CN110041519B - Long-chain branch poly (arylene ether nitrile) anion exchange membrane and preparation method thereof - Google Patents
Long-chain branch poly (arylene ether nitrile) anion exchange membrane and preparation method thereof Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 46
- -1 poly (arylene ether nitrile Chemical class 0.000 title claims abstract description 46
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000005266 casting Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000001226 reprecipitation Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 4
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 2
- 229920000412 polyarylene Polymers 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 24
- 239000000446 fuel Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000090 poly(aryl ether) Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- JQKHNBQZGUKYPX-UHFFFAOYSA-N tris(2,4,6-trimethoxyphenyl)phosphane Chemical compound COC1=CC(OC)=CC(OC)=C1P(C=1C(=CC(OC)=CC=1OC)OC)C1=C(OC)C=C(OC)C=C1OC JQKHNBQZGUKYPX-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
-
- 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
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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
- C08J5/2287—After-treatment
- C08J5/2293—After-treatment of fluorine-containing membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
-
- 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
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of alkaline anion exchange membranes, and relates to a long-chain branched poly (arylene ether nitrile) anion exchange membrane and a preparation method thereof. The prepared membrane not only has higher ionic conductivity, but also keeps good dimensional stability, and can be applied to alkaline fuel cells.
Description
Technical Field
The invention belongs to the technical field of alkaline anion exchange membranes, and relates to a long-chain branched poly (arylene ether nitrile) anion exchange membrane and a preparation method thereof.
Background
With the increasing energy crisis and the worsening global environmental pollution, the development of clean and efficient new energy utilization by human beings is urgent. Fuel cells have attracted attention of many researchers in recent years due to their high energy conversion efficiency, environmental friendliness, and the like. The proton exchange membrane fuel cell has been developed greatly in recent years by virtue of its excellent performance, but the proton exchange membrane fuel cell greatly increases the production cost of the fuel cell and seriously hinders the development of the proton exchange membrane fuel cell because noble metal platinum is used as a catalyst. Compared with proton exchange membrane fuel cells, alkaline anion exchange membrane fuel cells have similar working principles, but can allow the use of fewer catalysts or non-noble metal catalysts under alkaline conditions, so that the cost is greatly reduced, and therefore, the alkaline anion exchange membrane fuel cells gradually become a hotspot of research in the field of fuel cells.
As a core component of an alkaline anion exchange membrane fuel cell, the alkaline anion exchange membrane has a shallower research than a proton exchange membrane, and has the following problems: low hydroxide ion conductivity, poor membrane dimensional stability, low alkaline stability, and the like. In order to improve the hydroxide conductivity of the basic anion-exchange membrane, long-chain branches can be introduced into the membrane structure, and partial research shows that the anion-exchange membrane with longer chain branches has more excellent performance in ion conductivity compared with the anion-exchange membrane with short chain branches. In order to improve the dimensional stability of the membrane, a crosslinking method is generally adopted, however, the crosslinking causes poor solubility of the product in an organic solvent, and is not beneficial to the preparation of the membrane. It has been shown that the introduction of cyano groups into the main chain of the film reduces the degree of water swelling of the film without sacrificing the solubility of the product.
Therefore, in order to simultaneously solve the problems of low hydroxide ion conductivity and poor membrane dimensional stability in the preparation of the existing anion exchange membrane material, the invention introduces cyano groups into the membrane, inhibits membrane swelling through enhanced intermolecular interaction and does not sacrifice membrane solubility on the other hand. In addition, a long branched chain structure is introduced by taking amino as a site on a polymer skeleton with nitrile groups, so that the microphase separation of hydrophilic-hydrophobic parts is further promoted, the generation of ion clusters is promoted, and a penetrating ion transmission channel is formed, so that the ion-conducting polymer has high ion conductivity and wide application prospect of fuel cells.
