阅读说明：本技术 一种侧链含卟啉水解离催化基团单片型聚芳醚酮双极膜制备方法 (Preparation method of monolithic polyaryletherketone bipolar membrane with side chain containing porphyrin water dissociation catalytic group ) 是由 黄雪红 张睫灵 贾玉婷 宁金凤 李晓燕 丁富传 于 2020-05-12 设计创作，主要内容包括：本发明涉及一种侧链含卟啉水解离催化基团单片型聚芳醚酮双极膜制备方法,以溴甲基化聚砜、溴甲基化聚砜聚合物为出发原料,分别合成含有卟啉和环氧基团侧基的聚砜基膜混合液,将他们混合后流延在洁净的玻璃板上,烘干制备含有卟啉和环氧基团侧基的聚砜基膜；基膜经磺化、铵化和季铵化后,去离子水洗涤,得到单片型含酞菁基侧基的聚芳醚酮双极膜。本发明制备的双极膜通过亲核取代反应,在聚砜侧基上引入环氧基团,在聚砜分子链中引入阴、阳离子交换膜方法,省去了成膜工序和避免致癌物氯甲醚的使用。制备的双极膜带有自催化作用,双极膜电阻低,跨膜电压低。长期使用,也不会出现中间界面层鼓泡、开裂等复合型双极膜在使用过程中容易出现的问题。(The invention relates to a preparation method of a monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups, which takes bromomethylated polysulfone and bromomethylated polysulfone polymers as raw materials to respectively synthesize polysulfone-based membrane mixed liquor containing porphyrin and epoxy group side groups, the mixed liquor is cast on a clean glass plate after being mixed, and the polysulfone-based membrane containing porphyrin and epoxy group side groups is prepared by drying; and after the base membrane is sulfonated, aminated and quaternized, washing with deionized water to obtain the monolithic polyaryletherketone bipolar membrane containing the phthalocyanine group side group. The bipolar membrane prepared by the invention introduces epoxy groups on the polysulfone side groups through nucleophilic substitution reaction, and introduces anion and cation exchange membranes in polysulfone molecular chains, thereby omitting a film forming process and avoiding the use of carcinogenic chloromethyl ether. The prepared bipolar membrane has an autocatalytic effect, and is low in resistance and transmembrane voltage. The problems that the composite bipolar membrane is easy to bubble and crack at the middle interface layer in the using process can not occur after long-term use.)

1. A preparation method of a monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups is characterized by comprising the following steps:

(1) dissolving bromomethylated polysulfone in an organic solvent I, introducing nitrogen to remove oxygen after dissolving, heating to a certain temperature, adding 20-100 moles of an epoxy group-containing substituent monomer, 1 mole of CuBr and 2 moles of bipyridine into a reaction system according to 1 mole of bromomethyl in a bromomethylated polyaryletherketone substituent, reacting at a constant temperature for 5-40 hours under the protection of nitrogen, pouring the reaction solution into water, precipitating a polyaryletherketone grafted polymer, soaking the polymer in running water for 24 hours, removing copper ions, bipyridine and unreacted epoxy group-containing substituent monomer, filtering and drying to obtain a polyaryletherketone grafted epoxy group-containing side chain copolymer PEEK-g-PGMA base membrane material;

(2) dissolving polyaryletherketone grafted epoxy group-containing side chain copolymer in an organic solvent II, adding 0.2-1.2 mol of hydroxyl group-containing substituent porphyrin and 0.2-1.2 mol of NaHCO into the copolymer according to 1 mol of epoxy group in the copolymer after the grafted copolymer is fully dissolved₃Heating to 60-110 ℃ under the protection of nitrogen, and reacting for 3-8 h at constant temperature; after the reaction is finished, immediately cooling the system to room temperature by using an ice water bath, using a mixed solution of distilled water and methanol as a precipitator to precipitate polymer precipitate, washing the polymer precipitate for multiple times by using the mixed solution, and performing vacuum drying to obtain a polymer PL-PEEK-g-PGMA with a polyaryletherketone grafted side chain bonded with porphyrin;

