阅读说明：本技术 侧基含卟啉催化基团的单片型聚芳醚酮双极膜制备方法 (Preparation method of monolithic polyaryletherketone bipolar membrane with side group containing porphyrin catalysis group ) 是由 黄雪红 李晓燕 丁富传 于 2020-05-12 设计创作，主要内容包括：本发明涉及一种侧基含有卟啉基团单片型聚芳醚酮双极膜制备方法。其方案：溴甲基化聚芳醚酮与含甲氧基苯酚反应制得含甲氧基苯酚聚芳醚酮聚合物；含甲氧基苯酚聚芳醚酮聚合物与三溴化硼溶液进行反应得到含羟基聚芳醚酮聚合物；含羟基聚芳醚酮聚合物加入环氧氯丙烷反应制得含环氧基团取代基聚芳醚酮聚合物；溴甲基化聚芳醚酮聚合物与含羟基取代基卟啉、NaHCO<Sub>3</Sub>反应得聚芳醚酮侧基键合有卟啉的聚合物；PAEK-EG和Pc-PAEK混合后流延、烘干,再将将聚芳醚酮基膜进行磺化反应和胺化反应、季胺化反应得到单片型含卟啉催化基团的聚芳醚酮双极膜。本发明单片型双极膜在使用过程中不产生“鼓泡”现象,有利于提高稳定性和使用寿命。(The invention relates to a preparation method of a monolithic polyaryletherketone bipolar membrane with side groups containing porphyrin groups. The scheme is as follows: bromomethylation of polyaryletherketone and methoxyl-containing phenol reaction to prepare methoxyl-containing polyaryletherketone polymer; reacting the methoxyphenol-containing polyaryletherketone polymer with a boron tribromide solution to obtain a hydroxyl-containing polyaryletherketone polymer; adding the hydroxyl-containing polyaryletherketone polymer into epoxy chloropropane to react to prepare an epoxy group-containing substituent polyaryletherketone polymer; bromomethylation polyaryletherketone polymer and hydroxyl substituent-containing porphyrin and NaHCO 3 Reacting to obtain a polymer with porphyrin bonded on a polyaryletherketone side group; mixing PAEK-EG and Pc-PAEK, casting, drying, and mixing with polyaryletherketoneAnd carrying out sulfonation reaction, amination reaction and quaternization reaction on the membrane to obtain the monolithic bipolar membrane of the polyaryletherketone containing the porphyrin catalysis group. The single-chip bipolar membrane does not generate a bubbling phenomenon in the using process, and is favorable for improving the stability and prolonging the service life.)

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

(1) preparing a methoxyphenol-containing polyaryletherketone polymer:

dissolving a polymer containing bromomethylated polyaryletherketone in an organic solvent I, adding a mixed solution containing methoxyphenol and a catalyst, wherein the molar number of the substituent bromomethyl in the bromomethylated polyaryletherketone is 1.0-1.5 times that of the mixed solution, reacting at room temperature for 5-24 hours, pouring the reaction solution into a water/ethanol mixed solvent, precipitating, and filtering; soaking the precipitate in flowing water for 24 hr, filtering, and oven drying to obtain methoxyphenol-containing polyaryletherketone polymer;

the volume ratio of the mixture liquid containing the methoxyphenol and the catalyst is 1: 0.5-1, wherein the molar ratio of the methoxyphenol to the catalyst is 1: 1;

the volume ratio of the water to the ethanol in the mixed solvent is 1: 0.5 to 1;

(2) preparing a hydroxyl-containing polyaryletherketone polymer:

dissolving a methoxyphenol-containing polyaryletherketone polymer in an organic solvent II, loading a constant-pressure dropping funnel after dissolving, vacuumizing, and protecting with nitrogen; dropwise adding a boron tribromide solution under an ice bath condition, after dropwise adding within 2h, heating to room temperature, continuing to react for 12h, and stopping the reaction; after the reaction is finished, filtering, washing with dichloromethane, methanol and water sequentially for multiple times to obtain a hydroxyl-containing polyaryletherketone polymer, and drying for 24 hours in a vacuum drying oven at 80 ℃ for later use;

the boron tribromide and boron tribromide solution is prepared by dissolving boron tribromide in an organic solvent II;

