阅读说明：本技术 含咔咯水解离催化基团单片型聚芳醚腈双极膜的制备方法 (Preparation method of monolithic poly (arylene ether nitrile) bipolar membrane containing corrole water dissociation catalytic 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：本发明涉及一种含咔咯水解离催化基团单片型聚芳醚腈双极膜的制备方法。本发明以甲氧基双酚、非甲氧基的双酚、二卤代氰基苯、二卤二苯酮或二卤二苯砜和摩尔催化剂Ⅰ为出发原料,分别合成PAEN-EG和Corrole-PAEN聚合物,混合后流延在玻璃板上；经磺化、铵化和季铵化后,得到聚芳醚腈双极膜。本发明通过缩聚反应,将含甲氧基引入聚芳醚腈分子链中,经三溴化硼反应得到含羟基聚芳醚腈,再与环氧氯丙烷反应,在聚芳醚腈侧基上引入环氧基团,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 poly (arylene ether nitrile) bipolar membrane containing a corrole water dissociation catalytic group. Methoxy bisphenol, non-methoxy bisphenol, dihalogenated cyanobenzene, dihalogenated benzophenone or dihalogenated diphenylsulfone and a molar catalyst I are taken as raw materials to respectively synthesize PAEN-EG and Corrole-PAEN polymers, and the PAEN-EG and the Corrole-PAEN polymers are mixed and cast on a glass plate in a flow casting way; and (3) sulfonating, aminating and quaternizing to obtain the bipolar membrane of the poly (arylene ether nitrile). The method introduces methoxyl into a poly (arylene ether nitrile) molecular chain through polycondensation reaction, obtains poly (arylene ether nitrile) containing hydroxyl through boron tribromide reaction, and introduces epoxy group on the side group of poly (arylene ether nitrile) through reaction with epichlorohydrin, 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 poly (arylene ether nitrile) bipolar membrane containing a corrole catalytic group is characterized by comprising the following steps:

(1) placing x mol of methoxyl bisphenol, y mol of non-methoxyl bisphenol, e mol of dihalogenated cyanobenzene, (x + y-e) mol of dihalogenated benzophenone or dihalogenated diphenylsulfone and (1.2-3) (x + y) mol of catalyst I into a reactor, adding organic solvent I, dissolving in N₂Reacting for 1-5 h at 130-150 ℃ under the action of airflow, reacting for 3-20 h at 150-170 ℃, pouring the reaction solution into water, and precipitatingPrecipitating, filtering, soaking the precipitate in active water for 20h, and drying the filtered solid to obtain a methoxy-containing polyaryl ether nitrile polymer;

in the above step, X, y and e are not 0, and X + y is more than e;

(2) dissolving a methoxy-containing poly (arylene ether nitrile) polymer in an organic solvent II, vacuumizing after dissolving, dropwise adding a boron tribromide solution under the ice bath condition under the protection of nitrogen, heating to room temperature to continue reacting for 12 hours after finishing dropwise adding within 1-6 hours, stopping the reaction, filtering, washing with dichloromethane, methanol and water sequentially for multiple times to obtain a hydroxy-containing poly (arylene ether nitrile) polymer, and drying for 24 hours at 80 ℃ in a vacuum drying oven for later use;

(3) dissolving a poly (arylene ether nitrile) polymer containing hydroxyl in an organic solvent III, heating to 40-70 ℃, respectively adding epoxy chloropropane and a catalyst II in an equal molar ratio, reacting at a constant temperature for 3-10 h, pouring the reaction solution into a water/ethanol mixed solvent, precipitating the poly (arylene ether nitrile) polymer containing an epoxy group, filtering, and soaking the precipitate in running water for 24h to prepare a poly (arylene ether nitrile PAEN-EG) polymer containing an epoxy group substituent;

