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Phosphorylated(polyolefin-g-polybenzimidazole) graft copolymer as well as preparation method and application thereof

A technology of graft copolymer and polybenzimidazole is applied in the field of phosphonated graft copolymer and its preparation, and can solve the problems of loss of phosphoric acid, decrease of proton conductivity and the like

Active Publication Date: 2020-04-10
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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  • Phosphorylated(polyolefin-g-polybenzimidazole) graft copolymer as well as preparation method and application thereof
  • Phosphorylated(polyolefin-g-polybenzimidazole) graft copolymer as well as preparation method and application thereof
  • Phosphorylated(polyolefin-g-polybenzimidazole) graft copolymer as well as preparation method and application thereof

Examples

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preparation example Construction

[0078] The preparation method of the present invention will be further described in detail below in conjunction with specific examples. It should be understood that the following embodiments are only illustrative and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the foregoing contents of the present invention are covered by the scope of 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, unless otherwise specified, can be obtained from commercial sources.

Embodiment 1

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

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

[0105] (2) After the reaction is completed, add 5.916 g of amino-containing alendronic acid (1.2 times the molar amount of carboxyl groups in the remaining PAA) to the above solution, reflux and stir the reaction at 160°C for 10 hours, and then rotate the solvent after the reaction is completed Control the total solid content to 10%, then pour the solution onto the glass plate and coat it with a 400μm doctor blade, and then volatilize the solvent at 60~120℃. After the solvent is completely volatilized, perform a 400μm doctor blade coating and dry to get 65μm The P-PAA-g-mPBI film.

[0106] (3) The P-PAA-g-mPBI membrane was i...

Embodiment 2

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

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

[0112] (2) The same as Example 1, except that the amino group-containing phosphonic acid is 5.797 g of alendronic acid (1.2 times the molar amount of carboxyl groups 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 immersion is 0.0703S / cm, and the conductivity retention rate is 79.3 %, compared with the mPBI conductivity retention rate (69.7%) in Comparative Example 1, the improvement ratio is 13.8%.

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Abstract

The invention relates to a phosphorylated(polyolefin-g-polybenzimidazole) graft copolymer as well as a preparation method and application thereof. According to the graft copolymer, soft polyolefin isused as a main chain, rigid PBI is used as a branched chain, and the phosphorylated graft copolymer which contains phosphonic acid and has a soft-hard chain segment is further prepared through amino-containing phosphonic acid grafting. The polymers with two properties are subjected to microcosmic phase separation to construct a proton transmission channel, so that the proton conductivity is improved. In addition, the flexible main chain drives the PBI branched chain to move so as to reduce proton migration activation energy, promote migration of phosphoric acid or protons and improve proton conductivity. The grafted amino-containing phosphonic acid can reduce the doping amount of inorganic phosphoric acid, so that the loss of phosphoric acid in the use process is reduced, and the proton conductivity retention rate of the membrane is improved.

Description

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

Claims

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Application Information

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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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