CN111530298A - Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group - Google Patents

Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group Download PDF

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CN111530298A
CN111530298A CN202010398462.9A CN202010398462A CN111530298A CN 111530298 A CN111530298 A CN 111530298A CN 202010398462 A CN202010398462 A CN 202010398462A CN 111530298 A CN111530298 A CN 111530298A
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phthalocyanine
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polyarylethersulfone ketone
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黄雪红
李晓燕
丁富传
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Fujian Normal University
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Abstract

The invention relates to a preparation method of a monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic groups. The preparation method comprises the steps of taking methoxy bisphenol, non-methoxy bisphenol, dihalo-benzophenone and dihalo-diphenylsulfone as raw materials, catalytically synthesizing PPBESK-EG and Pc-PPBESK, mixing the materials, casting the mixture on a glass plate, sulfonating, aminating, quaternizing, and washing with deionized water to obtain the monolithic polyarylether sulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group. According to the bipolar membrane prepared by the invention, through polycondensation, methoxy is introduced into a polyarylethersulfone ketone molecular chain, boron tribromide is used for reaction to obtain hydroxyl-containing polyarylethersulfone ketone, and then the hydroxyl-containing polyarylethersulfone ketone is reacted with epoxy chloropropane, and an epoxy group is introduced into a polyarylethersulfone ketone side group, so that a membrane forming process is omitted, and the use of carcinogenic chloromethyl ether is avoided. The prepared bipolar membrane has an autocatalytic effect, and the resistance and transmembrane voltage of the bipolar membrane are low. The problems of bubbling and cracking of the intermediate interface layer and the like do not occur after long-term use.

Description

Preparation method of monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic group
Technical Field
The invention relates to a preparation method of a monolithic poly (aryl ether sulfone ketone) bipolar membrane containing phthalocyanine water dissociation catalytic groups, in particular to a method for introducing an epoxy group-containing substituent group to a main chain of poly (aryl ether sulfone ketone), and introducing phthalocyanine and an epoxy group into a poly (aryl ether sulfone ketone) molecular structure through reaction. The preparation method comprises the steps of blending phthalocyanine-containing polyarylethersulfone ketone and epoxy-containing agglomerated polyarylethersulfone ketone 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 epoxy groups to synthesize the phthalocyanine group-containing monolithic polyarylethersulfone ketone 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 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.
The polyarylethersulfone ketone (PPBESK) is a novel high-performance engineering plastic, the glass transition temperature of the PPBESK is between 230 ℃ and 370 ℃, the heat resistance of the PPBESK is superior to that of polyether ether ketone (PEEK), the PPBESK is soluble, the PPBESK is a novel soluble polyarylether product with the highest heat resistance level at present, the comprehensive performance is excellent, and the PPBESK has a good application prospect. The metal phthalocyanine with the photocatalysis function is introduced into the bipolar membrane, and the metal phthalocyanine plays a role in catalyzing the water dissociation of the middle layer of the bipolar membrane when a light source is injected, 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 (aryl ether sulfone ketone) bipolar membrane containing phthalocyanine water dissociation catalytic groups.
According to the invention, an epoxy group side group is introduced into a polyarylethersulfone ketone molecular chain, the polyarylethersulfone ketone containing the epoxy group and polyarylethersulfone ketone containing phthalocyanine 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 phthalocyanine group-containing monolithic polyarylethersulfone ketone 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 polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic groups comprises the following steps:
(1) base film material: placing x mol of bisphenol containing methoxyl, y mol of bisphenol not containing methoxyl, e mol of dihalo benzophenone, (x + y) -e) mol of dihalo diphenyl sulfone and (1.2-3) (x + y) mol of catalyst I in organic solvent I, and reacting 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 waterAnd (3) precipitating, filtering, soaking the precipitate in running water for 20 hours, and drying the filtered solid to obtain the methoxy polyarylethersulfone ketone. x, y, e are not 0, and x + y > e.
