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Triazolyl long side chain-containing polyphenyl ether anion membrane as well as preparation method and application thereof

An anionic membrane and a technology with a long triazole group, which is applied in the field of polyphenylene ether anionic membrane and its preparation, can solve the problems of decreased ionic conductivity and the inability to meet the large-scale industrialization of alkaline fuel cells, etc., and achieve improved alkali resistance stability, The effect of improving hydroxide conductivity and good mobility

Pending Publication Date: 2022-07-29
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

On the other hand, due to the strong nucleophilic basic working conditions of functional organic cations in AEMs, multiple degradation reactions such as Hofmann elimination, SN2 nucleophilic substitution or ylide may occur at high temperature, resulting in a decrease in ionic conductivity, so it cannot meet Large-Scale Industrialization of Alkaline Fuel Cells

Method used

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  • Triazolyl long side chain-containing polyphenyl ether anion membrane as well as preparation method and application thereof
  • Triazolyl long side chain-containing polyphenyl ether anion membrane as well as preparation method and application thereof
  • Triazolyl long side chain-containing polyphenyl ether anion membrane as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] (1) Alkynyl functionalization of quaternary ammonium salts: Propynyl bromide (30 mmol), trimethylamine (150 mmol in 20 mL of tetrahydrofuran solution) and 100 mL of toluene were added to a 250 mL round bottom flask. After stirring at room temperature for 24 h, the white precipitate was filtered, washed three times with ether, and dried in vacuo to obtain alkynyl-functionalized quaternary ammonium salt QA-1 with a yield of 82%.

[0047] (2) Cu(I)-catalyzed azide-alkynyl cycloaddition (CuAAC) reaction: PPO-N3-m copolymer, m is 30% (1.814mmol azide group), QA-1 (2.177 mmol), catalyst pentamethyldiethylenetriamine (PMDETA) (0.227 mL, 1.089 mmol), CuBr (0.544 mmol) and 10 mL of NMP were added to a Shrek flask. Degassed by several freeze-thaw pump cycles, filling the bottle with argon and stirring at 50°C for 48h. The polymer solution was poured into deionized water, and the solid product (PPO-G-QA) was washed several times with water to remove the catalyst, and then vacuum-...

Embodiment 2

[0051] (1) Alkynyl functionalization of quaternary ammonium salts: 4-bromo-1-butyne (30 mmol), trimethylamine (150 mmol in 20 mL of tetrahydrofuran solution) and 100 mL of toluene were added to a 250 mL round bottom flask. After stirring at room temperature for 24 h, the white precipitate was filtered, washed with ether three times, and dried in vacuo to obtain alkynyl-functionalized quaternary ammonium salt QA-2 with a yield of 82%.

[0052] (2) Cu(I) catalyzed azide-alkynyl cycloaddition (CuAAC) reaction: with embodiment 1, just replace QA-1 in embodiment 1 step (2) with QA-2, obtain solid product (PPO-G-2QA).

[0053] (3) Membrane preparation and ion exchange: the same as in Example 1, except that the raw material PPO-G-QA in step (3) of Example 1 was replaced with PPO-G-2QA.

[0054] The test shows that the water content of the long-chain branched polyphenylene ether anion exchange membrane prepared in this example is 38%, and the ionic conductivity is 19mS·cm -1 , its a...

Embodiment 3

[0056] (1) Alkynyl functionalization of quaternary ammonium salts: 5-iodo-1-pentyne (30 mmol), trimethylamine (150 mmol in 20 mL of tetrahydrofuran solution) and 100 mL of toluene were added to a 250 mL round bottom flask. After stirring at room temperature for 24 h, the white precipitate was filtered, washed with ether three times, and dried in vacuo to obtain alkynyl-functionalized quaternary ammonium salt QA-3 with a yield of 82%.

[0057] (2) Cu(I) catalyzed azide-alkynyl cycloaddition (CuAAC) reaction: with embodiment 1, just replace QA-1 in embodiment 1 step (2) with QA-3, obtain solid product (PPO-G-3QA).

[0058] (3) Membrane preparation and ion exchange: the same as in Example 1, except that the raw material PPO-G-QA in step (3) of Example 1 was replaced with PPO-G-3QA.

[0059] The test shows that the water content of the long-chain branched polyphenylene ether anion exchange membrane prepared in this example is 44%, and the ionic conductivity is 24mS·cm -1 , its a...

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Abstract

The invention discloses a triazolyl long side chain-containing polyphenyl ether anionic membrane as well as a preparation method and application thereof, and belongs to the technical field of membranes. According to the membrane material, polyphenyl ether is taken as a main chain, quaternary ammonium salt alkynyl functionalization, azide functionalization and a Cu (I) catalytic azide-alkynyl cycloaddition (CuAAC) reaction are carried out, a long-chain branch with a triazolyl group is introduced, and a novel alkaline anion exchange membrane is prepared after ionization. According to the present invention, by introducing the triazolyl-containing long-chain branch, the membrane has advantages of good alkali resistance, high ionic conductivity and excellent dimensional stability, and by introducing the triazolyl group, the hydroxyl conductivity of the membrane is further improved, such that the triazolyl-containing anion exchange membrane material can be used as the alkaline fuel cell anion exchange membrane material.

Description

technical field [0001] The invention belongs to the technical field of membranes, and in particular relates to a polyphenylene ether anion membrane containing a long side chain of a triazole group and a preparation method and application thereof. Background technique [0002] Polymer electrolyte membrane fuel cells (PEMFCs) are an important new type of energy battery with the advantages of green environmental protection, high specific power, high reliability, low operating temperature, and fast start-up speed. Polymer electrolyte membrane fuel cells include proton exchange membrane fuel cells and hydroxide ion exchange membrane fuel cells. Compared with the proton exchange membrane fuel cell, the working environment of the hydroxide ion exchange membrane fuel cell is alkaline, and the catalytic activity of the electrode is greatly improved, so that non-precious metals can be selected as the catalyst, and the catalyst is more stable, which is expected to solve the cost and st...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M8/1025H01M8/1069C08G65/48
CPCH01M8/1025H01M8/1069C08G65/485Y02E60/50
Inventor 庄小东刘刚袁佳熙朱金辉柯长春陆陈宝张清
Owner SHANGHAI JIAO TONG UNIV
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