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Preparation method of anion exchange membrane through crosslinking by using 4,4'-trimethylenedipiperidine (TMDP)

A technology of anion exchange membrane and cross-linking agent, which is applied in the direction of chemical instruments and methods, membrane, membrane technology, etc., can solve the limitation of practical application, reduce the swelling degree and water absorption rate of anion exchange membrane, and the deterioration of mechanical properties and dimensional stability and other problems, to achieve the effect of improving anti-swelling performance, good physical and chemical stability, and good thermal stability

Active Publication Date: 2019-02-01
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

In order to enhance the ion transport capacity of the ion exchange membrane, the ion exchange membrane usually needs to have a higher IEC, which often leads to poor mechanical properties and dimensional stability of the membrane. Therefore, without reducing the IEC, the membrane can be simultaneously Having high mechanical strength and dimensional stability is also a problem that needs to be solved at present
Cross-linking is an effective method to reduce the swelling degree and water absorption of anion exchange membrane; at the same time, the current anion exchange membrane will be degraded under high temperature and alkaline environment, because the quaternary ammonium group will undergo Hoffman elimination and nucleophilic substitution reaction, from The detachment of polymer chains makes the anion exchange membrane unable to maintain its stability in alkaline solution for a long time, which limits its practical application. In addition, long-term alkaline stability is also critical for evaluating the life of anion exchange membranes

Method used

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  • Preparation method of anion exchange membrane through crosslinking by using 4,4'-trimethylenedipiperidine (TMDP)
  • Preparation method of anion exchange membrane through crosslinking by using 4,4'-trimethylenedipiperidine (TMDP)
  • Preparation method of anion exchange membrane through crosslinking by using 4,4'-trimethylenedipiperidine (TMDP)

Examples

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preparation example Construction

[0024] Preparation of chloromethylated polysulfone (CMPSF):

[0025] Pour 10g of polysulfone (PSF) into a three-necked flask, then add 500mL of chloroform, stir for 12h to completely dissolve, then add 13.56g of paraformaldehyde, 57.36mL of trimethylchlorosilane and 0.53mL of tetra Tin chloride was sequentially added to the above solution, heated and stirred for 60 h, and the temperature was set at 50°C. Finally, the solution was precipitated in an ethanol solution to precipitate the product, and then the product was suction-filtered and dried to obtain chloromethylated polysulfone (CMPSF).

Embodiment 1

[0027] Accurately weigh 0.5 g of chloromethylated polysulfone into 7 mL of 1-methyl-2-pyrrolidone (NMP), stir and dissolve at room temperature for 5 h to obtain a colorless transparent solution. Add 0.023g of 4,4'-trimethylenedipiperidine (TMDP) to the resulting solution, and then stir the reaction at room temperature for 2h to cause a cross-linking reaction to obtain a light yellow liquid, then add 0.112g of N- Methylpyrrolidine (MPY) was added to the above solution, stirred for 4 hours, and then the obtained casting solution was defoamed in a vacuum drying oven. Then pour it on a clean glass plate and scrape the film with a spatula, and dry it under vacuum for 24 hours at 80°C. Take out the dried membrane, soak it in deionized water, let it fall off freely, and use it for future use (denoted as CAPSF-5 membrane).

Embodiment 2

[0029] Accurately weigh 0.5 g of chloromethylated polysulfone (CMPSF) into 7 mL of 1-methyl-2-pyrrolidone (NMP), stir and dissolve at room temperature for 5 h to obtain a colorless transparent solution. Add 0.039g of 4,4'-trimethylenedipiperidine (TMDP) to the resulting solution, and then stir the reaction at room temperature for 1.5h to cause a cross-linking reaction to obtain a light yellow liquid, then add 0.099g of N - Methylpyrrolidine (MPY) was added to the above solution, stirred for 4 hours, and then the casting solution was defoamed in a vacuum drying oven. Then pour it on a clean glass plate and scrape the film with a spatula, and dry it under vacuum for 24 hours at 80°C. Take out the dried membrane, soak it in deionized water, let it fall off freely, and use it for future use (denoted as CAPSF-10 membrane).

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Abstract

The invention disclose a preparation method of an anion exchange membrane by using 4,4'-trimethylenedipiperidine (TMDP) as a cross-linking agent. The preparation method is implemented according to thefollowing steps: (1) dissolving chloromethylated polysulfone in 1-methyl-2-pyrrolidinone (NMP) at room temperature to obtain a colorless transparent chloromethylated polysulfone solution A; (2) adding a certain amount of 4,4'-trimethylenedipiperidine into the chloromethylated polysulfone solution A at room temperature, and carrying out stirring for 0.5-2 hours to carry out a cross-linking reaction on the 4,4'-trimethylenedipiperidine with the chloromethylated polysulfone to obtain a chloromethylated polysulfone solution B; (3) adding N-methylpyrrolidine into the chloromethylated polysulfone solution B at room temperature, carrying out stirring for 0.5-4 hours to carry out a quaternization reaction until the reaction is completed to obtain a membrane casting solution; and (4) completely deforming the membrane casting solution, pouring the membrane casting solution on a clean glass plate, carrying out film scraping by using a scraper, then carrying out vacuum drying, soaking the glass plate in deionized water so that a membrane naturally falls off from the glass plate, and carrying out washing with deionized water to obtain the anion exchange membrane. The anion exchange membrane has good alkali resistant stability and swelling resistance.

Description

(1) Technical field [0001] The invention belongs to the technical field of preparation of anion exchange membranes, and in particular relates to a preparation method of anion exchange membranes cross-linked by TMDP. (2) Background technology [0002] In recent years, technologies related to ion exchange membranes and electrodialysis have developed rapidly, and have been widely used in water treatment, environmental protection, energy and clean production. At present, in order to meet the harsh chemical application conditions, it is urgent to develop ion exchange membranes with excellent ion selective permeability, low electrical resistance, high mechanical strength, chemical stability, and dimensional stability. In order to enhance the ion transport capacity of the ion exchange membrane, the ion exchange membrane usually needs to have a higher IEC, which often leads to poor mechanical properties and dimensional stability of the membrane. Therefore, without reducing the IEC, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01D71/68B01D69/02B01D67/00C08K5/3435
CPCB01D67/0009B01D69/02B01D71/68B01D2325/42C08K5/3435
Inventor 沈江南姜玉良阮慧敏潘杰锋
Owner ZHEJIANG UNIV OF TECH
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