Disclosure of Invention
The invention aims to improve the hydroxide ion conductivity of an alkaline anion-exchange membrane and ensure the dimensional stability of the alkaline anion-exchange membrane, and provides a preparation method of a long side chain poly (arylene ether nitrile) anion-exchange membrane, which comprises the following steps: the poly (arylene ether nitrile) polymer with good solubility is successfully synthesized through polycondensation, then the long branched chain structure is introduced into the polymer by directly taking the amido of the polymer as a grafting site, and finally functionalization is carried out, so that a membrane material with a good ion conduction path is obtained, and finally a membrane is formed through a casting method. The prepared membrane not only has higher ionic conductivity, but also keeps good dimensional stability, and can be applied to alkaline fuel cells.
The technical scheme of the invention is as follows:
a long-chain branched poly (arylene ether nitrile) anion exchange membrane has the following structure:
wherein: x is 0-0.9, and y is 1-0.1; n is an integer of 1-16;
r is an introduced functional group and is one of N-methylpyrrolidine, N-methylmorpholine, N-methylpiperidine, 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole, trimethylamine, triethylamine, tris (2,4, 6-trimethoxyphenyl) phosphine, pyridine and guanidine.
The preparation method of the long-chain branched poly (arylene ether nitrile) anion exchange membrane comprises the following steps:
(1) and (3) synthesis of poly (arylene ether nitrile):
dissolving 2, 6-difluorobenzonitrile, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and potassium carbonate in a solvent A to prepare a solution with the mass concentration of 150-400 g/L, adding toluene in an amount which is 0.5-1.5 times the volume of the solvent A, condensing and refluxing for 3-12 h at 120-150 ℃ in a protective gas atmosphere until water and toluene are completely removed, and then heating to 160 ℃ to react for 12-20 h; pouring the obtained solution into a precipitator A under vigorous stirring to precipitate a white filamentous product, then carrying out re-precipitation operation to further improve the purity of the product, namely re-dissolving the obtained filamentous product into the solvent A to prepare a solution with the mass concentration of 100-350 g/L, then carrying out re-precipitation on the solution by the precipitator A, repeating the re-precipitation operation for about 2-5 times, and finally carrying out vacuum drying to obtain the poly (arylene ether nitrile);
the content of the 2,6 difluorobenzonitrile: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane: hexafluorobisphenol a: the molar ratio of potassium carbonate is 10: 10-1: 15;
dissolving 2, 6-difluorobenzonitrile, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, hexafluorobisphenol a and potassium carbonate in a solvent a, and adding hexafluorobisphenol a while controlling the molar ratio of 2, 6-difluorobenzonitrile to hexafluorobisphenol a to not less than 10: 9.
the solvent A is one of N, N-dimethylacetamide and N-methylpyrrolidone;
the precipitant A is one of methanol, ethanol and water;
the temperature of the poly (arylene ether nitrile) vacuum drying is 30-100 ℃, and the time is more than 6 hours;
(2) preparing a long-chain branched poly (arylene ether nitrile) anion exchange membrane:
preparing a poly (arylene ether nitrile)/solvent B solution with the mass concentration of 30-100 g/L, adding NaH under the protection of inert gas, reacting for 2-8 h at 20-60 ℃, adding a monomer A containing a fatty chain, and reacting for 12-48 h at 40-80 ℃; pouring the reaction solution into a precipitator B under rapid stirring, repeatedly washing and drying by using a solvent C, dissolving the product in the solvent B to prepare a solution with the mass concentration of 50g/L, adding a certain amount of ionizing reagent, and reacting for 48-72 h at the temperature of 80-120 ℃ to obtain a casting solution; spreading a film on a clean glass plate by using a casting method for the film casting solution, drying, then taking off the film from the glass plate, soaking the film in a solvent D for 24-48 h to remove anions from Cl-Conversion to OH-And repeatedly washing with deionized water to remove residual alkali liquor, thus obtaining the long-chain branched poly (arylene ether nitrile) anion exchange membrane.
