Preparation method of monolithic polyaryletherketone bipolar membrane containing porphyrin water dissociation catalytic group in side chain

A polyaryletherketone, bipolar membrane technology, applied in chemical instruments and methods, membrane technology, ion exchange and other directions, can solve the problems of poor graft uniformity, limited use range, increased synthesis steps, etc., and achieves low transmembrane voltage. , The effect of eliminating the film forming process and low resistance

Active Publication Date: 2022-03-15
FUJIAN NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

This method also has several obvious disadvantages: first, the grafting rate is low, and the grafting uniformity is also poor; second, because the porous material is used as the base membrane, the grafted monomers on both sides avoid mutual penetration, and the bipolar membrane The middle interface layer is not clear; the third is that the method of co-radiation grafting will cause a large amount of monomers to self-polymerize, and the utilization rate of the monomers is very low, which is not suitable for industrial production; the fourth is to achieve the required grafting rate. The grafted membrane is cleaned and grafted again (similar to the above-mentioned U.S. patent soaking the monomer solution multiple times and polymerizing), so that the synthesis steps are increased; the fifth is affected by the grafted monomer, the bipolar membrane prepared in the paper, Regardless of its positive or negative side, the chemical stability and thermal stability of its functional groups with ion exchange capabilities are not high, thus greatly limiting its scope of use

Method used

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  • Preparation method of monolithic polyaryletherketone bipolar membrane containing porphyrin water dissociation catalytic group in side chain
  • Preparation method of monolithic polyaryletherketone bipolar membrane containing porphyrin water dissociation catalytic group in side chain
  • Preparation method of monolithic polyaryletherketone bipolar membrane containing porphyrin water dissociation catalytic group in side chain

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] (1) Take 2.0g of bromomethylated polyaryletherketone (BPEEK) into a three-necked flask, dissolve it with 60mL of N-methylpyrrolidone, pass nitrogen gas to remove oxygen, and use methylated polyaryletherketone (based on bromomethyl Based on moles): glycidyl methacrylate (GMA): CuBr: N, N, N', N", N'" pentamethyldiethylenetriamine (PMDETA) molar ratio is 1:40: 1:2 Add glycidyl methacrylate and CuBr in turn, stir well and then add PMDETA. CuBr and PMDETA were used as the catalyst system, and the reaction was carried out at constant temperature for 12 hours at 70°C under the protection of nitrogen. The reaction solution was precipitated with ethanol, and the precipitate was soaked in running water for 24 hours to remove CuBr and CuBr in the precipitate. 2 , PMDETA and unreacted glycidyl methacrylate, filtered, and dried to obtain a solid. The dried graft polymer was dissolved in tetrahydrofuran and cast on a glass plate to form a film, and dried in a constant temperature ...

Embodiment 2

[0051] (1) PEEK-g-PGMA graft copolymer

[0052] Take 2g of bromomethylated polyaryletherketone (BPEEK) and add it into a three-neck flask, dissolve it with 60mL of N-methylpyrrolidone, and pass nitrogen to remove oxygen. ): glycidyl acrylate (GMA): CuBr: N, N, N', N", N'" pentamethyldiethylenetriamine (PMDETA) with a molar ratio of 1:40:1:2 followed by adding formaldehyde Glycidyl acrylate and CuBr, stir well and then add PMDETA. CuBr and PMDETA were used as the catalyst system, and the reaction was carried out at constant temperature for 16 hours at 70°C under nitrogen protection. The reaction solution was precipitated with ethanol, and the precipitate was soaked in running water for 24 hours to remove CuBr and CuBr in the precipitate. 2 , PMDETA and unreacted glycidyl methacrylate, filtered, and dried to obtain a solid. The dried graft polymer was dissolved in tetrahydrofuran and cast on a glass plate to form a film, and dried in a constant temperature oven at 80°C for 24...

Embodiment 3

[0062] (1) Take 2g of bromomethylated polyaryletherketone (BPEEK) and add it to a three-neck flask, dissolve it with 60mL of N-methylpyrrolidone, pass nitrogen to remove oxygen, and press methylated polyaryletherketone (with bromomethyl In terms of moles): vinyl phenyl glycidyl ether (GST): CuBr: N, N, N', N", N'" pentamethyldiethylenetriamine (PMDETA) molar ratio is 1:40: 1:2 Add vinyl phenyl glycidyl ether and CuBr in turn, stir well and then add PMDETA. CuBr and PMDETA were used as the catalytic system, and the reaction was carried out at constant temperature for 20 h at 70 °C under nitrogen protection. The reaction solution was precipitated with ethanol, and the precipitate was soaked in running water for 24 hours to remove CuBr and CuBr in the precipitate. 2 , PMDETA and unreacted glycidyl methacrylate, filtered, and dried to obtain a solid. The dried graft polymer was dissolved in tetrahydrofuran and cast on a glass plate to form a film, and dried in a constant tempera...

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Abstract

The invention relates to a method for preparing a monolithic polyaryl ether ketone bipolar membrane containing a porphyrin water dissociation catalytic group in the side chain, using bromomethylated polysulfone and bromomethylated polysulfone polymer as starting materials to synthesize The polysulfone-based membrane mixture containing porphyrin and epoxy group side groups is mixed and cast on a clean glass plate, and dried to prepare the polysulfone-based membrane containing porphyrin and epoxy group side groups; After the base membrane is sulfonated, ammonized and quaternized, it is washed with deionized water to obtain a monolithic polyaryletherketone bipolar membrane containing phthalocyanine side groups. The bipolar membrane prepared by the present invention adopts a nucleophilic substitution reaction, introduces an epoxy group on the polysulfone side group, introduces an anion and a cation exchange membrane method into the polysulfone molecular chain, and saves the film-forming process and avoids the carcinogen chlorine Use of methyl ether. The prepared bipolar membrane has self-catalysis, low bipolar membrane resistance and low transmembrane voltage. Long-term use, there will be no problems such as bubbling and cracking in the middle interface layer that are prone to occur during the use of composite bipolar membranes.

Description

technical field [0001] The invention relates to a method for preparing a monolithic polyaryl ether ketone bipolar membrane containing a porphyrin water dissociation catalytic group in the side chain, in particular to the introduction of epoxy group-containing polyaryl ether ketone grafted into the polyarylether ketone by living free radical polymerization The side chain, through the further reaction of the epoxy group, introduces the porphyrin group into the side chain of the polyaryletherketone as a water dissociation catalyst in the middle layer of the bipolar membrane, and synthesizes a monolithic polyaryletherketone bismuth containing porphyrin groups in the side chain. Preparation method of polar membrane. Background technique [0002] Bipolar membrane is a new branch developed on the basis of ion exchange membrane technology, and has rapidly developed into a research hotspot in the field of membrane technology. It is usually a functional membrane with a three-layer st...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01D71/72B01D71/82B01D67/00B01J45/00
CPCB01J45/00B01D71/72B01D71/82B01D67/0006
Inventor 黄雪红张睫灵贾玉婷宁金凤李晓燕丁富传
Owner FUJIAN NORMAL UNIV
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