Sulfonated polyaryletherketone copolymer containing benzothiazole group and preparation method thereof

A sulfonated polyaryletherketone and benzothiazole-based technology is applied in the field of sulfonated polyaryletherketone copolymer and its preparation, and can solve the problem of reducing the service life of the sulfonated polyaryletherketone membrane and reducing the ability to resist free radical oxidation. , reduce the mechanical properties of the membrane, etc., to achieve high anti-oxidative stability, good proton conductivity, and good dimensional stability.

Inactive Publication Date: 2017-09-15
INST OF CHEM MATERIAL CHINA ACADEMY OF ENG PHYSICS
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, in order to improve the proton conductivity, it is necessary to increase the degree of sulfonation of the material. At a high degree of sulfonation, the polyaryletherketone membrane swells severely when it encounters water, which reduces the mechanical properties of the membrane. At the same time, the ability to resist free radical oxidation decreases, resulting in The membrane is easy to break, and the existence of these shortcomings greatly reduces the service life of the sulfonated polyaryletherketone membrane, especially under high temperature and high humidity operating conditions

Method used

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  • Sulfonated polyaryletherketone copolymer containing benzothiazole group and preparation method thereof
  • Sulfonated polyaryletherketone copolymer containing benzothiazole group and preparation method thereof
  • Sulfonated polyaryletherketone copolymer containing benzothiazole group and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0031] In a three-necked flask equipped with a mechanical stirrer, a water dispenser, a thermometer, a condenser tube, and nitrogen protection, add 0.1 mol of bisphenol A, 0.02 mol of 2,6-dichlorobenzothiazole, and 0.03 mol of 4,4 '-Difluorobenzophenone, 0.05mol of 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, 0.105mol of potassium carbonate as salt-forming agent, and adding water-carrying agent and solvent Obtain a reaction system with a solid content of 20%; add water at 120°C for 3 hours, then distill off the water-carrying agent, and then raise the temperature to 140°C to continue the reaction for 20 hours; after the reaction is complete, pour the mixture into distilled water to obtain a light yellow strip solid, Grinding into fine powder, washing with acetone for 3 times and distilled water for 3 times; finally drying at 60°C to obtain a sulfonated polyaryletherketone copolymer containing benzothiazole groups with a sulfonation degree of 1.0.

Embodiment 2

[0033] In a three-neck flask equipped with a mechanical stirrer, a water dispenser, a thermometer, a condenser tube, and nitrogen protection, add 0.1mol of hexafluorobisphenol A, 0.03mol of 2,6-dichlorobenzothiazole, and 0.03mol of 4 , 4'-difluorobenzophenone, 0.04mol of 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, 0.11mol of sodium carbonate as salt-forming agent, dimethyl ethyl Amide as a solvent, xylene as a water-carrying agent, the solid content of the reaction system is 22%; carry water at 120°C for 4 hours, then steam the water-carrying agent, and then heat up to 150°C to continue the reaction for 16 hours; after the reaction is complete, the mixture Pour it into acetone to obtain a light yellow strip solid, crush it into a fine powder, wash it with acetone for 5 times, and then wash it with distilled water for 5 times; finally dry it at 80°C to obtain benzothiazole with a sulfonation degree of 0.8 Group of sulfonated polyaryletherketone copolymers.

Embodiment 3

[0035] In a three-necked flask equipped with a mechanical stirrer, a water dispenser, a thermometer, a condenser tube, and nitrogen protection, add 0.1mol of hydroquinone, 0.02mol of 2,6-dichlorobenzothiazole, and 0.02mol of 4, 4'-difluorobenzophenone, 0.06mol of 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, 0.12mol of potassium carbonate as salt-forming agent, and N-methylpyrrolidone As solvent, toluene is used as water-carrying agent, and the solid content of the reaction system is 15%; carry water at 130°C for 5 hours, then steam the water-carrying agent, and then heat up to 170°C to continue the reaction for 14 hours; after the reaction is complete, pour the mixture into In distilled water, a light yellow strip solid was obtained, crushed into fine powder, washed with acetone for 4 times, and then washed with distilled water for 4 times; finally dried at 70°C to obtain a benzothiazole group-containing compound with a sulfonation degree of 1.2 Sulfonated polyaryletherk...

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Abstract

The invention discloses a sulfonated poly(aryle ether ketone) copolymer containing benzothiazole groups and a preparation method of the sulfonated poly(aryle ether ketone) copolymer. The copolymer is prepared through steps as follows: bisphenol monomers, 2,6-dichlorobenzothiazole, 4,4'-difluorobenzophenone and 3,3'-disulfonic acid sodium salt-4,4'-difluorobenzophenone are taken as raw materials, a salt-forming agent and a water-carrying agent are added after the raw materials are dissolved and mixed by a solvent, solid content of a reaction system is adjusted to be 15%-30%, the reaction system carries water for 3-6 h at the temperature of 120-140 DEG C, and reacts for 6-20 h at the temperature of 140-200 DEG C after the water-carrying agent is steamed out, a mixture is discharged to acetone or distilled water after the reaction is finished, a coarse product is obtained and washed, and the sulfonated poly(aryle ether ketone) copolymer containing the benzothiazole groups is obtained. An electrolyte membrane prepared from the copolymer has better dimensional stability, lower methanol permeability, higher antioxidative stability and good proton conduction performance, and compared with a traditional aromatic polyelectrolyte membrane, the electrolyte membrane prepared from the copolymer is a novel proton exchange membrane material with excellent performance and has good application prospect in the field of the electrolyte membrane of a fuel cell.

Description

technical field [0001] The present invention belongs to the field of polymer materials, and more specifically, the embodiments of the present invention relate to a sulfonated polyaryletherketone copolymer containing benzothiazole groups and a preparation method thereof. Background technique [0002] The development of polymer electrolyte membrane materials is one of the key technologies of fuel cells. At present, perfluorosulfonic acid series membranes are widely used in fuel cells, such as Dupont's Nafion series membranes, because of their excellent proton conductivity and chemical stability. However, due to the disadvantages of complex preparation process, high price, high fuel permeability and low use temperature, the wide application of Nafion membrane is limited. Therefore, the development of new polyelectrolyte membrane materials with excellent conductivity, reasonable cost and low fuel permeation has always been a hot spot for researchers. Polyaryletherketone polyme...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G65/40
CPCC08G65/4056
Inventor 李野芦艾盖方圆余凤湄张倩王宪忠
Owner INST OF CHEM MATERIAL CHINA ACADEMY OF ENG PHYSICS
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