Novel branch-containing poly(arylpiperidinium) copolymer ionomer, anion exchange membrane, and method for producing the same.

Abstract

The present invention relates to a poly(arylpiperidinium) copolymer ionomer in which a branched piperidinium group is introduced into a repeating unit while having no aryl ether bond in the polymer backbone, which has excellent chemical stability, excellent mechanical properties while having a high molecular weight, a low expansion rate, high dimensional stability and ionic conductivity, and a limited phenyl adsorption effect. Further, an anion exchange membrane produced from the above branched poly(arylpiperidinium) copolymer ionomer can operate even under low humidity conditions and has excellent water management ability, and thus can be applied to membranes and binders for alkaline fuel cells, water electrolysis devices, carbon dioxide reduction, vanadium redox flow batteries, or metal-air batteries.

Claims

1. A branch-containing poly(arylpiperidinium) copolymer ionomer having repeating units represented by the following chemical formula. 【Chemistry 1】 Here, in the above chemical formula, Aryl monomers are two or more distinct compounds selected from the compounds represented by the following structural formula (Chemical Formula 2). 【Chemistry 2】 The branching agent is one of the compounds represented by the following structural formula (Chemical Formula 3). 【Transformation 3】

2. (I) As monomers, (a) Two or more different compounds selected from the compounds represented by the following structural formula (Chemical Formula 4), 【Chemistry 4】 (b) One or more compounds selected from those represented by the following structural formula (Chemical Formula 5), ​​and 【Transformation 5】 (c) A step of dissolving 1-methyl-4-piperidone in an organic solvent to form a solution, (II) A step of gradually adding a strong acid catalyst to the solution, stirring and reacting it to obtain a viscous solution, (III) A step of precipitating, washing and drying the viscous solution to obtain a solid polymer, (IV) K ２ CO ３ and a step of adding and reacting an excess amount of halomethane to form a quaternary piperidinium salt, (V) A step of precipitating, washing and drying the polymer solution, A method for producing a branch-containing poly(arylpiperidinium) copolymer ionomer.

3. In claim 2, A method for producing a branch-containing poly(arylpiperidinium) copolymer ionomer, wherein the organic solvent in step (I) is a halogenated solvent, one or more selected from the group consisting of dichloromethane, chloroform, dichloroethane, dibromomethane, and tetrachloroethane.

4. In claim 2, A method for producing a branch-containing poly(arylpiperidinium) copolymer ionomer, wherein the strong acid catalyst in step (II) is trifluoroacetic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, heptafluorobutyric acid, or a mixture thereof.

5. In claim 2, A method for producing a branch-containing poly(arylpiperidinium) copolymer ionomer, wherein the organic solvent in step (IV) is N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, or dimethylformamide.

6. An anion exchange membrane comprising a branch-containing poly(arylpiperidinium) copolymer ionomer as described in claim 1.

7. (i) A step of dissolving the branch-containing poly(arylpiperidinium) copolymer ionomer described in claim 1 in an organic solvent to form a polymer solution, (ii) A step of casting the polymer solution onto a glass plate and drying it to obtain a film, (iii) The obtained film is dissolved in 1 M NaHCO ３ Alternatively, the process involves treating with 1M NaOH, followed by several washes and drying with ultrapure water. A method for producing an anion exchange membrane, including [the specified component].

8. In claim 7, A method for producing an anion exchange membrane, wherein the concentration of the polymer solution is 2 to 30% by weight.

9. In claim 7, A method for producing an anion exchange membrane, wherein the drying in step (ii) above includes gradually removing the organic solvent in an oven at 80-90°C for 24 hours, and then completely removing the organic solvent by heating in a vacuum oven at 120-150°C for 12 hours.

10. A binder for an alkaline fuel cell comprising the branch-containing poly(arylpiperidinium) copolymer ionomer described in claim 1.

11. An alkaline fuel cell comprising the anion exchange membrane described in claim 6.

12. A water electrolysis apparatus comprising an anion exchange membrane as described in claim 6.

13. A carbon dioxide reduction apparatus comprising an anion exchange membrane as described in claim 6.

14. A vanadium redox flow battery comprising the anion exchange membrane described in claim 6.

15. A metal-air battery comprising the anion exchange membrane described in claim 6.

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