The solvent B is one of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the amount of the added substances of the NaH is 2-6 times of the amount of the substances of the amido substituted repeating units in the poly (arylene ether nitrile);
the structure of the monomer A containing the fatty chain is Cl- (CH)2)n-Br, added in a quantity of substance 1.5 to 3 times the quantity of substance of NaH; wherein n is a positive integer of 1-16;
the precipitant B is one of acetone, ethyl acetate and ethanol;
the solvent C is one of methanol, ethanol and water;
the product is repeatedly washed by the solvent C for 3-5 times;
the temperature required in the drying step after the product is repeatedly filtered and washed by the solvent C is 40-100 ℃, and the time is more than 8 hours;
the ionizing reagent is one of N-methylpyrrolidine, N-methylmorpholine, N-methylpiperidine, 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole, trimethylamine, triethylamine, tris (2,4, 6-trimethoxyphenyl) phosphine, pyridine and guanidine;
the amount of substances added into the ionizing reagent is 1.5-3 times of the amount of substances of the monomer A containing the fatty chain;
the solvent D is one of KOH and NaOH;
the number of times of repeatedly washing the membrane by the deionized water is 3-5;
the drying temperature of the film formed by the casting method is 50-80 ℃, and the time is 24-48 hours; the thickness of the film formed by the casting method is within the range of 30-60 mu m.
The invention has the beneficial effects that:
(1) due to the existence of nitrile groups in the ion side chain poly (arylene ether nitrile) anion exchange membrane, the membrane swelling can be effectively inhibited by enhancing the dipole-dipole intermolecular interaction.
(2) The long branched chain structure can improve the mobility of the branched chain, effectively promote the microphase separation of hydrophilic and hydrophobic phases in the membrane, and better form an ion transmission channel, thereby improving the conductivity.
(3) The ion exchange capacity of the anionic membrane can be achieved by preparing poly (arylene ether nitriles) with different degrees of amino substitution.
(4) The poly (arylene ether nitrile) has good solubility in various solvents, and the solvent selection range is wide.
(5) The amido in the amido substituted poly (arylene ether nitrile) can be directly used as a functional reaction site, and the reaction step is simple.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Synthesis of Polyarylethernitrile 1.4050g (10mmol) of 2, 6-difluorobenzonitrile, 0.7475g (2mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2.7447g (8mmol) of hexafluorobisphenol A and 1.3961g (10mmol) of potassium carbonate were placed in a 50mL three-necked flask, a mixed solution of 5mL of toluene and 9mL of N, N-dimethylacetamide was added thereto, the temperature was gradually raised to 140 ℃ under a protective gas atmosphere, the mixture was cooled and refluxed for about 4 hours until water was completely removed, and then the temperature was raised to 160 ℃ and reacted for about 15 hours. Slowly pouring the product into ethanol solution under mechanical stirring after the reaction is finished, separating out a filamentous polymer product, then further improving the purity of the product, carrying out re-separation operation, namely re-dissolving the obtained filamentous product into N, N-dimethylacetamide to prepare a solution with the mass concentration of 100g/L, then separating out the solution again through the ethanol solution, repeating the re-separation operation for about 3 times, and finally carrying out vacuum drying to obtain the polyarylether nitrile;
the preparation of the long-chain branched poly (arylene ether nitrile) anion exchange membrane comprises the steps of weighing 0.4g of poly (arylene ether nitrile) product obtained in the previous step under the protection of nitrogen, adding the poly (arylene ether nitrile) product into a 50mL single-neck flask, dissolving the poly (arylene ether nitrile) product with 10mL of N, N-dimethylacetamide, adding 0.02172g of NaH after the polymer is fully dissolved, reacting the reaction system at 60 ℃ for 5h, then adding 0.1653mL of 1, 6-dibromohexane, and reacting the system at 60 ℃ for 48 h. After the reaction is finished, the product is precipitated by ethanol, repeatedly washed and dried to obtain a white powder product, then the white powder product is dissolved by 8ml of N-methylpyrrolidone, namely the solution with the mass concentration of 50g/L is prepared, 1ml of N-methylpiperidine is added, and the reaction system reacts for 3 days at the temperature of 100 ℃. And obtaining the casting solution. Then casting the casting solution to form a film; finally, the membrane was soaked in 1M KOH solution for 36h to remove anions from Cl-Conversion to OH-. And finally, repeatedly washing with deionized water to remove residual alkali, thereby obtaining the long-chain branched poly (arylene ether nitrile) anion exchange membrane.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the ion conductivity of the long-chain branched poly (arylene ether nitrile) anion-exchange membrane prepared in the embodiment at 20 ℃ is 19mS cm-1The water absorption rate is 35 percent, the swelling degree is 16 percent, the film is not degraded after being soaked in 1mol/L KOH solution for 500 hours at the temperature of 60 ℃, and the film shows more excellent performance.