(3) preparing an epoxy group-containing substituent polyaryletherketone polymer:

dissolving a hydroxyl-containing polyaryletherketone polymer in an organic solvent III, heating to 40-70 ℃, adding epoxy chloropropane and a catalyst, reacting at a constant temperature for 3-10 h, pouring the reaction solution into a water/ethanol mixed solvent, precipitating an epoxy-containing polyaryletherketone polymer, and filtering; soaking the precipitate in flowing water for 24h, filtering and drying to obtain epoxy group-containing substituent polyaryletherketone polymer PAEK-EG;

the volume ratio of the water to the ethanol in the mixed solvent is 1: 0.5 to 1;

(4) preparing polyaryletherketone side group bonded porphyrin polymer:

dissolving the bromomethylated polyaryletherketone polymer in an organic solvent IV system according to the bromomethyl group, hydroxyl substituent-containing porphyrin and NaHCO in the molecular chain of the bromomethylated polyaryletherketone polymer₃In a molar ratio of 1: 0.2-1.02: 0.2-1.02 of hydroxyl substituent-containing porphyrin and NaHCO₃Adding the mixture into a reaction system, heating to 30-80 ℃ under the protection of nitrogen, and reacting for 3-10 hours at constant temperature; cooling after the reactionCooling to room temperature, precipitating a product polymer, washing for multiple times, and vacuum drying to obtain a polymer Pc-PAEK with a polyaryletherketone side group bonded with porphyrin;

(5) preparation of polyaryletherketone base membrane:

mixing PAEK-EG and Pc-PAEK polymers according to the weight ratio of 10: 0.1-1.0 mass percent of the raw materials are put into an organic solvent IV, and the raw materials are cast on a clean glass plate after being dissolved and dried to prepare a polyaryletherketone base film containing porphyrin and epoxy group side groups;

(6) introducing an ion exchange group:

vertically placing the polyaryletherketone base membrane into a reactor, and dividing the reactor into two chambers; adding a sulfonation reagent into one surface of a polyaryletherketone base membrane containing porphyrin, and adding an organic amine reagent into the other surface of the polyaryletherketone base membrane, so that the polyaryletherketone base membrane is in a completely soaked state; introducing nitrogen to remove air in the reactor, and sealing; then putting the reactor into a constant-temperature water bath kettle to synchronously carry out sulfonation reaction and amination reaction;

after the amination reaction is finished, replacing the organic amine reagent with a quaternization reagent, and carrying out quaternization reaction;

(7) and after the quaternization reaction is finished, washing by deionized water, and drying to obtain a cation exchange layer and an anion exchange layer, thus obtaining the single-chip type polyaryletherketone bipolar membrane containing the porphyrin catalysis group.

2. The method for preparing the bipolar membrane of the monolithic polyaryletherketone with porphyrin catalysis groups on the side groups, as claimed in claim, wherein in step (1), the bromomethylated polyaryletherketone polymer is polyaryletherketone with methyl substituents, wherein the polyaryletherketone with methyl substituents is structural units containing o-methyl hydroquinone, structural units containing trimethyl hydroquinone, structural units containing tetramethyl dihydroxy diphenyl ether or structural units containing amination reaction and quaternarized tetramethyl biphenyl diphenol; the bromomethylation rate is 5-100%.

3. The method for preparing a monolithic polyaryletherketone bipolar membrane with porphyrin catalysis group-containing pendant group as claimed in claim, wherein in step (1), said methoxy substituent-containing phenol is any one of p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, 2, 3-dimethoxyphenol, 2, 4-dimethoxyphenol, 2, 5-dimethoxyphenol, 2, 6-dimethoxyphenol, 3, 4-dimethoxyphenol, 3, 5-dimethoxyphenol, 3, 6-dimethoxyphenol, 2,3, 4-trimethoxyphenol, 3,4, 5-trimethoxyphenol, 2,3,4, 5-tetramethoxyphenol.

4. The preparation method of the monolithic polyaryletherketone bipolar membrane with porphyrin catalysis groups on its side groups as claimed in claim, wherein in step (1), the organic solvent I is any one or a combination of two of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any ratio; the catalyst is any one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

5. The method for preparing the monolithic polyaryletherketone bipolar membrane with the side group containing the porphyrin catalytic group as claimed in claim, wherein in step (2), the organic solvent II is one or a combination of two of dichloromethane, chloroform, 1, 2-dichloroethane and chlorobenzene in any proportion.