(3) PEEK-g-PGMA copolymer and PL-PEEK-g-PGMA polymer were mixed in 10: adding the mixture into an NMP solvent in a mass ratio of 0.1-1.0, after the polymer is completely dissolved, casting the mixture on a clean glass plate, and drying to prepare a polyaryletherketone base film containing porphyrin side chains;

(4) the double-sided reaction of the polyaryletherketone base membrane containing porphyrin side chains respectively introduces anion and cation groups: floating a base membrane on the liquid level of a sulfonation reaction solution in a reactor I with one side of the base membrane facing downwards, introducing nitrogen to remove air in the reactor, sealing, carrying out sulfonation reaction in a constant-temperature water bath kettle to open the ring of an epoxy group in a molecular chain of polyaryletherketone containing a porphyrin side chain to introduce a sulfonic acid group, washing with deionized water after the sulfonation reaction is finished, and transferring the sulfonated aromatic ketone into a reactor II to carry out amination reaction;

(5) soaking the sulfonated porphyrin-containing polyaryletherketone membrane obtained in the step (4) with the other side facing downwards in an amination reaction solution in a reactor II, introducing nitrogen to remove air in the reactor, sealing, carrying out amination reaction in a constant-temperature water bath kettle to open the ring of an epoxy group in the polyaryletherketone membrane and introduce an amino group, washing with deionized water after the amination reaction is finished, removing residual negative reaction solution in a basement membrane, and moving the basement membrane into a reactor III for quaternization;

(6) and (3) soaking the base membrane obtained in the step (5) in a reactor III filled with quaternary ammonium reaction liquid with the cathode facing downwards, introducing nitrogen to remove air in the reactor, sealing, carrying out quaternary ammonium reaction in a constant-temperature water bath kettle, washing with deionized water to remove residual quaternary ammonium reaction liquid in the base membrane after the reaction is finished, and drying to obtain the porphyrin-containing water dissociation catalytic group monolithic polyaryletherketone bipolar membrane.

2. The preparation method of the monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups as claimed in claim 1, wherein in step (1):

the bromomethylated polyaryletherketone is polyaryletherketone containing o-methyl hydroquinone grafted monomers, polyaryletherketone containing trimethyl hydroquinone grafted monomers and polyaryletherketone containing tetramethyl biphenyl diphenol grafted monomers, and the methyl bromination rate is 3-60.0%;

the grafting monomer in the bromomethylated polyaryletherketone is any one of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl phenyl glycidyl ether and 4-vinylbenzyl glycidyl ether ethylene monomer containing epoxy group;

the organic solvent I is any one or the combination of two of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any proportion.

3. The preparation method of the monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups as claimed in claim 1, wherein in step (2):

the porphyrin containing the hydroxyl substituent is any one of 5- (4-hydroxyphenyl) -porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-triphenylporphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-nitrophenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-chlorophenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-alkylphenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-alkoxyphenyl) porphyrin, alkaline earth metal porphyrin containing hydroxyl and transition metal (M) porphyrin (MPP) containing hydroxyl; m in hydroxyl-containing transition metal porphyrin (MPP) is any one of Mg, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn;

the organic solvent II is any one or a combination of two of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.

4. The preparation method of the monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups as claimed in claim 1, wherein in step (4):

the reagent in the sulfonation reaction solution is any one of sodium bisulfite, potassium bisulfite and dilute sulfuric acid, the solvent of the reaction solution can be selected from water and one or two of DMF, DMAc, NMP, DMSO and the like in any proportion, and the cation exchange capacity of the reaction solution is 0.6-2.0mmol/g dry film;

the temperature of the sulfonation reaction can be 20-90 ℃, and the time of the sulfonation reaction can be 10-72 h.

5. The preparation method of the monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups as claimed in claim 1, wherein in step (5):

the reagent in the amination reaction liquid is any one of ethylenediamine, diethyltriamine, triethyltetramine, tetraethylpentamine, pentaethylhexamine, dimethylamine, diethylamine, 3-aminopyrazole, 5-aminotetrazole and 2-methyl-5-amino-2H-tetrazole; the solvent of the reaction solution can be selected from water and one or two of DMF, DMAc, NMP, DMSO and the like in any proportion;

the temperature of the amination reaction can be 20-90 ℃, and the reaction time of the epoxy group and the amination reagent can be 10-60 h;

the temperature of the amination reaction can be 20-70 ℃, and the reaction time of the epoxy group and the amination reagent can be 10-70 h.