Example 2
Synthesis of Polyarylethernitrile 1.4050g (10mmol) of 2, 6-difluorobenzonitrile, 0.7475g (2mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2.7447g (8mmol) of hexafluorobisphenol A and 1.3961g (10mmol) of potassium carbonate were placed in a 50mL three-necked flask, a mixed solution of 5mL of toluene and 9mL of N, N-dimethylacetamide was added thereto, the temperature was gradually raised to 140 ℃ under a protective gas atmosphere, the mixture was cooled and refluxed for about 4 hours until water was completely removed, and then the temperature was raised to 160 ℃ and reacted for about 15 hours. Slowly pouring the product into ethanol solution under mechanical stirring after the reaction is finished, separating out a filamentous polymer product, then further improving the purity of the product, carrying out re-separation operation, namely re-dissolving the obtained filamentous product into N, N-dimethylacetamide to prepare a solution with the mass concentration of 100g/L, then separating out the solution again through the ethanol solution, repeating the re-separation operation for about 3 times, and finally carrying out vacuum drying to obtain the polyarylether nitrile;
the preparation of the long-chain branched poly (arylene ether nitrile) anion exchange membrane comprises the steps of weighing 0.4g of poly (arylene ether nitrile) product obtained in the previous step under the protection of nitrogen, adding the poly (arylene ether nitrile) product into a 50mL single-neck flask, dissolving the poly (arylene ether nitrile) product with 10mL of N, N-dimethylacetamide, adding 0.02172g of NaH after the polymer is fully dissolved, reacting the reaction system at 60 ℃ for 5h, then adding 0.2050mL of 1, 10-dibromohexane, and reacting the system at 60 ℃ for 48 h. After the reaction is finished, the product is precipitated by ethanol, repeatedly washed and dried to obtain a white powder product, then the white powder product is dissolved by 8ml of N-methylpyrrolidone, namely the solution with the mass concentration of 50g/L is prepared, 1ml of N-methylpiperidine is added, and the reaction system reacts for 3 days at the temperature of 100 ℃. And obtaining the casting solution.Then casting the casting solution to form a film; finally, the membrane was soaked in 1M KOH solution for 36h to remove anions from Cl-Conversion to OH-. And finally, repeatedly washing with deionized water to remove residual alkali, thereby obtaining the long-chain branched poly (arylene ether nitrile) anion exchange membrane.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the ion conductivity of the long-chain branched poly (arylene ether nitrile) anion-exchange membrane prepared in the embodiment at 20 ℃ is 16mS cm-1The water absorption rate is 33 percent, the swelling degree is 13 percent, the film is not degraded after being soaked in 1mol/L KOH solution for 500 hours at the temperature of 60 ℃, and the film shows more excellent performance.