6. The preparation method of the monolithic polyaryletherketone bipolar membrane with porphyrin catalysis groups on its side groups as claimed in claim, wherein in step (3), the organic solvent III is one or a combination of two of N, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone; the catalyst is any one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

7. The method for preparing a monolithic polyaryletherketone bipolar membrane with porphyrin catalysis group on its side group as claimed in claim, wherein in step (4), said porphyrin containing hydroxyl group is 5- (4-hydroxyphenyl) -porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-triphenylporphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tris (4-nitrophenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tris (4-chlorophenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, 20-tris (4-alkylphenyl) porphyrin, 5- (4-hydroxyphenyl) -10,15, any one of 20-tri (4-alkoxyphenyl) porphyrin; the hydroxyl-containing metal is any one of Mg, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.

8. The method for preparing the monolithic polyaryletherketone bipolar membrane with porphyrin catalysis groups on its side groups as claimed in claim, wherein in steps (4) and (5), the organic solvent IV is one or a combination of N, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone.

9. The method for preparing the bipolar membrane of the monolithic polyaryletherketone with porphyrin catalytic groups on its side groups as claimed in claim, wherein in step (6), said sulfonating agent is A, B, C mixed agent, wherein A is any one of sodium bisulfite, potassium bisulfite and dilute sulfuric acid; b is water; c is one or the combination of two of DMF, DMAc, NMP, DMSO and the like in any proportion; A. b, C mass ratio of mixed reagents = 1: 6-8: 1-3; the organic amine reagent is D, E, F mixed reagent, wherein D is any one of ethylenediamine, diethyltriamine, triethyltetramine, dimethylamine, diethylamine, 3-aminopyrazole, 5-aminotetrazole and 2-methyl-5-amino-2H-tetrazole; e is water; f is one or the combination of two of ethanol, methanol and the like in any proportion; D. e, F mass ratio of mixed reagents = 1: 6-9: 1 to 3.

10. The method for preparing a monolithic polyaryletherketone bipolar membrane with porphyrin catalytic groups on its side groups as claimed in claim, wherein said quaternizing agent is halogenated alkane, specifically any one of methyl iodide, ethyl bromide, n-bromobutane and benzyl chloride; the sulfonation reaction and the amination reaction are carried out at the reaction temperature of 20-90 ℃ for 10-75 h; the quaternization reaction is carried out at the reaction temperature of 0-30 ℃ for 4-60 h.

Technical Field

The invention relates to a preparation method of a monolithic polyaryletherketone bipolar membrane with a side group containing a porphyrin catalytic group, in particular to a method for introducing an epoxy group-containing substituent on a polyaryletherketone molecular chain and bonding porphyrin with a catalytic water dissociation function on the polyaryletherketone side group. The preparation method is characterized in that porphyrin-containing polyaryletherketone and epoxy-containing polyaryletherketone are blended to form a film as a base film material, and anions and cations are introduced to two sides of the base film through epoxy group reaction to synthesize the porphyrin-containing monolithic polyaryletherketone bipolar film.

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-chip bipolar membrane, which uses a polyolefin film or a polyhalogenated olefin film to immerse into a monomer of styrene-divinylbenzene and perform radiation polymerization to prepare a basement membrane, or uses a polyethylene and ethylene-octene copolymer 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.

Polyaryletherketones (PAEKs) are a class of crystalline polymers formed by linking phenylene rings to carbonyl groups (ketones) via ether linkages. The polyaryletherketone molecular structure contains a rigid benzene ring and a flexible ether bond, and has the characteristics of excellent high-temperature performance, mechanical property, electrical insulation, radiation resistance, chemical resistance and the like. The polyaryletherketone is used as a bipolar membrane substrate material, and the acid and alkali resistance of the material is superior to that of polystyrene, polyethylene and ethylene-octene copolymer. Porphyrin is bonded on the side group of the polyaryletherketone in a side group form, and the porphyrin can catalyze the water dissociation of the middle layer of the bipolar membrane and reduce the membrane resistance and the cell voltage.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a simple and feasible preparation method of a porphyrin-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 technical scheme is as follows:

(1) preparing a methoxyphenol-containing polyaryletherketone polymer:

dissolving a polymer containing bromomethylated polyaryletherketone in an organic solvent I, and adding a mixed solution containing methoxyphenol and a catalyst which is 1.0-1.5 times of the molar number of a substituent bromomethyl in the bromomethylated polyaryletherketone after the polymer is completely dissolved, wherein the molar ratio of the methoxyphenol to the catalyst I in the mixed solution is 1: 1; after reacting for 5-24 h at room temperature, pouring the reaction solution into a mixed solvent of water and ethanol (the volume ratio of the two is 1 (0.5-1)), precipitating and filtering; and putting the precipitate into flowing water, soaking for 24h, removing the organic solvent, unreacted methoxyphenol and catalyst, filtering and drying to obtain the methoxyphenol-containing polyaryletherketone polymer.