6. The preparation method of the monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups, as claimed in claim 1, is characterized in that in step (6):

the reagent of the quaternary ammonium reaction solution is any one of methyl iodide, ethyl bromide, n-bromobutane and benzyl chloride; the solvent of the quaternary ammonium reaction solution is any one of methanol, ethanol, acetone or tetrahydrofuran; the temperature of the quaternary ammonium reaction can be 0-50 ℃, the time of the quaternary ammonium reaction can be 4-60 h, and the ion exchange capacity is 0.8-2.5mmol/g dry film.

Technical Field

The invention relates to a preparation method of a monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups, in particular to a preparation method of a monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin groups, which is synthesized by introducing epoxy group-containing side chains into polyaryletherketone grafting by adopting an active radical polymerization method, introducing porphyrin groups into the polyaryletherketone side chains through further reaction of the epoxy groups as a bipolar membrane middle layer water dissociation catalyst.

Background

The bipolar membrane is a branch newly developed on the basis of the ion exchange membrane technology and is rapidly developed as a research hotspot in the current membrane technical field. It is a functional membrane with three-layer structure, which is composed of anion exchange layer, cation exchange layer and intermediate catalytic layer for splitting water rapidly. Under the action of DC electric field, the interface layer in the middle of bipolar membrane is dissociated to obtain H on two sides of the membrane⁺And OH^-Immediate acid/base production/regeneration can be achieved. The application fields of the method include seawater desalination, industrial sewage treatment, food concentration and separation, pharmaceutical industry, acid and alkali manufacturing industry and the like, so that the processing process is more green and efficient, the traditional industrial separation and preparation process is changed, and new vitality and vitality are brought for solving the technical problems in the fields of environment, chemical industry, biology, ocean chemical industry and the like.

The preparation method of the bipolar membrane has two main types: (1) the double-membrane composite type structure enables physical interface adhesive to exist between the anion layer and the cation layer all the time, reduces the ion transmission capability in the bipolar membrane, has larger resistance of the membrane, and is limited in application due to low operating current density. Due to the limitation of the traditional composite process, the ion exchange layer cannot be made very thin; (2) the ion layer is on the same film, the traditional method adopts the mixed solution of polyethylene impregnated styrene, divinylbenzene and benzoyl peroxide to react to prepare the basement membrane, then the two sides are respectively sulfonated and quaternized to obtain the anion-cation exchange layer.

A bipolar membrane of a monolithic type has been recently gaining attention, and US 402404043 and US4057481 report a method for producing a bipolar membrane of a monolithic type by immersing a polymer base membrane in a styrene monomer solution and polymerizing it several times, followed by sulfonation and chloromethylation and quaternization on both sides of the membrane, respectively. Chinese patents CN 104861194B and CN 102061004B report a preparation method of a single-sheet bipolar membrane, which uses a polyolefin thin film or a polyhalogenated olefin thin film to immerse in a monomer of styrene-divinylbenzene and to irradiate and polymerize to make a basement membrane, or uses a polyethylene and ethylene-octene copolymer thin film as the basement membrane; one side of the base film is heated and sulfonated in concentrated sulfuric acid or chlorosulfonic acid, the other side of the base film is subjected to chloromethylation reaction in chloromethyl ether containing anhydrous stannic chloride, and the film is immersed in trimethylamine aqueous solution or dimethylamine-containing trimethylamine aqueous solution for amination or quaternization reaction to form a cathode film of the bipolar film, so that the monolithic bipolar film is prepared. However, there are some problems to be solved in this method for producing a bipolar membrane. For example, the reaction processes of sulfonation, chloromethylation, amination, etc. are all susceptible to various factors, and particularly, the sulfonation process performed in the first step is difficult to accurately control. And the strong carcinogenic chemical substance of chloromethyl ether still needs to be used, which causes great harm to the environment and human body.