(2) Dissolving the methoxyl group-containing polyarylethersulfone ketone 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 (a solution prepared by dissolving boron tribromide in an organic solvent II) under an ice bath condition, heating to room temperature, continuing to react for 12 hours, and stopping the reaction after the dropwise adding is finished within 1-6 hours. After the reaction is finished, filtering, washing with dichloromethane, methanol and water sequentially for many times to obtain the hydroxyl-containing polyarylethersulfone ketone polymer, and drying for 24 hours in a vacuum drying oven at 80 ℃ for later use.
(3) Dissolving a hydroxyl-containing polyarylethersulfone ketone 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 an epoxy group-containing polymerized polyarylethersulfone ketone polymer, filtering, soaking the precipitate in running water for 24h, removing the organic solvent, unreacted epoxy chloropropane and the catalyst, filtering and drying to obtain a base membrane material of the epoxy group-containing substituent polyarylethersulfone ketone polymer (PPBESK-EG).
(4) Preparing a catalyst capable of promoting the water dissociation of the bipolar membrane middle layer by bonding polyarylethersulfone ketone side groups with phthalocyanine: dissolving a bromomethylated polyarylethersulfone ketone polymer in an organic solvent IV, and taking 1 mol of bromomethyl in a molecular chain of the bromomethylated polyarylethersulfone ketone polymer as a basis, wherein (0.2-1.02) mol of phthalocyanine containing hydroxyl substituents and (0.2-1.02) NaHCO3Adding the mixture into a reaction system according to the molar ratio, 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-PPBESK) with the phthalocyanine bonded by the polyarylethersulfone ketone side group.
(5) PPBESK-EG and Pc-PPBESK polymers were polymerized in 10: (0.1-1.0) putting the mixture into an organic solvent V solvent in a mass ratio, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone base film containing the phthalocyanine and epoxy group side groups.
(6) The two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and epoxy group side groups respectively react to introduce ion exchange groups: the method comprises the steps of vertically placing a base membrane into a reactor, enabling two side faces of the base membrane to be soaked in a positive surface sulfonation reaction solution and a negative surface amination reaction solution respectively (the base membrane separates the two reaction solutions), then placing the reactor into a constant-temperature water bath kettle for reaction, and enabling the two side faces of the membrane to be reacted respectively to introduce different ion exchange groups.
(7) Quaternization: and reacting the anion membrane subjected to amination reaction with an amination reagent to carry out quaternization reaction, washing with deionized water to obtain an anion exchange layer, and thus obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
In step (1):
the bisphenol is any one or the combination of two of hydroquinone, resorcinol, bisphenol fluorene, bisphenol A, hexafluorobisphenol A, biphenol and 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.
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 phthalocyanine is any one of hydroxyl phthalocyanine, amino phthalocyanine and metal (M) phthalocyanine. Metal M ═ Mg, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn.
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 dichloromethane, the chloroform, the tetrahydrofuran, the N, N-dimethylformamide and the N, N-dimethylacetamide in any proportion.
In step (6):
the sulfonation reagent in the positive 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 cathode 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 the step (7), halogenated alkane can be used as the quaternizing agent, and 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 invention has the advantages and beneficial effects that:
1. introducing methoxyl into a polyarylethersulfone ketone molecular chain through polycondensation, reacting with boron tribromide to obtain the polyarylethersulfone ketone containing hydroxyl, and reacting with epichlorohydrin to introduce an epoxy group into a polyarylethersulfone ketone side group. The epoxy group reacts with the sulfonating agent and the aminating agent to introduce anion and cation exchange membranes into the molecular chain of the polyarylethersulfone ketone 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. The reaction of epoxy group and phthalocyanine containing hydroxyl (or amino) is utilized to introduce phthalocyanine group on the polyarylethersulfone ketone side group as bipolar membrane middle layer water dissociation catalyst. The phthalocyanine is bonded in the polymer molecule and no migratory motion occurs. The prepared bipolar membrane has the autocatalysis effect, and is low in resistance and low in 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 described with reference to the following examples and the accompanying drawings, 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 above descriptions are still within the scope of the present invention.
