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A kind of ammonium-crosslinked anion exchange membrane containing soft segment and hard segment copolymer and preparation method thereof

A technology of anion exchange membrane and copolymer, which is applied in the field of ammonium cross-linked anion exchange membrane containing soft segment and hard segment copolymer and its preparation, can solve the problems of performance degradation, easy swelling, application limitation, etc., and improve the use of Effect of high modulus of elasticity and high ion content on lifetime, fuel barrier capability and

Active Publication Date: 2018-07-27
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] (2) The preparation method of polyvinyl alcohol anion exchange membrane is simple, easy to form a film, and the raw material price is low. This type of membrane has high chemical stability in an alkaline environment and can work continuously for more than 120 days at room temperature, but At higher temperatures, the performance drops a lot, and its ionic conductivity drops from 0.19S / cm to 0.07S / cm, see Géraldine Merle, Seyed Schwan Hosseiny, Matthias Wessling, Kitty Nijmeijer, New cross-linked PVAbased polymer electrolyte membranes for alkaline fuel cells, Journal of Membrane Science, 2012, 409-410: 191-199, and this type of membrane is easy to swell, which limits the application, and there are still deficiencies to be improved
[0014] So far, there have been no reports on the ammonium cross-linked poly(styrene-b-isobutylene-b-styrene) anion exchange membrane containing soft segment and hard segment copolymer and its preparation method

Method used

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  • A kind of ammonium-crosslinked anion exchange membrane containing soft segment and hard segment copolymer and preparation method thereof
  • A kind of ammonium-crosslinked anion exchange membrane containing soft segment and hard segment copolymer and preparation method thereof
  • A kind of ammonium-crosslinked anion exchange membrane containing soft segment and hard segment copolymer and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] Chloromethylated poly(styrene-b-isobutylene-b-styrene) triblock copolymer (number average molecular weight is 100000, polystyrene segment mass percent is 48%, chloromethyl content is 1.7mmol / g copolymer) was dissolved in chloroform, the polymer concentration was 67g / L, 8.5mmol of tetramethylethylenediamine was added thereto, the molar ratio of chloromethyl to amine groups was 0.10:1, and the mixture was evenly stirred. Spread the polymer solution in a flat vessel, and volatilize the solvent at 25°C to obtain an ammonium chloride salt-substituted poly(styrene-b-isobutylene-b-styrene) anion exchange membrane, and further place the membrane at 25°C Soak in 1mol / L NaOH solution for 24 hours to obtain ammonium hydroxide cross-linked poly(styrene-b-isobutylene-b-styrene) anion exchange membrane with a film thickness of 250 μm and a nitrogen ion content of 1.2 mmol / g Copolymer, ionic conductivity at 30°C is 4.0×10 -2 S / cm, the methanol permeability is 7.4×10 -7 cm 2 / s, th...

Embodiment 2

[0046] Chloromethylated poly(styrene-b-isobutylene-b-styrene) triblock copolymer (number average molecular weight is 79000, polystyrene segment mass percent is 43%, chloromethyl content is 1.5mmol / g copolymer) was dissolved in chloroform, and the polymer concentration was 67g / L. 7.5 mmol of tetramethyl-1,3-propanediamine was added thereto, the molar ratio of chloromethyl groups to amine groups was 0.098:1, and the film-making method was the same as in Example 1. The prepared ammonium hydroxide cross-linked poly(styrene-b-isobutylene-b-styrene) anion exchange membrane has a film thickness of 190 μm, a nitrogen ion content of 1.3 mmol / g copolymer, and ion conduction at 30°C The rate is 2.7×10 -2 S / cm, methanol permeability 2.5×10 -7 cm 2 / s, the elastic modulus (60°C) is 716MPa.

Embodiment 3

[0048] Chloromethylated poly(styrene-b-isobutylene-b-styrene) solution is the same as in Example 2, to which 7.5mmol tetramethyl-1,6-hexamethylenediamine is added, the molar ratio of chloromethyl to amine groups It is 0.10:1, and the film-making method is the same as embodiment 1, obtains the ammonium hydroxide cross-linked poly(styrene-b-isobutylene-b-styrene) anion exchange membrane, and film thickness is 150 μ m, and nitrogen ion content is 1.0mmol / g copolymer, the ion conductivity at 30°C is 2.1×10 -2 S / cm, methanol permeability 0.7×10 -7 cm 2 / s, the modulus of elasticity (60°C) is 410MPa.

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Abstract

The invention relates to an ammonium cross-linked anion exchange membrane and a preparation method thereof, which uses chloromethylated poly(styrene-b-isobutylene-b-styrene) as a raw material and bifunctional or multifunctional organic amine compounds as The ammonium cross-linking reagent adopts the method of in-situ generation, and the cross-linking reaction is carried out at the same time as the ammonization reaction. The obtained anion exchange membrane has high methanol barrier property, high ion conductivity and high elastic modulus. And the preparation method is simple and efficient. The prepared ammonium cross-linked anion exchange membrane has improved ion conduction performance, fuel barrier performance and mechanical elasticity, making it suitable for alkaline fuel cell membrane materials.

Description

Technical field: [0001] The invention relates to an ammonium cross-linked anion exchange membrane containing a soft segment and a hard segment copolymer and a preparation method thereof. The obtained anion exchange membrane has higher gas-liquid barrier properties, higher ion conductivity and higher Mechanical properties, and the preparation method is simple and efficient. Background technique: [0002] Membrane materials have been widely used in various scientific research and industrial applications. It is particularly prominent in food processing, wastewater treatment, biomedicine and energy. Among many kinds of membranes, ion exchange membranes occupy an indispensable position in the field of clean energy due to their unique ion selective migration function. [0003] As a clean energy source, fuel cells can directly convert chemical energy into electrical energy with high conversion efficiency, no pollution to the environment, and no harmful gas emissions. At present,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01D71/82B01D69/02B01D67/00
Inventor 吴一弦代培修健徐日炜
Owner BEIJING UNIV OF CHEM TECH