Rongqiang Fu reports another preparation method of a monolithic bipolar membrane, and a porous polyethylene film is grafted with chloromethyl styrene and acrylic acid on two sides of a base membrane respectively through radiation grafting, and then is quaternized with trimethylamine to obtain the bipolar membrane. This approach also has several significant disadvantages: firstly, the grafting rate is low and the grafting uniformity is poor; secondly, because a porous material is adopted as a base membrane, the grafting monomers on the two sides are prevented from mutually permeating, and the middle interface layer of the bipolar membrane is unclear; thirdly, the adoption of the co-radiation grafting method can cause the self-polymerization of a large amount of monomers, the utilization rate of the monomers is very low, and the method is not suitable for industrial production; fourthly, in order to achieve the required grafting rate, the grafted membrane is usually cleaned and grafted again (similar to the above U.S. patent in which the monomer solution is soaked and polymerized for many times), so that the synthesis steps are increased; fifthly, under the influence of the grafted monomer, the bipolar membrane prepared in the method has low chemical stability and thermal stability of functional groups with ion exchange capacity on the positive side and the negative side, and therefore the application range of the bipolar membrane is greatly limited.

Porphyrin has good pigment activity to sunlight, has rich p electrons and large pi bonds, so that the porphyrin has good electron loss characteristics, and various compounds of porphyrin are widely applied to the fields of photosensitizers and photocatalysis. Research results show that under the same state of the same porphyrin, the separation energy of hydrogen protons is lower than that of hydrogen atoms, and any porphyrin conforms to the rule, which indicates that the hydrogen protons are separated from water molecules under the catalysis of the porphyrin. Porphyrin only needs light energy injection in the catalysis process, the products are hydrogen protons and oxygen atoms, no by-product is generated in the reaction process, and clean pollution-free catalysis is realized. Porphyrin serving as a side group is bonded in a polyaryletherketone molecular chain, and can be well fixed in a bipolar membrane to catalyze the water dissociation of the middle layer.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a simple and feasible preparation method of a monolithic polyaryletherketone bipolar membrane with side chains containing porphyrin water dissociation catalytic groups.

The invention utilizes active free radical polymerization to graft and introduce epoxy group side chains on the polyaryletherketone material, and the molecular weight of the side chains is controllable. Epoxy groups are utilized to react with porphyrin, and a catalytic interlayer water dissociation group is introduced into the polyaryletherketone base membrane. Porphyrin-containing polyaryletherketone and polyaryletherketone grafted epoxy group side chains are blended to be used as a base membrane material, and anion and cation exchange groups are introduced to two sides of the base membrane by utilizing the reaction of the epoxy group, a sulfonating agent and an aminating agent to prepare the porphyrin group-containing monolithic polyaryletherketone bipolar membrane. The cathode layer and the anode layer of the single-chip bipolar membrane can not generate the phenomenon of bubbling in the using process. The side chain of the ion exchange group reduces the oxidation of the free radical intermediate to the main chain of the polymer in the application process of the bipolar membrane, thereby being beneficial to improving the stability of the membrane and prolonging the service life. Convenient production, and good economic benefit and popularization value.

The preparation method of the monolithic polyaryletherketone bipolar membrane with the side chain containing porphyrin water dissociation catalytic group comprises the following steps:

(1) preparing a base film material: dissolving bromomethylated polyaryletherketone in an organic solvent I, introducing nitrogen to remove oxygen, heating to a certain temperature, and adding 20-100 moles of an epoxy group-containing substituent monomer, 1 mole of CuBr and 2 moles of bipyridine into a reaction system based on 1 mole of bromomethyl in a bromomethylated polyaryletherketone substituent. And (2) reacting at constant temperature for 5-40 h under the protection of nitrogen, pouring the reaction solution into water, precipitating the polyaryletherketone grafted polymer, soaking the polymer in running water for 24h, removing copper ions, bipyridine and unreacted epoxy group-containing substituted monomers, filtering and drying to obtain the polyaryletherketone grafted epoxy group-containing side chain copolymer (PEEK-g-PGMA) base membrane material.