Example 3
Synthesis of Polyarylethernitrile 1.4050g (10mmol) of 2, 6-difluorobenzonitrile, 1.495g (4mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2.0585g (6mmol) of hexafluorobisphenol A and 1.3961g (10mmol) of potassium carbonate were placed in a 50mL three-necked flask, a mixed solution of 5mL of toluene and 9mL of N, N-dimethylacetamide was added thereto, the temperature was gradually raised to 140 ℃ under a protective gas atmosphere, and after cooling and refluxing for about 4 hours, water was completely removed, and then the temperature was raised to 160 ℃ and reacted for about 15 hours. Slowly pouring the product into ethanol solution under mechanical stirring after the reaction is finished, separating out a filamentous polymer product, then further improving the purity of the product, carrying out re-separation operation, namely re-dissolving the obtained filamentous product into N, N-dimethylacetamide to prepare a solution with the mass concentration of 100g/L, then separating out the solution again through the ethanol solution, repeating the re-separation operation for about 3 times, and finally carrying out vacuum drying to obtain the polyarylether nitrile;
the preparation of the long-chain branched poly (arylene ether nitrile) anion exchange membrane comprises the steps of weighing 0.4g of poly (arylene ether nitrile) product obtained in the previous step under the protection of nitrogen, adding the poly (arylene ether nitrile) product into a 50mL single-neck flask, dissolving the poly (arylene ether nitrile) product with 10mL of N, N-dimethylacetamide, adding 0.04344g of NaH after the polymer is fully dissolved, reacting the reaction system at 60 ℃ for 5 hours, and then adding 0.3306m of NaHl of 1, 6-dibromohexane, and reacting the system at 60 ℃ for 48 hours. After the reaction is finished, the product is precipitated by ethanol, repeatedly washed and dried to obtain a white powder product, then the white powder product is dissolved by 8ml of N-methylpyrrolidone, namely the solution with the mass concentration of 50g/L is prepared, 2ml of N-methylpiperidine is added, and the reaction system reacts for 3 days at the temperature of 100 ℃. And obtaining the casting solution. Then casting the casting solution to form a film; finally, the membrane was soaked in 1M KOH solution for 36h to remove anions from Cl-Conversion to OH-. And finally, repeatedly washing with deionized water to remove residual alkali, thereby obtaining the long-chain branched poly (arylene ether nitrile) anion exchange membrane.
The anion-exchange membrane obtained in this example had the following structure:
tests show that the ion conductivity of the long-chain branched poly (arylene ether nitrile) anion-exchange membrane prepared in the embodiment at 20 ℃ is 28mS cm-1The water absorption rate is 51 percent, the swelling degree is 23 percent, the film is not degraded after being soaked in 1mol/L KOH solution for 500 hours at the temperature of 60 ℃, and the film shows more excellent performance.
Claims (9)
1. A preparation method of a long-chain branch poly (arylene ether nitrile) anion exchange membrane is characterized in that the structure of the long-chain branch poly (arylene ether nitrile) anion exchange membrane is as follows:
wherein: x is 0-0.9, and y is 1-0.1; n is an integer of 1-16;
r is an introduced functional group and is one of N-methylpyrrolidine, N-methylmorpholine, N-methylpiperidine, 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole, trimethylamine, triethylamine, pyridine and guanidine;
the preparation method comprises the following steps:
(1) and (3) synthesis of poly (arylene ether nitrile):
dissolving 2, 6-difluorobenzonitrile, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and potassium carbonate in a solvent A to prepare a solution with the mass concentration of 150-400 g/L, adding toluene in an amount which is 0.5-1.5 times the volume of the solvent A, condensing and refluxing for 3-12 h at 120-150 ℃ in a protective gas atmosphere until water and toluene are completely removed, and then heating to 160 ℃ to react for 12-20 h; pouring the obtained solution into a precipitator A under vigorous stirring to precipitate a white filamentous product, then carrying out re-precipitation operation to further improve the purity of the product, namely re-dissolving the obtained filamentous product into the solvent A to prepare a solution with the mass concentration of 100-350 g/L, then separating the solution out through the precipitator A again, repeating the re-precipitation operation for 2-5 times, and finally carrying out vacuum drying to obtain the poly (arylene ether nitrile);
