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Cross-linked block polymer anion exchange membrane, preparation method and applications thereof

An anion exchange membrane and block polymer technology, which is applied in the field of preparation of cross-linked block polymer anion exchange membranes, can solve the problem that low-level secondary amines cannot be highly cross-linked in the polymer skeleton, and there is little room for improvement in membrane stability. , The polymer substrate contains ether bonds and other problems, and achieves the effects of excellent dimensional stability and chemical stability, low cost and high reactivity

Inactive Publication Date: 2019-02-26
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The disadvantage is that its preparation process is relatively complicated, and the low-level secondary amines used cannot really achieve a high degree of cross-linking between the polymer backbones, so there is not much room for improvement in membrane stability, and at the same time, part of the chloromethyl group is occupied after cross-linking. Make it impossible to continue quaternization, thereby reducing the number of quaternary ammonium groups, resulting in a smaller ion exchange capacity
Dalian Institute of Chemical Physics (Chinese patent: a preparation method of cross-linked polymer anion exchange membrane, patent application number: 201110427128.2) discloses a preparation method of polyaryl ether sulfone ketone cross-linked anion exchange membrane. Compared with the preparation method of quaternization after film formation, the anion exchange membrane obtained by the present invention has a higher ion exchange capacity, but its polymer base contains ether bonds, etc. Degradation and other issues

Method used

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  • Cross-linked block polymer anion exchange membrane, preparation method and applications thereof
  • Cross-linked block polymer anion exchange membrane, preparation method and applications thereof
  • Cross-linked block polymer anion exchange membrane, preparation method and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Dissolve 5g of polystyrene-ethylene-butylene-styrene (SEBS) with molecular weight Mn≈130000 and 58wt.% styrene block content in 150mL of organic reagent chloroform, stir at 55°C for 5 hours, add 7mL of SnCl 4 and 46mL BCMB, reacted for 3h, poured the reacted solution into anhydrous methanol, precipitated the polymer, filtered it with suction, washed it with deionized water until neutral, and dried it in a vacuum oven at 60°C to obtain chloromethyl Polystyrene-ethylene-butylene-styrene (CMSEBS). Then it was dissolved in chloroform solution to form a 5wt.% solution, and N,N,N',N'-tetramethyl-1,6-hexamethylenediamine (TMHDA) was added to it, the number of moles of which was CMSEBS 1 times, stir at room temperature for 60 seconds, then pour into a glass box, put it in an oven at 60°C, heat for 24 hours, dry the solvent, and remove it.

[0034] Soak the membrane in trimethylamine aqueous solution at room temperature, take it out after soaking for 24 hours, and obtain the cr...

Embodiment 2

[0040] Dissolve 10 g of polystyrene-ethylene-butylene-styrene (SEBS) with a molecular weight of Mn≈130000 and a styrene block content of 42 wt.% in 150 mL of organic reagent chloroform, stir at 55 °C for 6 hours, and add 13 mL of SnCl 4 React with 88mL BCMB for 10h. Pour the reacted solution into anhydrous methanol. After the polymer is precipitated, filter it with suction, wash it with deionized water until neutral, and then dry it in a vacuum oven at 60°C to obtain chloromethyl Polystyrene-ethylene-butylene-styrene (CMSEBS). Then it was dissolved in chloroform solution to form a 3wt.% solution, and N,N,N',N'-tetramethyl-1,6-hexamethylenediamine (TMHDA) was added to it, the number of moles of which was CMSEBS 1.5 times, stirred at room temperature for 30 seconds, then poured into a glass frame, placed in an oven at 60°C, heated for 24 hours, dried the solvent, and removed.

[0041] Soak the membrane in trimethylamine aqueous solution at room temperature, take it out after so...

Embodiment 3

[0046] Dissolve 10g of polystyrene-ethylene-butylene-styrene (SEBS) with molecular weight Mn≈80000 and 3.7wt.% styrene block content in 300mL of organic reagent chloroform, stir at 60°C for 5 hours, add 15mL of SnCl 4 and 95mL BCMB, reacted for 10h, poured the reacted solution into anhydrous methanol, precipitated the polymer, filtered it with suction, washed it with deionized water until neutral, and dried it in a vacuum oven at 60°C to obtain chloromethyl Polystyrene-ethylene-butylene-styrene (CMSEBS). Then it was dissolved in chloroform solution to form a 5wt.% solution, and N,N,N',N'-tetramethyl-1,6-hexamethylenediamine (TMHDA) was added to it, the number of moles of which was CMSEBS 0.5 times, stirred at room temperature for 60 seconds, then poured into a glass frame, placed in an oven at 60°C, heated for 24 hours, dried the solvent, and removed.

[0047] Soak the membrane in trimethylamine aqueous solution at room temperature, take it out after soaking for 24 hours, and...

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Abstract

This invention relates to cross-linked block polymer anion exchange membrane, a preparation method and applications thereof. According to the method, during the membrane preparing, a chloromethylatedblock polymer is simultaneously cross-linked and aminated by using a one-step method; after the membrane is formed, the membrane is further quaternized with tertiary amine; and alkalization is performed to obtain the cross-linked anion exchange membrane. According to the present invention, the polymer is chloromethylated by using the environmentally-friendly low-toxicity 1,4-dichloromethoxybutaneas a chloromethylating agent, the cross-linking and amination of the polymer is performed with the tertiary amine during the membrane forming, and after the membrane forming, the re-amination is performed with the tertiary amine so as to increase the number of the quaternary ammonium groups; with the method, the cross-linking and the quaternization are performed simultaneously during the membraneforming, such that the mechanical strength and the dimensional stability of the cross-linked membrane are improved, and the quaternization efficiency is effectively increased; and the obtained cross-linked anion exchange membrane has high conductivity, and has potential application prospects in alkaline anion exchange membrane fuel cells.

Description

technical field [0001] The invention relates to an alkaline anion exchange membrane fuel cell, in particular to a preparation method of a cross-linked block polymer anion exchange membrane. Background technique [0002] Alkaline membrane fuel cell (AEMFC) has the advantages of fast oxygen reduction kinetics, the use of non-platinum catalysts, low material corrosion resistance requirements, and low cost. Still need to improve urgently. This is because the current anion exchange membranes are mainly composed of different polymer skeletons grafted with cationic groups, and the cationic groups are mainly quaternary ammonium groups. [0003] Studies have found that there is a certain degree of contradiction between the ion exchange capacity and mechanical strength of this type of anion exchange membrane. For example, when the ion exchange capacity is too large and the water content is too high, the membrane is easy to be brittle. The mechanical strength is guaranteed, but the i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J5/22C08J7/12C08J3/24C08F8/24C08F297/04C08L53/02
CPCC08F8/24C08J3/24C08J5/2243C08J5/2287C08J7/12C08J2353/02H01M8/1072C08F297/04Y02E60/50
Inventor 邵志刚郝金凯姜永燚高学强衣宝廉
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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