(2) Preparing a bipolar membrane middle layer water dissociation catalyst by grafting polyaryletherketone onto side chain bonded porphyrin: dissolving polyaryletherketone grafted epoxy group-containing side chain copolymer in an organic solvent II, adding 0.2-1.2 mol of hydroxyl group-containing substituent porphyrin and 0.2-1.2 mol of NaHCO into the copolymer according to 1 mol of epoxy group in the copolymer after the grafted copolymer is fully dissolved₃And heating to 60-110 ℃ under the protection of nitrogen, and reacting for 3-8 h at constant temperature. And after the reaction is finished, immediately cooling the system to room temperature by using an ice-water bath, using a mixed solution of distilled water and methanol as a precipitator to precipitate a polymer precipitate, washing the polymer precipitate for multiple times by using the mixed solution, and drying in vacuum to obtain the polyaryletherketone grafted polymer (PL-PEEK-g-PGMA) with porphyrin bonded on a side chain.

(3) PEEK-g-PGMA copolymer and PL-PEEK-g-PGMA polymer were mixed in 10: adding the mixture into NMP solvent in a mass ratio of 0.1-1.0, after the polymer is completely dissolved, casting the mixture on a clean glass plate, and drying to prepare the polyaryletherketone base film containing the porphyrin side chain.

(4) The double-sided reaction of the polyaryletherketone base membrane containing porphyrin side chains respectively introduces anion and cation groups: and (3) making one surface (marked as an anode surface) of the base film face downwards, floating on the liquid surface of the sulfonation reaction solution in the reactor I, introducing nitrogen to remove air in the reactor, sealing, carrying out sulfonation reaction in a constant-temperature water bath kettle to open the ring of an epoxy group in a polyaryletherketone molecular chain containing a porphyrin side chain to introduce a sulfonic acid group, washing with deionized water after the sulfonation reaction is finished, and transferring into the reactor II to carry out amination reaction.

(5) And (3) the other side (marked as cathode side) of the sulfonated porphyrin-containing polyaryletherketone membrane obtained in the step (4) is downward, the sulfonated porphyrin-containing polyaryletherketone membrane is soaked in amination reaction liquid in a reactor II, nitrogen is introduced to remove air in the reactor, then the reactor is sealed, amination reaction is carried out in a constant-temperature water bath kettle, epoxy groups in the polyaryletherketone membrane are subjected to ring opening to introduce amino groups, and after the amination reaction is finished, deionized water is used for washing, residual cathode side reaction solution in a basement membrane is removed, and the membrane is moved into a reactor III for quaternization.

(6) And (3) soaking the base membrane obtained in the step (5) in a reactor III filled with quaternary ammonium reaction liquid with the cathode facing downwards, introducing nitrogen to remove air in the reactor, sealing, carrying out quaternary ammonium reaction in a constant-temperature water bath kettle, washing with deionized water to remove residual quaternary ammonium reaction liquid in the base membrane after the reaction is finished, and drying to obtain the porphyrin-containing water dissociation catalytic group monolithic polyaryletherketone bipolar membrane.

In step (1):

the bromomethylated polyaryletherketone is polyaryletherketone containing o-methyl hydroquinone grafted monomers, polyaryletherketone containing trimethyl hydroquinone grafted monomers and polyaryletherketone containing tetramethyl biphenyl diphenol grafted monomers, and the methyl bromination rate is 3-60.0%.

The graft monomer in the bromomethylated polyaryletherketone is any one of glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl phenyl glycidyl ether and 4-vinylbenzyl glycidyl ether ethylene monomer containing epoxy group.

The organic solvent I is any one or the combination of two of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any proportion.

In step (2):

the porphyrin containing the hydroxyl substituent is any one of 5- (4-hydroxyphenyl) -porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-triphenylporphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-nitrophenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-chlorophenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-alkylphenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tri (4-alkoxyphenyl) porphyrin, alkaline earth metal porphyrin containing hydroxyl and transition metal (M) porphyrin (MPP) containing hydroxyl; m in hydroxyl-containing transition metal porphyrin (MPP) is any one of Mg, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.