According to the invention, an epoxy group side group is introduced into a polyarylethersulfone ketone molecular chain, the polyarylethersulfone ketone containing the epoxy group and polyarylethersulfone ketone containing phthalocyanine 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 phthalocyanine group-containing monolithic polyarylethersulfone ketone bipolar membrane.
In the figure, (n + m) is the polymerization degree of the main chain of the polyarylethersulfone ketone-based membrane, and n and m are integers which are not zero; y + is a cation, Y+Can be H+、Na+、K+Any one of (a); x-May be Cl-、Br-、I-、OH-、SO3H-Any one of the above.
Example 1
(1) 8.6898g (70mmol) of o-methyl hydroquinone, 1.1101g (10mmol) of resorcinol, 15.2749g (70mmol) of difluorobenzophenone, 2.5425g (10mmol) of difluorodiphenyl sulfone, 13.2664g (90mmol) of anhydrous potassium carbonate, 320mL of toluene and 400mL of DMAc are sequentially added into a three-neck flask, the mixture is reacted for 3 hours at 140 ℃ in nitrogen atmosphere, then the temperature is increased to 160 ℃ for reaction for 8 hours, and the reaction solution is immediately poured into deionized water for precipitation and filtration under stirring. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000061
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 3.6mL of boron tribromide solution diluted by 36mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000062
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, adding 1.5g of epoxy chloropropane and 1.6g of Na2CO3, reacting at a constant temperature of 70 ℃ for 5h, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)) after the reaction is finished, separating out a precipitate, leaching the precipitate with ethanol for multiple times, removing unreacted epoxy chloropropane, soaking the precipitate in water again, filtering after 24h, and drying the precipitate at 70 ℃ in vacuum to prepare an epoxy-containing agglomerated polyarylethersulfone ketone polymer (PPBESK-EG) serving as a base membrane material of the polyarylethersulfone ketone bipolar membrane.
Figure BDA0002488447250000063
(4) Side-chain bonded phthalocyanine substituent Pc-PPBESK polymer: 5.0g of PPBESK-EG polymer and 60mL of DMAc were added to a 100mL three-necked flask, and after the copolymer was sufficiently dissolved, 20mL of DMAc solution in which 6.8g of copper hydroxy phthalocyanine was dissolved and 1.0g of NaHCO were added3And adding the mixture into a three-neck flask, heating to 70 ℃ under the protection of nitrogen, reacting at constant temperature for 5 hours, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to a side chain.
Figure BDA0002488447250000071
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.6: adding the mixture into NMP solvent in a mass ratio of 0.4, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (mass ratio of NaHSO)3：H2O: DMF ═ 1: 8: 2) and the other side is soaked in a negative reaction solution (mass ratio of ethylene diamine: h2O: DMF ═ 1: 9: 1) the two reaction liquids are separated by the membrane, nitrogen is introduced to remove air in the reactor, then the reactor is sealed, the reactor is placed in a constant temperature water bath kettle at 70 ℃ for reaction for 70 hours, so that the two side surfaces of the membrane respectively react and introduce sulfonic acid groups and amino groups, and the ion exchange capacity of the positive surface is 1.36 mmol/g.
(7) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 1.67 mmol/g.