(2) Preparing a hydroxyl-containing polyaryletherketone polymer:

dissolving the methoxyphenol-containing polyaryletherketone polymer in an organic solvent II, after the polymer is fully dissolved, installing a constant-pressure dropping funnel, vacuumizing, and protecting with nitrogen. And (3) dropwise adding a boron tribromide solution (boron tribromide is dissolved in an organic solvent II to prepare a solution) under an ice bath condition, heating to room temperature to continue reacting for 12h after dropwise adding is finished within 2h, and stopping reacting. After the reaction is finished, filtering, washing with dichloromethane, methanol and water sequentially for many times to obtain the hydroxyl-containing polyaryletherketone polymer, and drying for 24 hours in a vacuum drying oven at 80 ℃ for later use.

(3) Preparing an epoxy group-containing substituent polyaryletherketone polymer:

dissolving a hydroxyl-containing polyaryletherketone polymer in an organic solvent III, heating to 40-70 ℃, adding epoxy chloropropane and a catalyst, reacting at a constant temperature for 3-10 h, pouring the reaction solution into a mixed solvent of water and ethanol (the volume ratio of the two is 1: 0.5-1), precipitating an epoxy group-containing polyaryletherketone polymer, and filtering; and putting the precipitate into flowing water, soaking for 24h, removing the organic solvent, unreacted epoxy chloropropane and the catalyst, filtering and drying to obtain the polyaryletherketone polymer (PAEK-EG) containing the epoxy group substituent as the base membrane material.

(4) Preparing polyaryletherketone side group bonded porphyrin polymer:

dissolving the bromomethylated polyaryletherketone polymer in an organic solvent IV system according to the bromomethyl group, hydroxyl substituent-containing porphyrin and NaHCO in the molecular chain of the bromomethylated polyaryletherketone polymer₃In a molar ratio of 1: (0.2-1.02): (0.2-1.02) of porphyrin containing hydroxyl substituent and NaHCO₃Adding the mixture into a reaction system, heating to 30-80 ℃ under the protection of nitrogen, and reacting for 3-10 hours at constant temperature. After the reaction is finished, cooling to room temperature, using a mixed solution of distilled water and methanol as a precipitator to precipitate a product polymer, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PAEK) with the side group of the polyaryletherketone bonded with the porphyrin.

(5) Preparation of polyaryletherketone base membrane:

mixing PAEK-EG and Pc-PAEK polymers according to the weight ratio of 10: (0.1-1.0) putting the mixture into an organic solvent IV according to the mass ratio, 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 and the epoxy group side groups.

(6) Introducing an ion exchange group:

vertically placing the polyaryletherketone base membrane into a reactor, and dividing the reactor into two chambers; adding a sulfonation reagent into one surface of a polyaryletherketone base membrane containing porphyrin, and adding an organic amine reagent into the other surface of the polyaryletherketone base membrane, so that the polyaryletherketone base membrane is in a completely soaked state; introducing nitrogen to remove air in the reactor, and sealing; then the reactor is put into a constant temperature water bath kettle to synchronously carry out sulfonation reaction and amination reaction.

After the amination reaction is finished, the organic amine reagent is replaced by a quaternization reagent for quaternization reaction.

(7) And after the reaction is finished, washing by deionized water, and drying to obtain a cation exchange layer and an anion exchange layer, thus obtaining the single-chip type polyaryletherketone bipolar membrane containing porphyrin catalytic groups.

The cation exchange capacity in the above process is 0.6-2.0mmol/g dry film.

In step (1):

the bromomethylation polyaryletherketone polymer is polyaryletherketone containing methyl substituent groups, and the methyl substituent groups of polyaryletherketone are structural units containing o-methyl hydroquinone, structural units containing trimethyl hydroquinone, structural units containing tetramethyl dihydroxy diphenyl ether or structural units containing amination reaction and quaternization tetramethyl biphenyl diphenol.

The bromomethylation rate is 5-100%.