(4) dissolving bromomethylation poly (arylene ether nitrile) polymer in an organic solvent IV, and taking 1 mol of bromomethyl in a molecular chain of the bromomethylation poly (arylene ether nitrile) polymer as a reference, and adding 0.2-1.02 mol of hydroxyl-containing corrole and 0.2-1.02 mol of NaHCO₃Adding the mixture into a reaction system, heating to 30-80 ℃ under the protection of nitrogen, reacting at a constant temperature for 3-10 h, cooling to room temperature, precipitating a polymer product by using a mixed solvent of distilled water and methanol as a precipitator, washing the polymer product for multiple times by using the mixed solvent of water and methanol, and drying in vacuum to obtain a polyarylene ether nitrile core-PAEN polymer with a carbazole bonded at a side group;

(5) mixing PAEN-EG and core-PAEN polymers in a ratio of 10: 0.01-1.0 mass percent of the organic solvent V solvent, casting on a clean glass plate after dissolving, and drying to prepare a poly (arylene ether nitrile) base film containing side groups of corrole and an epoxy group;

(6) putting a base membrane into a reactor, respectively soaking two side surfaces of the base membrane into a positive surface sulfonation reaction solution and a negative surface amination reaction solution, and then putting the reactor into a constant-temperature water bath kettle for sulfonation reaction and amination reaction;

(7) quaternization: and carrying out quaternization reaction on the sulfonated and aminated polyaryl ether nitrile membrane and a quaternization reagent, and washing with deionized water to obtain the monolithic polyaryl ether nitrile bipolar membrane containing the corrole side group.

2. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (1):

the dihalogenated cyanobenzene is any one or the combination of two of 2, 4-dichloroterephthalonitrile, 2, 4-difluoroterephthalonitrile, 2, 5-dichloroterephthalonitrile, 2, 5-difluoroterephthalonitrile, 2, 6-dichloroterephthalonitrile, 2, 6-difluoroterephthalonitrile, 2, 4-dichlorobenzonitrile, 2, 4-difluorodinitrile, 2, 5-dichlorobenzonitrile, 2, 5-difluorobenzonitrile, 2, 6-dichlorobenzonitrile, 2, 6-difluorobenzonitrile, 3, 5-dichlorobenzonitrile and 3, 5-difluorobenzonitrile in any proportion;

the dihalobenzophenone is any one or combination of two of difluorobenzophenone, dichlorobenzophenone, difluorodinitrile benzophenone and dichlorodinitrile benzophenone in any proportion;

the dihalo diphenyl sulfone is any one of difluoro diphenyl sulfone, dichloro diphenyl sulfone, difluoro dinitrile diphenyl sulfone and dichloro dinitrile diphenyl sulfone or the combination of two of them in any proportion.

3. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (1):

the bisphenol is any one or the combination of two of hydroquinone, resorcinol, bisphenol fluorene, bisphenol A, hexafluorobisphenol A, biphenol, dihydroxy diphenyl ether, 2-nitrile hydroquinone, 3-nitrile resorcinol, nitrile biphenol and nitrile dihydroxy diphenyl ether in any proportion;

the methoxyl-containing bisphenol is any one of p-2-methoxyl hydroquinone, 5-methoxyl resorcinol, 2, 3-dimethoxy hydroquinone, 2, 5-dimethoxy hydroquinone, 2, 6-dimethoxy hydroquinone, 2,3, 5-trimethoxy hydroquinone, 2,3,5, 6-tetramethoxy hydroquinone, 3',5,5' -tetramethoxy-4, 4 '-biphenol, tetramethoxy biphenol, 3',5,5 '-tetramethoxy-4, 4' -dihydroxy diphenyl ether and tetramethoxy-dihydroxy diphenyl ether or a combination of two of the two in any proportion.

4. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (1):

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

the catalyst I is anhydrous potassium carbonate or anhydrous sodium carbonate.

5. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (2):

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

the corrole is any one of hydroxyl corrole, amino corrole and hydroxyl metal (M) corrole (metal M = Co, Ni, Cu, Zn, Fe, Mg, Ba, Sc, Ti, V, Cr or Mn).

6. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (3):

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

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

7. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (4):

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

8. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein in the step (5):

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

9. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein the steps are as follows in step (6):

the sulfonation reagent in the cation sulfonation reaction solution 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; the cation exchange capacity is 0.6-2.0mmol/g dry film;

the amination reagent in the negative amination reaction solution 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 DMF, DMAc, NMP, DMSO and the like in any proportion;

the temperature of the sulfonation reaction can be 20-90 ℃, and the time of the sulfonation reaction can be 10-75 h;

the temperature of the amination reaction can be 20-90 ℃, and the time of the amination reaction can be 10-75 h.

10. The preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the corrole catalytic group according to claim 1, wherein the steps are as follows in step (7):

the quaternizing agent is any one of methyl iodide, ethyl bromide, n-bromobutane and benzyl chloride;

the temperature of the quaternization reaction can be 0-70 ℃, and the quaternization reaction time can be 4-60 h;

the ion exchange capacity of the negative side is 0.8-2.5mmol/g dry film.

Technical Field

The invention relates to a preparation method of a monolithic poly (arylene ether nitrile) bipolar membrane containing a corrole water dissociation catalytic group, and particularly relates to a method for introducing an epoxy group-containing substituent on a poly (arylene ether nitrile) main chain, wherein corrole reacts with an epoxy group and is introduced into a poly (arylene ether nitrile) molecular structure. The preparation method comprises the steps of mixing the polypyrrole-containing polyarylether nitrile with the epoxy group-containing polyarylether nitrile to form a film as a base film material, and introducing anions and cations into two sides of the base film through the reaction of the epoxy group to synthesize the monolithic polyarylether nitrile bipolar film containing the carbazole group.

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 CN102061004B report a preparation method of a single-sheet bipolar membrane, which uses a polyolefin film or a polyhalogenated olefin film to immerse in a monomer of styrene-divinylbenzene and to perform radiation polymerization to make 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.

Polyarylene ether nitrile polymers are a well-known class of thermoplastic engineering plastics. Because the molecular structure of the polymer contains a large number of rigid aromatic ring structures, the polymer has high thermal stability and excellent mechanical property; the heat resistance is further improved due to the synergistic effect of the ether bond with the sulfone group, ketone group, and nitrile group. Because of their excellent comprehensive properties such as high heat-resistant grade, radiation resistance, corrosion resistance, good dimensional stability, excellent electrical properties, etc., they are widely used in many fields such as aircraft manufacturing, electronic information, household appliances, automobile manufacturing, petrochemical industry, medical health, etc. The cobalt corrole is bonded on the side group of the poly (arylene ether nitrile) in a side group form, the cobalt corrole with the function of catalyzing water dissociation is introduced into the bipolar membrane, and when a light source is injected, the cobalt corrole plays a role of catalyzing the water dissociation of the middle layer of the bipolar membrane, so that the membrane resistance and the cell voltage are reduced.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a simple, convenient and feasible preparation method of the monolithic poly (arylene ether nitrile) bipolar membrane containing the carbazole water dissociation catalytic group.

According to the invention, an epoxy group side group is introduced into a poly (arylene ether nitrile) molecular chain, the poly (arylene ether nitrile) containing the epoxy group and the poly (arylene ether nitrile) containing the corrole capable of promoting 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 corrole group-containing monolithic poly (arylene ether nitrile) 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 poly (arylene ether nitrile) bipolar membrane containing the corrole water dissociation catalytic group comprises the following steps:

(1) base film material: x mol of methoxy bisphenol, y mol of non-methoxy bisphenol, e mol of dihalocyanobenzene, (x + y-e) mol of dihalobenzophenone or dihalodiphenylsulfone and (1.2-3) (x + y) mol of catalystPutting the reagent I into a reactor, adding an organic solvent I for dissolving and dissolving in N₂Reacting for 1-5 h at 130-150 ℃ under the action of airflow, reacting for 3-20 h at 150-170 ℃, pouring the reaction liquid into water, separating out a precipitate, filtering, soaking the precipitate in running water for 20h, and drying the filtered solid to obtain the methoxy-containing poly (arylene ether nitrile) polymer.

X, y, e are not 0, and X + y > e.

