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Preparation method of monolithic polyaryletherketone bipolar membrane with porphyrin hydrolytic dissociation catalytic group on 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: 2020-09-04
FUJIAN NORMAL UNIV
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  • Summary
  • 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 with porphyrin hydrolytic dissociation catalytic group on side chain
  • Preparation method of monolithic polyaryletherketone bipolar membrane with porphyrin hydrolytic dissociation catalytic group on side chain
  • Preparation method of monolithic polyaryletherketone bipolar membrane with porphyrin hydrolytic dissociation catalytic group on 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 flowing 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 preparation method of a monolithic polyaryletherketone bipolar membrane with a porphyrin hydrolysis catalytic group on a side chain. The preparation method comprises the following steps: respectively synthesizing polysulfone base membrane mixed solutions containing porphyrin and epoxy group side groups by taking bromomethylated polysulfone and a bromomethylated polysulfone polymer as starting raw materials, mixing the polysulfone base membrane mixed solutions, performing casting on a clean glass plate, and performing drying to obtain a polysulfone base membrane containing porphyrin and epoxy group side groups; and sulfonating, aminating and quaternizing the base membrane, and washing the base membrane with deionized water to obtain the monolithic polyaryletherketone bipolar membrane containing a phthalocyanine side group. According to the bipolar membrane prepared by the invention, through nucleophilic substitution reaction, an epoxy group is introduced intoa polysulfone side group, and anion and cation exchange membranes are introduced into a polysulfone molecular chain, so that a membrane forming process is omitted, and the use of carcinogen chloromethyl ether is avoided. The prepared bipolar membrane has a self-catalysis effect, and is low in resistance and low in transmembrane voltage. After long-term use, the problems of bubbling, cracking and the like of a middle interface layer, which are easily caused in the use process of a composite bipolar membrane, can be avoided.

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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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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