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A kind of phosphonated (polyolefin-g-polybenzimidazole) graft copolymer and its preparation method and application

A technology of graft copolymer and polybenzimidazole, which is applied in the field of phosphonated graft copolymer and its preparation, can solve the problems of decreased proton conductivity and loss of phosphoric acid, and can improve proton conductivity, reduce loss, and increase proton Effect of conductivity retention

Active Publication Date: 2022-03-01
ZHUHAI COSMX BATTERY CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] As mentioned above, the current proton exchange membrane materials of benzimidazole polymers need to use a large amount of phosphoric acid to achieve high proton conductivity, and the loss of phosphoric acid during long-term use leads to a decrease in proton conductivity.

Method used

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  • A kind of phosphonated (polyolefin-g-polybenzimidazole) graft copolymer and its preparation method and application
  • A kind of phosphonated (polyolefin-g-polybenzimidazole) graft copolymer and its preparation method and application
  • A kind of phosphonated (polyolefin-g-polybenzimidazole) graft copolymer and its preparation method and application

Examples

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preparation example Construction

[0078] The preparation method of the present invention will be further described in detail in conjunction with specific examples below. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies realized based on the above contents of the present invention are covered within the scope of protection intended by the present invention.

[0079] The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents and materials used in the following examples can be obtained from commercial sources unless otherwise specified.

Embodiment 1

[0103] Phosphonated polyacrylic acid grafted with m-polybenzimidazole (P-PAA-g-mPBI, figure 1 Middle 1#) Preparation of proton exchange membrane

[0104] (1) Dissolve 6.16g of mPBI (polymerization degree 100, 0.2mmol) and polyacrylic acid 1.44g (20mmol carboxyl group) of PBI: carboxyl = 1:100 (molar ratio) in 100mL of DMF and react at 160°C for 15h.

[0105] (2) After the reaction, add 5.916 g of amino-containing phosphonic acid alendronic acid (1.2 times the molar weight of the carboxyl groups in the remaining PAA) to the above solution, and reflux and stir the reaction at 160°C for 10 hours. After the reaction, the solvent is rotary evaporated Control the total solid content to 10%, then pour the solution on a glass plate and apply it with a 400μm scraper, then volatilize the solvent at 60-120°C, and after the solvent is completely volatilized, apply a 400μm scraper and dry to get 65μm P-PAA-g-mPBI membrane.

[0106] (3) The above P-PAA-g-mPBI membrane was soaked in 85% ph...

Embodiment 2

[0110] Phosphonated polymethacrylic acid grafted m-polybenzimidazole (P-PMAA-g-mPBI, figure 1 Middle 2#) preparation of proton exchange membrane

[0111] (1) Dissolve mPBI 9.24g (polymerization degree 50, 0.6mmol) and PMAA 1.74g (20mmol carboxyl) with a molar ratio of PBI: carboxyl = 1:33.33 (molar ratio) in 100mL of DMF and react at 160°C 15h.

[0112] (2) Same as Example 1, except that the amino-containing phosphonic acid is 5.797 g of alendronic acid (1.2 times the carboxyl molar weight in the remaining PMAA).

[0113] (3) Same as Example 1.

[0114] After testing, the ADL of the high-temperature proton exchange membrane is 9.09, the proton conductivity at 180°C is 0.0888S / cm, the proton conductivity after 10 deionized water immersions is 0.0703S / cm, and the conductivity retention rate is 79.3 %, compared to the mPBI conductivity retention rate (69.7%) in Comparative Example 1, the improvement ratio was 13.8%.

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Abstract

The invention relates to a phosphonated (polyolefin-g-polybenzimidazole) graft copolymer and its preparation method and application. The graft copolymer of the present invention uses soft polyolefins as the main chain, takes rigid PBI as the branch chain, and further prepares through amino-containing phosphonic acid grafting to obtain both phosphonic acid and soft-hard chains. segmented phosphonated graft copolymers. The polymers with two properties will undergo microscopic phase separation to construct proton transport channels, thereby improving proton conductivity; in addition, the flexible main chain drives the movement of PBI branch chains to reduce the activation energy of proton migration, and promote the migration of phosphoric acid or protons to improve proton conductivity. Rate. The grafted amino-containing phosphonic acid can reduce the doping amount of inorganic phosphoric acid, thereby reducing the loss of phosphoric acid during use, so as to improve the proton conductivity retention rate of the membrane.

Description

technical field [0001] The invention relates to the field of graft copolymer materials, in particular to a phosphonated (polyolefin-g-polybenzimidazole) graft copolymer and its preparation method and application. Background technique [0002] Benzimidazole polymers (PBIs) are polymers containing benzimidazole rings in the main chain structure, which have excellent physical and chemical properties such as chemical stability, thermal stability, flame retardancy and mechanical properties, and are widely used Used in high temperature resistant fabrics, fire retardant materials and filter materials for industrial products, etc. With the rise of fuel cell research, the commonly used perfluorosulfonic acid proton exchange membrane cannot meet the operation of fuel cells under high temperature and low humidity conditions due to defects such as the decrease of proton conductivity and mechanical properties under high temperature and low humidity conditions. Researchers began to look ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G81/02H01M8/1034H01M8/1048H01M8/1069H01M8/1072H01M8/1086
CPCC08G81/024H01M8/1048H01M8/1069H01M8/1072H01M8/1086H01M8/1034Y02E60/50
Inventor 莫肇华李素丽李俊义徐延铭
Owner ZHUHAI COSMX BATTERY CO LTD
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