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Low-swelling sulfonation polyimide proton exchanging membrane and preparation thereof

A technology of sulfonated polyimide and proton exchange membrane, applied in the field of low-swelling sulfonated polyimide proton exchange membrane and its preparation, can solve the problem of increasing methanol permeability, reducing fuel utilization efficiency, reducing proton exchange membrane mechanical In order to improve the fuel utilization rate, enhance the high temperature swelling stability and reduce the permeability of methanol

Inactive Publication Date: 2009-01-14
SHANGHAI INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the sulfonic acid groups in the molecular structure of most sulfonated polyimide proton exchange membranes are directly substituted on the aromatic ring of the main chain. As the degree of sulfonation increases, the strongly hydrophilic sulfonic acid groups will lead to protons The exchange membrane swells excessively in the high heat and acidic working environment, which reduces the mechanical strength of the proton exchange membrane, increases the methanol permeability, and reduces the fuel utilization efficiency

Method used

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  • Low-swelling sulfonation polyimide proton exchanging membrane and preparation thereof
  • Low-swelling sulfonation polyimide proton exchanging membrane and preparation thereof
  • Low-swelling sulfonation polyimide proton exchanging membrane and preparation thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0030] (1) Dissolve 11g (0.1mol) of resorcinol monomer and 14.6g (0.11mol) of aluminum trichloride in 100g of dichloromethane, cool to 0°C with an ice bath under a nitrogen atmosphere, and stir for 10 minutes , then 17.15g (0.1mol) 3-bromopropionyl chloride was added dropwise within 15 minutes, stirred at 0°C for 4 hours, after the reaction was completed, the reaction product was poured into 100g of ice water containing 10g of concentrated hydrochloric acid, and the Separate the organic phase, then wash once with 100g10% sodium hydroxide, then wash twice with 100g deionized water, and finally dry with 20g anhydrous magnesium sulfate, after filtering, distill off most of the solvent in the mixed solution, and use 30g The sherwood oil recrystallization obtains 20.8g (productive rate 85%) to have the diphenol monomer of bromopropyl group branch;

[0031] (2) the above-mentioned obtained diphenol monomer with bromopropyl branched chain gets 24.5g (0.1mol) and 25.5g (0.2mol) of 4-c...

Embodiment 2

[0037] (1) Dissolve 11g (0.1mol) of resorcinol monomer and 14.6g (0.11mol) of aluminum trichloride in 100g of dichloromethane, cool to 0°C with an ice bath under a nitrogen atmosphere, and stir for 10 minutes , then 19.95g (0.1mol) 5-bromovaleryl chloride was added dropwise within 15 minutes, stirred at 0°C for 4 hours, after the reaction was completed, the reaction product was poured into 100g of ice water containing 10g of concentrated hydrochloric acid, and the Separate the organic phase, then wash once with 100g10% sodium hydroxide, then wash twice with 100g deionized water, and finally dry with 20g anhydrous magnesium sulfate, after filtering, distill off most of the solvent in the mixed solution, and use 30g The sherwood oil recrystallization obtains 22.1g (productive rate 81%) to have the diphenol monomer of bromopentyl branch;

[0038] (2) the above-mentioned obtained diphenol monomer with bromopentyl branch gets 27.3g (0.1mol) and 25.5g (0.2mol) of 4-chloroaniline, an...

Embodiment 3

[0044] (1) Dissolve 11g (0.1mol) of resorcinol monomer and 14.6g (0.11mol) of aluminum trichloride in 100g of dichloromethane, cool to 0°C with an ice bath under a nitrogen atmosphere, and stir for 10 minutes , then 21.35g (0.1mol) 6-bromohexanoyl chloride was added dropwise within 15 minutes, stirred at 0°C for 4 hours, after the reaction was completed, the reaction product was poured into 100g of ice water containing 10g of concentrated hydrochloric acid, and the Separate the organic phase, then wash once with 100g10% sodium hydroxide, then wash twice with 100g deionized water, and finally dry with 20g anhydrous magnesium sulfate, after filtering, distill off most of the solvent in the mixed solution, and use 30g The sherwood oil recrystallization obtains 25.8g (90% of productive rate) the diphenol monomer that has bromohexyl branch;

[0045] (2) get the 4-chloroaniline of 28.7g (0.1mol) and 25.5g (0.2mol) of the diphenol monomer with bromohexyl branch obtained above, the sa...

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Abstract

The invention relates to a low-swelling sulfonated polyimide proton exchange membrane and the preparation method thereof. The preparation method of the low-swelling sulphonation polyimide proton exchange membrane adopts the steps that novel diamine monomer with terminal sulfonic acid alkyl branched chain is obtained through friedel-acrafts acylation reaction, polycondensing and ether becoming reaction and sulfurous acid displacing reaction, then the novel diamine monomer and aromatic dianhydride monomer generate reaction, polyimide copolymer with sulfonic acid alkyl branched chain is obtained and dissolved in N-methyl-2-ketoyrrolidine, finally the solution is poured on a glass flat plate and coated in a flow-casting way, the vacuum drying operation is performed, and the low-swelling sulfonated polyimide proton exchange membrane is obtained. The low-swelling sulfonated polyimide proton exchange membrane obtained by utilizing the preparation method has the advantages of high proton conductivity and low methanol penetrability; simultaneously, good low-swelling property is provided, therefore, the low-swelling sulfonated polyimide proton exchange membrane has extensive application prospect in the methanol fuel cell field.

Description

technical field [0001] The invention relates to a polymer material membrane and a preparation method thereof, in particular to a low-swelling sulfonated polyimide proton exchange membrane used in a fuel cell and a preparation method thereof. Background technique [0002] In the era of surging energy demand in the 21st century, new fuel cells, as a green energy source and an important supplement to conventional energy sources, have attracted widespread attention from research and development institutions around the world. Proton exchange membrane is the core component of fuel cell, and its performance determines the service life, operation stability and fuel utilization efficiency of fuel cell. Sulfonated polyimide proton exchange membrane not only has high proton conductivity, but also has low methanol permeability, so it has great application prospects in direct methanol fuel cells. However, the sulfonic acid groups in the molecular structure of most sulfonated polyimide p...

Claims

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Application Information

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IPC IPC(8): C08G73/10C08J5/22C08L79/08H01M8/10H01M8/103H01M8/1072
CPCY02E60/523Y02E60/50
Inventor 韩生吴锡慧高峰石勇
Owner SHANGHAI INSTITUTE OF TECHNOLOGY
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