Preparation of glyoxalinyl-containing sulphonation polyimides covalence-ionomer membrane

A technology based on sulfonated polyimide and sulfonated polyimide membrane, which is applied in the field of polymer membrane preparation, can solve the problems of low proton conductivity, poor compatibility, decreased proton conductivity and the like, and achieves proton conductivity. High rate, water resistance and good mechanical properties

Inactive Publication Date: 2009-04-15
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Another literature (Chemistry ofMaterials 2007, 19, 350-352) reported a polybenzimidazole cross-linked film with anti-free radical oxidation performance equivalent to that of Nafion, but this film has higher Proton conductivity, and the phosphoric acid in the membrane will gradually leak out over time, resulting in a decrease in proton conductivity, or even loss
Documents (Journal of Applied Scien

Method used

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  • Preparation of glyoxalinyl-containing sulphonation polyimides covalence-ionomer membrane
  • Preparation of glyoxalinyl-containing sulphonation polyimides covalence-ionomer membrane
  • Preparation of glyoxalinyl-containing sulphonation polyimides covalence-ionomer membrane

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Experimental program
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Effect test

Embodiment 1

[0021] Add 1.44 g (4.0 mmol) of 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (English abbreviation: ODADS) to a dry 100 mL three-neck flask equipped with a condenser tube and a nitrogen inlet and outlet , 0.348 grams (1.0mmol) 9,9-two (4-aminophenyl) fluorene (English abbreviation: BAPF), 0.224 grams (1.0mmol) 2- (4-aminophenyl) -5-aminobenzimidazole (English abbreviation name: APABI), 25mL m-cresol and 1.4mL triethylamine. After all the diamine monomers were completely dissolved, 1.608 g (6.0 mmol) of 1,4,5,8-naphthalene dioic anhydride (English abbreviation: NTDA) and 1.04 g of benzoic acid were added. The reaction mixture was stirred at room temperature for 0.5 hours, then heated to 80°C for 4 hours, and then heated to 180°C for 20 hours. After the reaction, the reaction solution was cooled, and then slowly poured into 250 mL of acetone to obtain a filamentous precipitate. Filter, wash with acetone, dry under vacuum condition, obtain imidazole-containing sulfonated pol...

Embodiment 2

[0027] Add 2.112 grams (4.0 mmol) of 3,3-bis(4-sulfonic acid phenoxy)benzidine (English abbreviation: BSPOB) to a dry 100 mL three-necked bottle equipped with a condenser tube and a nitrogen inlet and outlet, 0.348 Gram (1.0mmol) 9,9-bis(4-aminophenyl) fluorene (English abbreviation: BAPF), 0.224 gram (1.0mmol) 2-(4-aminophenyl)-5-aminobenzimidazole (English Abbreviated name: APABI), 30 mL m-cresol and 1.22 mL triethylamine. After the diamine monomer was completely dissolved, 1.608 g (6.0 mmol) of 1,4,5,8-naphthalene dicarboxylic anhydride (English abbreviation: NTDA) and 1.04 g of benzoic acid were added. The reaction mixture was stirred at room temperature for 0.5 hours, then heated to 80°C for 4 hours, and then heated to 180°C for 20 hours. After the reaction, the reaction system was cooled and 20 mL of m-cresol was added to dilute the highly viscous mixture, and then the diluted liquid was slowly poured into 300 mL of acetone to obtain a fibrous precipitate. Filter, wash...

Embodiment 3

[0033] Add 2.112 grams (4.0 mmol) of 4,4'-bis(4-aminophenoxy)biphenyl-3,3'-disulfonic acid ( English abbreviation name: BAPBDS), 0.348 grams (1.0mmol) 9,9-two (4-aminophenyl) fluorene (English abbreviation name: BAPF), 0.224 grams (1.0mmol) 2-(4-aminophenyl)- 5-aminobenzimidazole (English abbreviation name: APABI), 30 mL of m-cresol and 1.22 mL of triethylamine. After the diamine monomer was completely dissolved, 1.608 g (6.0 mmol) of 1,4,5,8-naphthalene dicarboxylic anhydride (English abbreviation: NTDA) and 1.04 g of benzoic acid were added. The reaction mixture was stirred at room temperature for 0.5 hours, then heated to 80°C for 4 hours, and then heated to 180°C for 20 hours. After the reaction, the reaction system was cooled and 20 mL of m-cresol was added to dilute the highly viscous mixture, and then the diluted liquid was slowly poured into 300 mL of acetone to obtain a fibrous precipitate. Filter, wash with acetone, and vacuum dry to obtain imidazole-containing sul...

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Abstract

The invention relates to a preparation method of a covalent-ion cross-linked film of sulfonated polyimide containing imidazolyl. The preparation method comprises the following steps: 1, 4, 5, 8-naphthoic tetracarboxylic dianhydride, sulfonated diamine, common non-sulfonated diamine and diamine containing imidazolyl are added into a metacresol medium, the sulfonated polyimide containing imidazolyl is obtained by copolycondensation under the presence of triethylamine and benzoic acid and the protection of nitrogen; a solution casting method and proton exchange are adopted to prepare non-covalent cross-linked sulfonated polyimide film containing imidazolyl which is then processed by methane-sulfonic acid/phosphorus pentoxide solution or phosphoric acid solution or polyphosphoric acid containing phosphorus petoxide so as to prepare the covalent-ion cross-linked film of sulfonated polyimide containing imidazolyl. The covalent-ion cross-linked film obtained by the preparation method has anti-free radical oxidation susceptibility which is far better than the common sulfonated polyimide or non-covalent cross-linked film without containing imidazolyl and has potential application prospect in the fields of fuel cells and the like.

Description

technical field [0001] The invention relates to a preparation method of a polymer membrane, in particular to a preparation method of a covalent-ion cross-linked membrane containing imidazole group-containing sulfonated polyimide. The prepared cross-linked membrane can be used in technical fields such as fuel cells. Background technique [0002] Proton exchange membrane fuel cell is a clean, efficient, portable and environment-friendly energy device, which has broad application prospects in electric vehicles, electronic equipment and military fields. The proton exchange membrane is the core component of the fuel cell. The commonly used proton exchange membrane is a perfluorosulfonated polymer membrane named Nafion produced by DuPont of the United States. This type of membrane has high proton conductivity and good mechanical properties. Strength, excellent chemical and electrochemical stability, and long service life, but its high price, sharp drop in proton conductivity at hi...

Claims

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Application Information

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IPC IPC(8): C08J5/22C08J3/24C08L79/08C08K5/42C08K3/32C08G73/10H01M8/02H01M2/16H01M8/0239H01M50/403H01M50/411H01M50/489H01M50/497
CPCY02E60/12Y02E60/50
Inventor 房建华郭晓霞张桂梅徐楠徐宏邢韬徐宏杰
Owner SHANGHAI JIAO TONG UNIV
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