the content of the 2,6 difluorobenzonitrile: 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane: the molar ratio of potassium carbonate is 10: 10-1: 15;
the solvent A is one of N, N-dimethylacetamide and N-methylpyrrolidone;
the precipitant A is one of methanol, ethanol and water;
(2) preparing a long-chain branched poly (arylene ether nitrile) anion exchange membrane:
preparing a poly (arylene ether nitrile)/solvent B solution with the mass concentration of 30-100 g/L, adding NaH under the protection of inert gas, reacting for 2-8 h at 20-60 ℃, adding a monomer A containing a fatty chain, and reacting for 12-48 h at 40-80 ℃; pouring the reaction solution into a precipitator B under rapid stirring, repeatedly washing and drying by using a solvent C, dissolving the product in the solvent B to prepare a solution with the mass concentration of 50g/L, adding a certain amount of ionizing reagent, and reacting for 48-72 h at the temperature of 80-120 ℃ to obtain a casting solution; spreading a film on a clean glass plate by using a casting method for the film casting solution, drying, then taking off the film from the glass plate, soaking the film in a solvent D for 24-48 h to remove anions from Cl-Conversion to OH-Repeatedly washing with deionized water to remove residual alkali liquor, and obtaining the long-chain branched poly (arylene ether nitrile) anion exchange membrane;
the amount of the added substances of the NaH is 2-6 times of the amount of the substances of the amido substituted repeating units in the poly (arylene ether nitrile);
the structure of the monomer A containing the fatty chain is Cl- (CH)2)n-Br, added in a quantity of substance 1.5 to 3 times the quantity of substance of NaH; wherein n is a positive integer of 1-16;
the amount of substances added into the ionizing reagent is 1.5-3 times of the amount of substances of the monomer A containing the fatty chain;
the solvent B is one of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the precipitant B is one of acetone and ethyl acetate;
the solvent C is one of methanol, ethanol and water;
the ionizing reagent is one of N-methylpyrrolidine, N-methylmorpholine, N-methylpiperidine, 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole, trimethylamine, triethylamine, pyridine and guanidine;
the solvent D is one of KOH and NaOH.
2. The production method according to claim 1, wherein 2, 6-difluorobenzonitrile, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and potassium carbonate are dissolved in a solvent a, and hexafluorobisphenol a is added while controlling the molar ratio of 2, 6-difluorobenzonitrile to hexafluorobisphenol a to not less than 10: 9.
3. the production method according to claim 1 or 2, wherein in the step (1), the temperature of the polyarylene ether nitrile in vacuum drying is 30 to 100 ℃ and the time is 6 hours or more.
4. The preparation method according to claim 1 or 2, wherein in the step (2), the product is repeatedly washed by the solvent C for 3 to 5 times, and the temperature required in the drying step after repeatedly filtering and washing the product by the solvent C is 40 to 100 ℃ for 8 hours or more.
5. The preparation method according to claim 3, wherein in the step (2), the product is repeatedly washed by the solvent C for 3 to 5 times, and the temperature required in the drying step after repeatedly filtering and washing the product by the solvent C is 40 to 100 ℃ for 8 hours or more.
6. The preparation method according to claim 1,2 or 5, wherein in the step (2), the drying temperature for the film formed by the casting method is 50-80 ℃ and the time is 24-48 hours; the thickness of the film formed by the casting method is within the range of 30-60 mu m.
7. The preparation method according to claim 3, wherein in the step (2), the drying temperature of the film formed by the casting method is 50-80 ℃ and the time is 24-48 hours; the thickness of the film formed by the casting method is within the range of 30-60 mu m.
8. The preparation method according to claim 4, wherein in the step (2), the drying temperature of the film formed by the casting method is 50-80 ℃ and the time is 24-48 hours; the thickness of the film formed by the casting method is within the range of 30-60 mu m.
9. The method according to claim 1,2, 5, 7 or 8, wherein in the step (2), the deionized water is repeatedly used for washing the film for 3-5 times.
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