Preparation method of monolithic polyaryletherketone bipolar membrane containing phthalocyanine group in side group

A polyaryletherketone-based membrane and polyaryletherketone technology, applied in chemical instruments and methods, membrane technology, semi-permeable membrane separation, etc., can solve problems such as increased synthesis steps, self-polymerization of monomers, and limited use range, etc. Achieve the effects of low resistance, low transmembrane voltage, and save the film forming process

Active Publication Date: 2022-05-06
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 film is cleaned and regrafted (similar to US Patents US4024043 and US4057481 soaking the monomer solution multiple times and polymerizing), which increases the number of synthesis steps; the fifth is affected by the grafted monomers. The chemical and thermal stability of the functional groups with ion exchange capacity of the membrane, whether it is its positive side or its negative side, is not high, which greatly limits its application range

Method used

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  • Preparation method of monolithic polyaryletherketone bipolar membrane containing phthalocyanine group in side group
  • Preparation method of monolithic polyaryletherketone bipolar membrane containing phthalocyanine group in side group
  • Preparation method of monolithic polyaryletherketone bipolar membrane containing phthalocyanine group in side group

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] (1) Side group bonded phthalocyanine substituent PL-PAEK polymer: In a 100mL three-necked bottle, add 10.0g of bromomethylated polyaryletherketone and 100mL of DMAc, and after the copolymer is fully dissolved, dissolve 17.1g in 40mL The DMAc solution of copper hydroxyphthalocyanine and 1.24g NaOH were added together into a three-necked flask, heated to 40°C under nitrogen protection, and reacted at a constant temperature for 8h. The mixed solution is used as a precipitant, and the product polymer is precipitated, washed with the mixed solution for several times, and dried in vacuum to obtain a polymer (Pc-PAEK) with phthalocyanine (Pc) bonded to the side chain.

[0044]

[0045] (2) 10.0 g of bromomethylated polyaryl ether ketone was added into a three-necked flask, dissolved with 100 mL of N-methylpyrrolidone, and set aside. Then weigh 5.74g 3,5-trimethoxyphenol and 1.45g NaOH, dissolve with 20mL N-methylpyrrolidone, stir at room temperature for 0.5h, add dropwise t...

Embodiment 2

[0056] (1) Synthesis of bipolar membrane interlayer water catalyst-side chain-bonded phthalocyanine substituent Pc-PAEK polymer: in a 100mL three-necked flask, add 5.0g bromomethylated polyaryletherketone polymer and 60mL DMAc, After the copolymer was fully dissolved, 20 mL of DMAc solution containing 11.7 g of manganese hydroxyphthalocyanine and 1.7 g of NaHCO were dissolved. 3 , were added into a three-necked flask, heated to 50°C under nitrogen protection, and reacted at a constant temperature for 5 hours. After the reaction, the system was immediately cooled to room temperature with an ice-water bath, and a mixture of distilled water and methanol was used as a precipitant to precipitate the product polymerization. The compound was washed with the mixed solution for several times and dried in vacuum to obtain a polymer (Pc-PAEK) with phthalocyanine (Pc) bonded to the side chain.

[0057]

[0058] (2) 10.0g of bromomethylated polyaryletherketone was added into a three-nec...

Embodiment 3

[0069] (1) Synthesis of bipolar membrane intermediate layer water catalyst-side chain bonded phthalocyanine substituent Pc-PAEK polymer: in a three-necked flask, add 8.0g bromomethylated polyaryletherketone polymer and 80mL DMAc, After the copolymer was fully dissolved, 9.18g of zinc hydroxyphthalocyanine, 50mL of DMAc solution and 1.47g of NaHCO were dissolved. 3 , were added into a three-necked flask, heated to 45°C under nitrogen protection, and reacted at a constant temperature for 8 hours. After the reaction was completed, the system was immediately cooled to room temperature with an ice-water bath, and a mixture of distilled water and methanol was used as a precipitant to precipitate the product polymerization. The compound was washed with the mixed solution for several times and dried in vacuum to obtain a polyaryletherketone polymer (Pc-PAEK) with phthalocyanine (Pc) bonded to the side chain.

[0070]

[0071] (2) 10.0 g of bromomethylated polyaryl ether ketone was ...

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Abstract

The invention relates to a method for preparing a monolithic polyaryletherketone bipolar membrane containing a phthalocyanine catalytic group in a side group. The present invention uses bromomethylated polyaryletherketones and phthalocyanines as starting materials to synthesize polyaryletherketone polymers containing epoxy groups and polymers with phthalocyanines bonded to the side groups of polyaryletherketones. After casting on a clean glass plate, the polyarylether ketone base film containing phthalocyanine and epoxy group side groups was prepared; after the base film was sulfonated, ammonized and quaternized, it was washed with deionized water to obtain a monolithic Type polyaryletherketone bipolar membranes containing phthalocyanine side groups. The present invention utilizes epoxy groups to react with sulfonating agents and aminating agents to introduce anion and cation exchange membranes into polyaryletherketone molecular chains, thereby eliminating the film-forming process and avoiding carcinogen chlorine in the traditional bipolar membrane preparation process. Use of methyl ether. The prepared bipolar membrane has self-catalysis, low bipolar membrane resistance, low transmembrane voltage, long-term use, and no problems such as bubbling and cracking of the intermediate interface layer that are prone to occur during use of the composite bipolar membrane.

Description

technical field [0001] The invention relates to a preparation method of a monolithic polyaryletherketone bipolar membrane containing a phthalocyanine catalytic group in a side group, in particular to the introduction of a substituent containing an epoxy group on the main chain of a polyaryletherketone, and a phthalocyanine-containing polyarylide Ether ketone and epoxy group-containing polyaryl ether ketone are blended to form a film as a base film material, and anions and cations are introduced on both sides of the base film through a ring-opening reaction of epoxy groups to synthesize a side-group containing phthalocyanine group. Monolithic polyarylene Preparation method of ether ketone bipolar membrane. Background technique [0002] Bipolar membrane is a new branch developed on the basis of ion exchange membrane technology, and it has rapidly developed into a research hotspot in the current membrane technology field. It is usually a functional membrane with a three-layer ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08J7/12C08J5/22C08L71/10C08G65/48B01D61/44
CPCC08J7/12C08J5/2256C08G65/48B01D61/445C08J2371/10C08J2471/10
Inventor 黄雪红李晓燕丁富传
Owner FUJIAN NORMAL UNIV
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