The methoxy-containing phenol is any one of p-methoxyphenol, m-methoxyphenol, o-methoxyphenol, 2, 3-dimethoxyphenol, 2, 4-dimethoxyphenol, 2, 5-dimethoxyphenol, 2, 6-dimethoxyphenol, 3, 4-dimethoxyphenol, 3, 5-dimethoxyphenol, 3, 6-dimethoxyphenol, 2,3, 4-trimethoxyphenol, 3,4, 5-trimethoxyphenol and 2,3,4, 5-tetramethoxyphenol.

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.

The catalyst is any one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

In step (2):

the organic solvent II is any one or a combination of two of dichloromethane, trichloromethane, 1, 2-dichloroethane and chlorobenzene in any proportion.

In the step (3), the organic solvent III is any one or a combination of two of N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.

The catalyst is any one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.

In step (4):

the hydroxyl-containing substituent porphyrin 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 and 5- (4-hydroxyphenyl) -10,15, 20-tri (4-alkylphenyl) porphyrin; the hydroxyl-containing metal is any one of Mg, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.

In steps (4) and (5):

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

In step (6):

the sulfonation reagent is A, B, C mixed reagent, wherein A is any one of sodium bisulfite, potassium bisulfite and dilute sulfuric acid; b is water; c is one or the combination of two of DMF, DMAc, NMP, DMSO and the like in any proportion. A. B, C mass ratio of mixed reagent 1: 6-8: 1 to 3.

The organic amine reagent is D, E, F mixed reagent, wherein D is any one of ethylenediamine, diethyltriamine, triethyltetramine, dimethylamine, diethylamine, 3-aminopyrazole, 5-aminotetrazole and 2-methyl-5-amino-2H-tetrazole; e is water; f is one or the combination of two of ethanol, methanol and the like in any proportion. D. E, F mass ratio of mixed reagent 1: 6-9: 1 to 3.

The quaternizing agent adopts halogenated alkane, and specifically is any one of methyl iodide, ethyl bromide, n-bromobutane and benzyl chloride;

the sulfonation reaction and the amination reaction are carried out at the reaction temperature of 20-90 ℃ for 10-75 h.

The quaternization reaction is carried out at the reaction temperature of 0-30 ℃ for 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. through nucleophilic substitution reaction, an epoxy group is introduced on a polyaryletherketone side group, and an anion exchange membrane and a cation exchange membrane are introduced in a polyaryletherketone molecular chain by utilizing the reaction of the epoxy group, a sulfonating agent and an aminating agent to prepare the monolithic bipolar membrane, so that a membrane forming process in the traditional bipolar membrane preparation process is omitted, and the use of carcinogenic chloromethyl ether is avoided.

2. Benzyl bromide is reacted with hydroxyl (or amino) porphyrin to introduce porphyrin group as bipolar membrane middle layer water dissociation catalyst to the side group of polyaryletherketone. 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 shows the IR spectrum of PAEK-g-PGMA graft copolymer-based membrane.

FIG. 2 is a schematic diagram of a preparation method of the monolithic polyaryletherketone bipolar membrane with porphyrin catalysis groups on side groups.

Detailed Description

The present invention is further illustrated by the following examples, but it should be understood that the following examples are not intended to limit the scope of the present invention, and that the insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the present invention.

In the IR spectrum of FIG. 1, 1650cm^-1Shows the stretching vibration absorption peak of carbonyl in the PAEK molecular structure, 1598 cm and 1498cm^-1The plane vibration absorption peak of Ar-O-Ar in the PAEK molecular structure appears, 1237 and 1160cm^-1An asymmetric stretching vibration absorption peak of Ar-O-Ar in the PAEK molecular structure is shown, 908cm^-1The characteristic absorption of epoxy bonds of GMA mer units of the grafted side chains appears, which indicates that the samples contain both PAEK backbone and PGMA grafted side chains.

In the schematic diagram of the preparation method in fig. 2, an epoxy group side group is introduced into a polyaryletherketone molecular chain, epoxy group-containing agglomerated polyaryletherketone and porphyrin-containing polyaryletherketone which can promote water dissociation of a bipolar membrane middle layer are blended, dissolved and cast to form a membrane 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.

In the figure, n is the polymerization degree of the main chain of the polyaryletherketone, and n is an integer which is not zero; y is⁺Is a cation, Y⁺Can be H⁺、Na⁺、K⁺Any one of (a); x^-Is an anion, X^-May be Cl^-、Br^-、I^-、OH^-、SO₃H^-Any one of the above.