(2) Dissolving a methoxy-containing poly (arylene ether nitrile) polymer in an organic solvent II, after the polymer is fully dissolved, installing a constant-pressure dropping funnel, vacuumizing, dropwise adding a boron tribromide solution (the boron tribromide is dissolved in the organic solvent II to prepare a solution) under the ice bath condition under the protection of nitrogen, after dropwise adding within 1-6 h, 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 for multiple times in sequence to obtain the poly (arylene ether nitrile) polymer containing hydroxyl, and drying for 24 hours in a vacuum drying oven at 80 ℃ for later use.

(3) Dissolving a hydroxyl-containing poly (arylene ether nitrile) polymer in an organic solvent III, heating to 40-70 ℃, respectively adding epoxy chloropropane and a catalyst II in equal molar ratio, reacting at constant temperature for 3-10 h, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), precipitating the poly (arylene ether nitrile) polymer containing an epoxy group, filtering, soaking the precipitate in running water for 24h, removing the organic solvent, unreacted epoxy chloropropane and the catalyst II, filtering and drying to obtain the poly (arylene ether nitrile) (PAEN-EG) polymer containing the epoxy group substituent.

(4) Preparing a catalyst capable of promoting the water dissociation of the bipolar membrane intermediate layer by bonding the side group of the poly (arylene ether nitrile) with the corrole: dissolving bromomethylation poly (arylene ether nitrile) polymer in an organic solvent IV, and taking 1 mol of bromomethyl in a molecular chain of the bromomethylation poly (arylene ether nitrile) polymer as a reference, and adding 0.2-1.02 mol of hydroxyl-containing corrole and 0.2-1.02 mol of 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 solvent of distilled water and methanol as a precipitator to precipitate a polymer product, washing the polymer product for multiple times by using the mixed solvent of water and methanol, and drying in vacuum to obtain the polyaromatic hydrocarbon with side groups bonded with corroleEther nitrile (core-PAEN) polymers.

(5) Mixing PAEN-EG and core-PAEN polymers in a ratio of 10: and (2) putting the mixture into an organic solvent V solvent according to the mass ratio of 0.01-1.0, after the polymer is completely dissolved, casting the mixture on a clean glass plate, and drying to prepare the poly (arylene ether nitrile) base film containing the side groups of the corrole and the epoxy group.

(6) The two sides of the poly (arylene ether nitrile) base membrane containing the corrole and the epoxy group side group are respectively reacted to introduce ion exchange groups: putting a base membrane into a reactor, respectively soaking two side surfaces of the base membrane into a positive surface sulfonation reaction solution and a negative surface amination reaction solution (the base membrane separates the two reaction solutions), and then putting the reactor into a constant-temperature water bath kettle for sulfonation reaction and amination reaction, so that the two side surfaces of the membrane respectively react with introduced sulfonic acid groups and amine groups.

(7) Quaternization: and carrying out quaternization reaction on the sulfonated and aminated poly (arylene ether nitrile) membrane and a quaternization reagent, washing with deionized water to obtain an anion exchange layer, and thus obtaining the monolithic poly (arylene ether nitrile) bipolar membrane containing the side groups of the corrole.

In step (1):

the dihalogenated cyanobenzene is any one or the combination of two of 2, 4-dichloroterephthalonitrile, 2, 4-difluoroterephthalonitrile, 2, 5-dichloroterephthalonitrile, 2, 5-difluoroterephthalonitrile, 2, 6-dichloroterephthalonitrile, 2, 6-difluoroterephthalonitrile, 2, 4-dichlorobenzonitrile, 2, 4-difluorodinitrile, 2, 5-dichlorobenzonitrile, 2, 5-difluorobenzonitrile, 2, 6-dichlorobenzonitrile, 2, 6-difluorobenzonitrile, 3, 5-dichlorobenzonitrile and 3, 5-difluorobenzonitrile in any proportion.

The bisphenol is any one or a combination of two of hydroquinone, resorcinol, bisphenol fluorene, bisphenol A, hexafluorobisphenol A, biphenol, dihydroxy diphenyl ether, 2-cyano hydroquinone, 3-cyano resorcinol, cyano biphenol and cyano dihydroxy diphenyl ether in any proportion.

