Preparation method of cross-linking type composite anion-exchange membrane

A composite anion and exchange membrane technology, which is applied to fuel cell components, fuel cells, electrical components, etc., can solve the problems of low impregnation rate, ion exchange capacity limitation, low monomer impregnation rate, etc., and achieve simple and efficient reaction , the effect of good dimensional stability

Active Publication Date: 2013-11-13
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Application Information

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Problems solved by technology

The disadvantages of this method are: (1) Due to the high crystallinity of polyethylene film, the impregnation rate of monomer is not high, up to 45%; (2) Divinylbenzene is used as a crosslinking agent to introduce into the base film to replace a certain amount The ionic functional group monomer loses a certain amount of ion exchange capacity, which limits the preparation of higher ion exchange capacity; (3) The monomer mixed impregnation solution cannot be stored for a long time, resulting in a lot of waste of raw materials
This method has similar disadvantages as above: (1) Since the C-F polarity of the tetrafluoroethylene membrane is very strong, it is difficult for the polymerized monomer to enter the interior of the tetrafluoroethylene membrane, which leads to a low monomer impregnation rate; (2) using divinylbenzene Introduced into the basement membrane as a crosslinking agent, replacing a certain amount of ionic functional group monomers, and losing a certain amount of ion exchange capacity, which limits the preparation of higher ion exchange capacities; (3) The monomer mixed impregnation solution cannot last for a long time Preservation, resulting in a large waste of raw materials; (4) Since monomers need to be thermally initiated to polymerize to form high polymers, the polymerization reaction cannot be carried out 100%, and there may be residual monomers remaining in the film. In addition, the initiator benzoyl peroxide reacts Finally, there will be products generated, and they will also remain in the membrane, which will lead to the loss of membrane performance.

Method used

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  • Preparation method of cross-linking type composite anion-exchange membrane
  • Preparation method of cross-linking type composite anion-exchange membrane
  • Preparation method of cross-linking type composite anion-exchange membrane

Examples

Experimental program
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Effect test

Embodiment 1

[0032] Cut out 10×10cm 2 PTFE porous membrane with a thickness of 10 μm is soaked in ethanol solution for 24 hours to remove surface organic matter.

[0033] To prepare a quaternized polymer solution, weigh 1 weight unit (eg: g) (eg: g) (eg: g) of chloromethylated polystyrene (PVBC) (chloromethylation degree 100%) solution Dissolve in 20 weight units (eg: g) (eg: g) (eg: g) of N,N-dimethylformamide (DMF), and stir overnight at room temperature. Add 30% PVBC chloromethylated diethylamine solution under stirring at 40°C, add 5 weight units (eg: g) (eg: g) (eg: g) DMF to it, and stir for 4 hours at 40°C , to obtain a partially tertiary aminated polymer solution (crosslinking precursor). The reaction temperature of the system is lowered to 30° C., the trimethylamine aqueous solution is heated, and the trimethylamine gas is passed into the reaction system for 1 hour to obtain a quaternized polymer solution.

[0034] Take 5 weight units (eg: g) (eg: g) (eg: g) of the quaternized ...

Embodiment 2

[0043] Adopt the same operation process as embodiment 1. But the addition of diethylamine is 50% of PVBC chloromethylation molar weight. The prepared cross-linked composite anion exchange membrane is denoted as TPPVBN50.

[0044] The dimensional change rate and ion exchange capacity tests of the membrane prepared in this embodiment show that the ion exchange capacity of the membrane at room temperature is 2.19 mmol / g.

[0045] In this case, the following alternative conditions can be used to obtain membranes with similar properties: (1) Polymers: chloromethylated polysulfone (PSFC), chloromethylated polyaryletherketone (PPEKC), chloromethylated polyaryletherketone (PPEKC), chloromethylated (2) Organic solvents: N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP ) or dimethyl sulfoxide (DMSO); (3) secondary amine reagents: dipropylamine or dibutylamine.

[0046] figure 2 In B, the ion conductivity of the membrane in this embodiment, the ion conductivity of the membrane...

Embodiment 3

[0048] Adopt the same operation process as embodiment 1. But the addition of diethylamine is 70% of PVBC chloromethylation molar weight. The prepared cross-linked composite anion exchange membrane is denoted as TPPVBN70.

[0049] The ion exchange capacity test of the membrane prepared by this embodiment shows that the ion exchange capacity of the membrane at room temperature is 2.05mmol / g.

[0050] In this case, the following alternative conditions can be used to obtain membranes with similar properties: (1) High polymer: chloromethylated polysulfone (PSFC) or chloromethylated polyaryletherketone (PPEKC), chloromethylated (2) Organic solvents: N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP ) or dimethyl sulfoxide (DMSO); (3) secondary amine reagents: dipropylamine or dibutylamine.

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Abstract

A preparation method of a cross-linking type composite anion-exchange membrane comprises the following steps: soaking a (polytetrafluoroethylene) PTFE porous membrane in an ethanol solution for removing organic matters on the surface of the PTFE porous membrane; dissolving a chloromethylated polymer in an organic solvent, and adding a lower secondary amine reagent for configuration of a partly tertiary aminated polymer solution (a cross-linking precursor solution); letting in a lower tertiary amine reagent for quaternization; casting to prepare a PTFE composite membrane by a phase transformation method; immersing the prepared composite membrane in the lower tertiary amine reagent for the quaternization to obtain the anion-exchange membrane based on PTFE. The preparation method of the cross-linking type composite anion-exchange membrane is simple and efficient, and the prepared anion-exchange membrane has high ion-exchange capacity, high ionic conductivity and good dimensional stability and has wide application prospect in the alkaline fuel cells.

Description

technical field [0001] The invention relates to a preparation method of a cross-linked composite anion exchange membrane. Background technique [0002] Anion exchange membranes are widely used in water treatment, material purification, concentration, separation, chlor-alkali industry, heavy metal recovery, alkaline anion exchange membrane fuel cells, liquid flow energy storage batteries, new supercapacitors, etc. Since the anion exchange membrane is more complicated and difficult to prepare than the cation, and it is most likely to be contaminated by precipitation corrosion and organic substances in the electrodialysis process, which directly affects the life of the desalinator, so the development of anion exchange membrane is more special and important. significance. [0003] Chinese patent 200810047595.0 discloses a preparation method of polymer anion exchange membrane, which is composed of the steps of chloromethylation, quaternization and film formation of the polymer i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08J7/12C08J5/22C08J3/24C08L27/18C08L81/06C08L25/06C08L71/10C08L61/16H01M8/02H01M2/16H01M8/1072H01M50/409
CPCY02E60/12Y02E60/50
Inventor 俞红梅赵云邵志刚衣宝廉
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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