24 hours, then the mixed solution is paved on a glass plate, the mixed solution is placed in a vacuum oven to dry the solvent, an anion exchange membrane is obtained, the anion exchange membrane is stripped out, and the anion exchange membrane is placed in a 1M sodium hydroxide solution at room temperature to be soaked for 48 hours, so that the alkaline anion exchange membrane is obtained.
Example 3
1) Phosphazene substitution reaction: and (3) placing 12.6g of sodium metal oxide with the surface removed into a flask, adding anhydrous Tetrahydrofuran (THF), introducing nitrogen, slowly dripping 54g of anhydrous THF solution of p-methylphenol into the flask, carrying out reflux reaction for 8 hours, and obtaining the p-methylphenol sodium nucleophile after the reaction is finished. And 3.04g of metal sodium is put into a flask, anhydrous tetrahydrofuran THF is added, nitrogen is introduced, 15.8g of anhydrous THF solution of diethylene glycol monovinyl ether is slowly dripped into the flask, reflux reaction is carried out for 8 hours, and the diethylene glycol monovinyl ether sodium nucleophile is obtained after the reaction is finished. 34.76g of hexachlorocyclotriphosphazene HCCP is weighed and placed into a flask, anhydrous THF is added to dissolve the hexachlorocyclotriphosphazene HCCP, a sodium p-methylphenolate reagent is slowly dripped into the flask under the condition of nitrogen, and the reaction lasts for 12 hours after the dripping. And slowly dropping a diethylene glycol monovinyl ether sodium reagent into the flask to replace the residual P-Cl, and reacting for 16 hours after the dropping is finished. After the reaction is finished, filtering, carrying out rotary evaporation to remove THF, dissolving the product in chloroform, washing with a large amount of deionized water, drying with anhydrous sodium sulfate, and carrying out rotary evaporation to remove chloroform to obtain a product I;
2) polymer preparation: under the protection of nitrogen, dissolving 10.4g of styrene and 80g of product I in anhydrous chlorobenzene, adding an initiator AIBN with the weight ratio of 2%, magnetically stirring, carrying out reflux reaction at 70 ℃ for 24 hours, cooling, pouring the reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer again in ethanol, separating out the polymer by using the petroleum ether, repeating the reaction for 2 times, and drying in vacuum to obtain a copolymer II;
3) NBS bromination: under the protection of nitrogen, adding 1.64g of AIBN and 26.7g of N-bromosuccinimide NBS into an anhydrous chlorobenzene solvent containing 45.2g of copolymer II, heating and refluxing for reaction for 12 hours, concentrating, washing with a large amount of ethanol, filtering, and drying to obtain a brominated polymer III;
4) quaternization of the polymer: under the protection of nitrogen, 56g of polymer III is dissolved in a solvent DMF, 15.5g of 1-methylpiperidine is added, magnetic stirring is carried out, reflux is carried out at 65 ℃, reaction is carried out for 24h, then a mixed solution is paved on a glass plate, the mixed solution is placed in a vacuum oven to dry the solvent, an anion exchange membrane is obtained, the anion exchange membrane is stripped out and is placed in a 1M sodium hydroxide solution at room temperature to be soaked for 48h, and the alkaline anion exchange membrane is obtained.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and it will be apparent to those skilled in the art that the present invention may be modified and varied in various ways. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An alkaline anion exchange membrane for a fuel cell and a preparation method thereof are characterized by comprising the following steps:
1) phosphazene substitution reaction: putting the surface oxide-removed metal sodium into 2 flasks, adding anhydrous tetrahydrofuran THF, introducing nitrogen, slowly dripping an anhydrous THF solution of P-methylphenol and diethylene glycol monovinyl ether into the 2 flasks, carrying out reflux reaction for 8h, obtaining a nucleophilic reagent of P-methylphenol sodium and diethylene glycol monovinyl ether sodium after the reaction is finished, weighing hexachlorocyclotriphosphazene HCCP of one fifth of the molar weight of the P-methylphenol sodium, putting the HCCP into the flasks, adding anhydrous THF to dissolve the anhydrous THF, slowly dripping a P-methylphenol sodium reagent into the flasks under the nitrogen condition, reacting for 12h after the dripping is finished, slowly dripping a diethylene glycol monovinyl ether sodium reagent into the flasks to replace the residual P-Cl, reacting for 16h after the dripping is finished, filtering, carrying out rotary evaporation to remove the THF, dissolving the product into trichloromethane, washing with a large amount of deionized water, drying the product with anhydrous sodium sulfate, and removing trichloromethane by rotary evaporation to obtain a product I;
2) polymer preparation: under the protection of nitrogen, dissolving styrene and a product I in anhydrous chlorobenzene, adding an initiator AIBN with the weight ratio of 2%, magnetically stirring, carrying out reflux reaction at 70 ℃ for 24 hours, cooling, pouring a reaction mixed solution into petroleum ether to separate out a polymer, dissolving the polymer again with ethanol, separating out the polymer with the petroleum ether, repeating the reaction for 2 times, and drying in vacuum to obtain a copolymer II;
3) NBS bromination: under the protection of nitrogen, adding AIBN and N-bromosuccinimide NBS into an anhydrous chlorobenzene solvent containing a copolymer II, heating and refluxing for 12 hours, concentrating, washing with a large amount of ethanol, filtering, and drying to obtain a brominated polymer III;
4) quaternization of the polymer: under the protection of nitrogen, dissolving the polymer III in a solvent DMF, adding a certain amount of tertiary amine, magnetically stirring, refluxing at 30-65 ℃, reacting for 24 hours, then paving the mixed solution on a glass plate, putting the glass plate into a vacuum oven to dry the solvent to obtain an anion exchange membrane, stripping the anion exchange membrane, and soaking in 1M sodium hydroxide solution at room temperature for 48 hours to obtain the alkaline anion exchange membrane.
2. The method for preparing a basic anion-exchange membrane according to claim 1, wherein the step 1) is performed by
The molar ratio of the p-methylphenol, the hexachlorocyclotriphosphazene and the diethylene glycol monovinyl ether is 1:0.2 (0.2-0.3).
3. The method for preparing a basic anion-exchange membrane according to claim 1, wherein the step 1) is performed by
The molar ratio of p-methylphenol to sodium is 1 (1.01-1.2), the molar ratio of diethylene glycol monovinyl ether to sodium is 1: (1.01-1.2).
4. The method for preparing the basic anion-exchange membrane according to claim 1, wherein the step 2) is performed by
The molar ratio of the styrene to the product I is 1 (0.1-3).
5. The method for preparing a basic anion-exchange membrane according to claim 1, wherein the step 3) is performed by
The molar ratio of the copolymer II to the NBS to the AIBN is 1 (0.1-4) to 0.03-0.2.
6. The method for preparing the basic anion-exchange membrane according to claim 1, wherein the step 4) is performed by
The molar ratio of the copolymer III to the tertiary amine is 1 (0.1-4).
7. The method for preparing the basic anion-exchange membrane according to claim 1, wherein the step 4) is performed by
The tertiary amine is one or more of trimethylamine, triethylamine, 1-methylimidazole, pyridine, N-methylpiperidine, N-methylbenzimidazole and the like.
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| US4657993A (en) * | 1985-02-11 | 1987-04-14 | Consiglio Nazionale Delle Ricerche | Phosphazene homopolymers and copolymers having hydroxylated or amino derivatives of carbazole or of naphthalene as substituents |
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