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A side chain type sulfonated polyquinoxaline and its proton exchange membrane

A sulfonated polyquinoxaline and sulfonated technology, applied in the field of proton exchange membranes, to achieve excellent thermal hydrolysis stability, simple and mild reaction conditions, and good solubility

Active Publication Date: 2022-03-18
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of them fail to meet the high proton conductivity at high operating temperature, strong hydrolytic stability and long-lasting stability required by high-performance proton exchange membranes [Asano N, Aoki M, Suzuki S, Miyatake K, Uchida H, Watanabe M. J Am Chem Soc 2006; 128:1762–9]

Method used

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  • A side chain type sulfonated polyquinoxaline and its proton exchange membrane
  • A side chain type sulfonated polyquinoxaline and its proton exchange membrane
  • A side chain type sulfonated polyquinoxaline and its proton exchange membrane

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Experimental program
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Effect test

Embodiment 1

[0028] In this embodiment, the tetraamine (4) skeleton is used as an example to synthesize sulfonated polyquinoxaline from the monomer (7) of the polyquinoxaline structural unit (a) before sulfonation, and the structure is as follows:

[0029]

[0030] The specific preparation method is:

[0031] (1) Polymerization

[0032] Weigh 4,4'-bis(2-(4-(4-phenylphenoxy)phenyl)acyl)biphenyl 0.7551g and 2-amino-4-((3,4-diaminophenyl )sulfonyl)aniline 0.2802g, mixed and poured into a flask, added m-cresol to dissolve, reacted at room temperature under nitrogen atmosphere for about 24h, poured the solution into ethanol to precipitate the polymer, washed repeatedly until it was cleaned, filtered, and collected the solid , dried in vacuum to obtain polymer fibers.

[0033] (2) Sulfonation

[0034] Pour the polymer fibers into a flask, add fuming sulfuric acid at a ratio of 10-15wt% solid content, react under a nitrogen atmosphere, pour the liquid into water, the sulfonated product is p...

Embodiment 2

[0038] In this embodiment, the monomer (2) of the polyquinoxaline structural unit (a) and the monomer (3) of the structural unit (b) before sulfonation are used as raw materials to synthesize sulfonated polyquinoxaline with the tetraamine (1) skeleton Taking morphine as an example, the structure is as follows (wherein x:y=4:1):

[0039]

[0040] The specific preparation method is:

[0041] (1) Polymerization

[0042] Weigh 1.2335g of 4,4'-bis(2-(4-(4-phenoxyphenyl)phenyl)acyl)diphenyl ether, 0.1741g of diphenil and 3,3',4,4 0.4285 g of '-tetraaminobiphenyl was reacted in m-cresol. After the reaction, the solution was poured into ethanol to precipitate the polymer, washed repeatedly until cleaned, filtered, and dried to obtain polymer fibers.

[0043] (2) Sulfonation

[0044] React the obtained polymer with concentrated sulfuric acid, pour the solution into water after the reaction, the sulfonated product is precipitated, wash repeatedly until pH=3~4, add appropriate amount...

Embodiment 3

[0048] In this embodiment, the monomer (5) of the polyquinoxaline structural unit (a) and the monomer (3) of the structural unit (b) before sulfonation are used as raw materials to synthesize sulfonated polyquinoxaline with the tetraamine (3) skeleton Taking morphine as an example, the structure is as follows (wherein x:y=4:1):

[0049]

[0050] The specific preparation method is:

[0051] (1) Polymerization

[0052] Weigh 0.9643g of 4,4'-bis(2-(4-phenoxyphenyl)acyl)biphenyl, 0.1739g of 4,4'-benziloxy and 3,3',4,4'- Tetraaminodiphenyl ether 0.4695g was reacted in m-cresol. After the reaction, the solution was poured into ethanol to precipitate the polymer, washed repeatedly until cleaned, filtered, and dried to obtain polymer fibers.

[0053] (2) Sulfonation

[0054] React the obtained polymer with concentrated sulfuric acid, pour the solution into water after the reaction, the sulfonated product is precipitated, wash repeatedly until pH=3~4, add appropriate amount of so...

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Abstract

The invention discloses a side chain type sulfonated polyquinoxaline and a preparation method thereof for a proton exchange membrane, belonging to the field of proton exchange membranes. In order to solve the problems of low proton conductivity and poor chemical stability of the aromatic sulfonated polymer proton exchange membrane working at high temperature. The following technical scheme is used to copolymerize diisoyl monomers with clear sulfonatable sites, non-sulfonatable diisoyl monomers and different tetraamine monomers in different molar ratios, and through a mild post-sulfonation method, A side-chain type sulfonated polyquinoxaline with clear sulfonation position, predictable ion exchange capacity and reproducible results is obtained. The preparation process of the side chain type sulfonated polyquinoxaline involved in the present invention is simple, the reaction conditions are mild, the degree of sulfonation is controllable, and the obtained proton exchange membrane has good proton conductivity, excellent hydrolysis stability and dimensional stability And good fuel cell performance, as a fuel cell proton exchange membrane has great application potential.

Description

(2) Technical field [0001] The invention belongs to the field of proton exchange membranes, in particular to a side chain type sulfonated polyquinoxaline proton exchange membrane. (3) Background technology [0002] Proton exchange membrane fuel cells (PEMFCs) enable higher efficiencies at lower environmental costs than current renewable fuel power sources. Polymer proton exchange membrane (PEM) plays a key role in the fuel cell system, both to isolate the fuel gas between the two electrodes and to transfer protons from the anode to the cathode [Feixiang Gong, Nanwen Li, Suobo Zhang. Synthesis and properties of novel sulfonated poly(phenylquinoxaline)s asproton exchange membranes [J]. Polymer. 50(2009) 6001–6008]. At present, perfluorosulfonic acid PEM is the only commercialized proton exchange membrane, which has excellent proton conductivity, chemical stability and mechanical properties, and the representative one is the PEM of Nafion series in the United States. However,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G73/06C08J5/22H01M8/103C08L79/04
CPCC08G73/0694C08J5/2256H01M8/103C08J2379/04Y02E60/50
Inventor 陈康成陈星刘璐
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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