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Sulfonated polymer/modified polystyrene compound and ion exchange membrane

A technology of sulfonated polymers and polystyrene, applied in electrochemical generators, fuel cells, electrical components, etc., can solve problems such as poor hydrolysis stability, improve water retention capacity, improve proton transmission capacity, and improve barrier properties Effect

Pending Publication Date: 2022-06-03
国家电投集团氢能科技发展有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Some studies have grafted phosphate groups into polymers through C-O-P or Si-O-P, but this technology has the problem of poor hydrolytic stability

Method used

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  • Sulfonated polymer/modified polystyrene compound and ion exchange membrane
  • Sulfonated polymer/modified polystyrene compound and ion exchange membrane
  • Sulfonated polymer/modified polystyrene compound and ion exchange membrane

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preparation example Construction

[0124] The embodiment of the present invention also provides a method for preparing a sulfonated polymer / modified polystyrene composite, which is characterized in that it includes the following steps: 0.1%-95% of modified polystyrene and 5%-99.9% of sulfonic acid The polymers, on a mass basis, were prepared by a blending method.

[0125] In some embodiments of the present invention, the preparation method of modified polystyrene (PS-A / PS-B) comprises the following steps:

[0126] a. Disperse halomethylated polystyrene in an organic medium to prepare a polymer dispersion;

[0127] b, adding phosphoric acid functionalization reagent to the polymer dispersion of step a, and carrying out functionalization reaction;

[0128] c, adding a precipitant to the reaction solution in step b, and drying to obtain a polymer (PS-A) of a halomethylated polystyrene grafted phosphate group;

[0129] d-1, adding an acidifying agent to the reaction solution in step b, performing acidification, t...

Embodiment 1

[0174] Example 1: Thermally induced preparation of phosphorylated polystyrene

[0175] Weigh 10g of halomethylated polystyrene, dissolve it in 240g of N,N dimethylacetamide at 60°C, add 5 times the molar amount of halomethyl phosphite, and react at 140°C for 48h . Add acetone for precipitation to obtain an intermediate product, and acidify the intermediate product in 2M hydrochloric acid at 40 °C for 12 h to obtain phosphorylated polystyrene.

[0176] Halomethylated polystyrenes include:

[0177] The homopolymer polychloromethyl styrene (PVBC) obtained by the polymerization of the monomers, the functionality of the polymer is 100%, and the Mw is 27kg / mol;

[0178] The copolymer (Cl-PS-1) obtained by the polymerization of p-chloromethylstyrene and p-methylstyrene monomer, the functionality of the polymer is 61.6%, and the Mw is 72kg / mol;

[0179] Chloromethylated polystyrene (Cl-PS-2) prepared by trimethylchlorosilane and trioxane as chloromethylation reagents, and tin tetrach...

Embodiment 2

[0184] Example 2: Photoinitiated Preparation of Phosphorylated Polystyrene

[0185] Weigh 10 g of the halomethylated polystyrene in Example 1, dissolve it in 190 g of chloroform at room temperature, add 2 times the molar amount of halomethyl triethyl phosphite, at 50 ° C, 365 nm wavelength The reaction was carried out under ultraviolet light irradiation for 8 hours, and 10 g of trimethylbromosilane was added for acidification at 40 °C for 12 hours, then precipitated by adding water, and dried in vacuum at 60 °C to obtain phosphorylated polystyrene. The parameters of phosphorylated polystyrene are shown in Table 2.

[0186] Table 2

[0187]

[0188] In this example, the photo-induced phosphorylation reaction has few cross-linking side reactions, the Mw of phosphorylated polystyrene is close to the theoretical value, and it is easier to dissolve and blend, and the non-cross-linked structure is conducive to the transport of ions in the ion exchange membrane.

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Abstract

The invention relates to a sulfonated polymer / modified polystyrene compound and an ion exchange membrane, the sulfonated polymer / modified polystyrene compound comprises 0.1-95% by mass of modified polystyrene and 5-99.9% by mass of sulfonated polymer, and the sulfonated polymer / modified polystyrene compound is prepared by a blending method; the modified polystyrene is at least one of a polymer of a halomethylated polystyrene grafted phosphate group, a polymer of a halomethylated polystyrene grafted phosphate group, and a polymer of halomethylated polystyrene grafted polyvinyl phosphate. The sulfonated polymer / modified polystyrene compound provided by the embodiment of the invention has good comprehensive performance under different temperature and humidity when being applied to the fuel cell. The conductivity of the ion exchange membrane under full temperature and humidity can be improved through a hydrogen bond network and complexing action formed between the phosphate group and the sulfonic acid group, the water absorption rate is regulated and controlled, and the stability is enhanced.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, in particular to a sulfonated polymer / modified polystyrene composite, and in particular to a sulfonated polymer / modified polystyrene ion exchange membrane. Background technique [0002] Clean hydrogen energy and high energy density fuel cells are essential for the sustainable development of global energy. Sulfonated polymers are the main materials of low-temperature fuel cell proton exchange membranes, and currently commercialized proton exchange membranes for vehicle fuel cells all use perfluorosulfonic acid resin as the polyelectrolyte. Phosphorylated polymers also have a certain proton conductivity, but their electrical conductivity is low when used alone as proton exchange membrane materials, and there is no high-performance phosphorylated polymer-based proton exchange membrane. [0003] In the existing research, the application of phosphorylated polymers, small molecular compounds...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L29/10C08L25/18C08L25/06C08L51/00C08L61/16C08L81/06C08J5/22H01M8/1044H01M8/1041
CPCC08J5/2237C08J5/2256C08J5/2231H01M8/1044H01M8/1041C08J2329/10C08J2425/18C08J2425/06C08J2451/00C08J2361/16C08J2381/06C08J2325/18C08J2325/06Y02E60/50
Inventor 李丹刘昊张泽天张亚欢董天都杨云菲焦佳佳
Owner 国家电投集团氢能科技发展有限公司
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