The dihalobenzophenone is any one or combination of two of difluorobenzophenone, dichlorobenzophenone, difluorodinitrile benzophenone and dichlorodinitrile benzophenone in any proportion.

The dihalo diphenyl sulfone is any one of difluoro diphenyl sulfone, dichloro diphenyl sulfone, difluoro dinitrile diphenyl sulfone and dichloro dinitrile diphenyl sulfone or the combination of two of them in any proportion.

The methoxyl-containing bisphenol is any one of p-2-methoxyl hydroquinone, 5-methoxyl resorcinol, 2, 3-dimethoxy hydroquinone, 2, 5-dimethoxy hydroquinone, 2, 6-dimethoxy hydroquinone, 2,3, 5-trimethoxy hydroquinone, 2,3,5, 6-tetramethoxy hydroquinone, 3',5,5' -tetramethoxy-4, 4 '-biphenol, tetramethoxy biphenol, 3',5,5 '-tetramethoxy-4, 4' -dihydroxy diphenyl ether and tetramethoxy-dihydroxy diphenyl ether or a combination of two of the two in any proportion.

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

The catalyst I is anhydrous potassium carbonate or anhydrous sodium carbonate.

In step (2):

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

The corrole is any one of hydroxyl corrole, amino corrole and hydroxyl metal (M) corrole (metal M is Co, Ni, Cu, Zn, Fe, Mg, Ba, Sc, Ti, V, Cr or Mn).

In step (3):

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

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

In the step (4), the organic solvent IV is any one or a combination of two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone in any proportion.

In the step (5), the organic solvent V is any one of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone or a combination of two of the two in any proportion

In step (6):

the sulfonation reagent in the cation sulfonation reaction solution 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. The cation exchange capacity is 0.6-2.0mmol/g dry film.

The amination reagent in the negative amination reaction solution 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 a combination of two of DMF, DMAc, NMP, DMSO and the like in any proportion.

The temperature of the sulfonation reaction can be 20-90 ℃, and the time of the sulfonation reaction can be 10-75 h.

The temperature of the amination reaction can be 20-90 ℃, and the time of the amination reaction can be 10-75 h.

In step (7):

the quaternizing agent is any one of methyl iodide, ethyl bromide, n-bromobutane and benzyl chloride;

the temperature of the quaternization reaction can be 0-70 ℃, and the quaternization reaction time 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. through polycondensation, methoxy-containing is introduced into a poly (arylene ether nitrile) molecular chain, boron tribromide reaction is carried out to obtain poly (arylene ether nitrile) containing hydroxyl, and then the poly (arylene ether nitrile) is reacted with epoxy chloropropane to introduce an epoxy group into a poly (arylene ether nitrile) side group. The epoxy group reacts with the sulfonating agent and the aminating agent to introduce an anion-cation exchange membrane into a poly (arylene ether nitrile) molecular chain to prepare the single-chip 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. Epoxy groups and hydroxyl-containing corrole are utilized to react, corrole groups are introduced on the side groups of the poly (arylene ether nitrile) to serve as a bipolar membrane intermediate layer water dissociation catalyst. The corrole is bonded in the polymer molecule and does not move. The blend of the corrole-containing poly (arylene ether nitrile) copolymer and the epoxy group-containing poly (arylene ether nitrile) copolymer is used as a base membrane material, and the prepared bipolar membrane has an autocatalytic 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 process of the present invention.

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 figure 1, firstly, an epoxy group side group is introduced into a poly (arylene ether nitrile) molecular chain, the poly (arylene ether nitrile) containing the epoxy group and the corrole-containing poly (arylene ether nitrile) capable of promoting 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 corrole-group-containing monolithic poly (arylene ether nitrile) bipolar membrane. In the figure, (n + m) is the degree of polymerization of the main chain of the polyarylene ether nitrile, and n, m are integers other than zero; y is⁺Is a cation, Y⁺Is H⁺、Na⁺、K⁺Any one of (a); x^-Is a cation, X^-Is Cl^-、Br^-、I^-、OH^-、SO₃H^-Any one of the above.