The organic solvent II is any one or a combination of two of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.

In step (4):

the reagent in the sulfonation reaction solution is any one of sodium bisulfite, potassium bisulfite and dilute sulfuric acid, and the solvent of the reaction solution can be selected from water and one or two of DMF, DMAc, NMP, DMSO and the like in any proportion. The cation exchange capacity is 0.6-2.0mmol/g dry film.

The temperature of the sulfonation reaction can be 20-90 ℃, and the time of the sulfonation reaction can be 10-72 h.

In step (5):

the reagent in the amination reaction liquid is any one of ethylenediamine, diethyltriamine, triethyltetramine, tetraethylpentamine, pentaethylhexamine, dimethylamine, diethylamine, 3-aminopyrazole, 5-aminotetrazole and 2-methyl-5-amino-2H-tetrazole; the solvent of the reaction solution can be selected from water and one or two of DMF, DMAc, NMP, DMSO and the like in any proportion;

the temperature of the amination reaction can be 20-90 ℃, and the reaction time of the epoxy group and the amination reagent can be 10-60 h;

the temperature of the amination reaction can be 20-70 ℃, and the reaction time of the epoxy group and the amination reagent can be 10-70 h.

In step (6):

the reagent of the quaternary ammonium reaction solution is any one of methyl iodide, ethyl bromide, n-bromobutane and benzyl chloride; the solvent of the quaternary ammonium reaction solution is any one of methanol, ethanol, acetone or tetrahydrofuran; the temperature of the quaternary ammonium reaction can be 0-50 ℃, and the time of the quaternary ammonium reaction can be 4-60 h. The ion exchange capacity of the negative side is 0.8-2.5mmol/g dry film.

The invention has the advantages and beneficial effects that:

1. by means of active free radical polymerization, monomer side chain with epoxy group is grafted onto the side chain of polyaryletherketone, and the side chain with epoxy group has controllable molecular weight. The epoxy group and corresponding reagents are introduced into the anion-cation exchange membrane and the cation-exchange membrane to prepare the single-chip bipolar membrane, so that the film forming process in the traditional bipolar membrane preparation process is omitted, and the use of carcinogenic chloromethyl ether is avoided.

2. Epoxy groups and porphyrin are reacted to introduce porphyrin groups on the side chain of polyaryletherketone as a bipolar membrane middle layer water dissociation catalyst. The prepared bipolar membrane has the autocatalysis effect, low resistance and low transmembrane voltage.

3. The problem that the composite bipolar membrane such as bubbling and cracking of an intermediate interface layer is easy to occur in the using process can not occur even if the single-chip bipolar membrane prepared by the method is used for a long time.

Drawings

FIG. 1 is a schematic diagram of the preparation method of the present invention.

Detailed Description

The present invention is further described with reference to the following examples and four figures, but it should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that the following insubstantial modifications and adaptations of the present invention by those skilled in the art based on the foregoing description of the present invention are still within the scope of the present invention.

In FIG. 1, firstly, an epoxy group side chain is grafted and introduced on a polyaryletherketone material by using living radical polymerization, and the molecular weight of the side chain is controllable. Epoxy groups are utilized to react with porphyrin, and a catalytic interlayer water dissociation group is introduced into the polyaryletherketone base membrane. Porphyrin-containing polyaryletherketone and polyaryletherketone grafted epoxy group side chain blendingAs a basement membrane material, an epoxy group reacts with a sulfonating agent and an aminating agent to introduce anion and cation exchange groups on two sides of the basement membrane to prepare the porphyrin group-containing monolithic polyaryletherketone bipolar membrane. The cathode layer and the anode layer of the single-chip bipolar membrane can not generate the phenomenon of bubbling in the using process. In the figure: n is the polymerization degree of the main chain of the polyaryletherketone base membrane, m is the polymerization degree of a substituent side chain containing an epoxy group, and n and m are integers which are not zero; r is a hydrogen atom or a methyl group; y is⁺Is H⁺、Na⁺、K⁺Any one of (a); x^-Is Cl^-、Br^-、I^-、OH^-、SO₃H^-Any one of the above.