(8) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Figure BDA0002488447250000081
The bipolar membrane prepared in example 1 was found to have an electrical conductivity of 0.03 S.cm at 30 ℃-1The water content is 25.8%; the cation exchange capacity was 1.54 mmol/g-1(ii) a The anion exchange capacity was 2.01 mmol/g-1。
And (3) performing structural characterization on the basement membrane and the prepared bipolar membrane by using an infrared spectrometer, wherein the result is shown in figure 1, and figure 1 is an infrared spectrogram of the PPBESK-EG basement membrane. In the IR spectrum, 1650cm-1The stretching vibration absorption peak of carbonyl in the molecular structure of PPBESK is 1598 cm and 1498cm-1The plane vibration absorption peak of Ar-O-Ar in the molecular structure of the PPBESK appears, 1237 and 1160cm-1The asymmetric stretching vibration absorption peak of Ar-O-Ar in the PPBESK molecular structure is shown, 1047 cm and 1014cm-1The absorption peak of the stretching vibration of O ═ S ═ O in the molecular structure of PPBESK appears at 908cm-1The characteristic absorption of the side-group epoxy bond appears, which indicates that the PPBESK molecule contains epoxy groups.
Example 2
(1) Preparing methoxy-containing polyarylethersulfone ketone: sequentially adding the components into a three-neck flask5.1369g (30mmol) of 2, 5-dimethoxyhydroquinone, 1.1101g (10mmol) of resorcinol, 7.6275g (30mmol) of difluorodiphenyl sulfone, 2.1820g (10mmol) of difluorobenzophenone, 6.9002g (50mmol) of anhydrous potassium carbonate, 160mL of toluene, DMAc200mL in N2Reacting at 140 ℃ for 3h in the atmosphere, then heating to 175 ℃ for 9h, immediately pouring the reaction solution into deionized water under stirring for precipitation, and filtering. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000082
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 3.2mL of boron tribromide solution diluted by 32mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000091
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, and then adding 2.54g of epichlorohydrin and 2.57g of Na2CO3And reacting for 5 hours at a constant temperature of 70 ℃, after the reaction is finished, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), separating out a precipitate, leaching the precipitate for multiple times by using ethanol, removing epichlorohydrin, soaking the precipitate in water again, filtering after 24 hours, and drying the precipitate in vacuum at 70 ℃ to prepare the epoxy group-containing poly (aryl ether sulfone ketone) (PPBESK-EG).
Figure BDA0002488447250000092
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of epoxy group-containing poly (aryl ether sulfone ketone) polymer and 60mLNMP into a 100mL three-necked bottle, after the copolymer is fully dissolved, adding 20mL of NMP solution in which 12.6g of hydroxyl iron phthalocyanine is dissolved and 2.2g of NaHCO3 into the three-necked bottle, heating to 50 ℃ under the protection of nitrogen, reacting at constant temperature for 5h, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded on the side chain.
Figure BDA0002488447250000093
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.8: adding the mixture into NMP solvent in a mass ratio of 0.2, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (mass ratio of NaHSO)3：H2O: DMF ═ 1: 8: 2) and soaking the negative surface of the other side in deionized water, separating the two liquids by the membrane, introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a constant-temperature water bath kettle at 70 ℃ for reaction for 75 hours to enable the epoxy group on the positive surface of the membrane to react with a sulfonating agent to introduce sulfonic acid groups, wherein the ion exchange capacity of the positive surface is 1.74 mmol/g.
(7) The positive surface solution of the reactor is changed into deionized water, and the negative surface reaction solution of the membrane is changed into amination agent solution (dimethylamine: H in mass ratio)2O: DMF ═ 1: 8: 1) introducing nitrogen to remove air in the reactor, sealing, putting the reactor into a constant-temperature water bath kettle at 50 ℃ for reaction for 40 hours, and introducing amino into the film on the negative surface of the amination agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 1.92 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Example 3
(1) Preparing methoxy-containing polyarylethersulfone ketone: a three-necked flask was charged with 2.0223g (10mmol) of 2,3, 5-trimethoxyhydroquinone, 1.1101g (10mmol) of resorcinol, 2.5425g (10mmol) of difluorodiphenyl sulfone, 2.1820g (10mmol) of difluorobenzophenone, 2.07g (15mmol) of anhydrous potassium carbonate, 160mL of toluene, and DMAc200mL in that order in N2Reacting at 140 ℃ for 3h in the atmosphere, then heating to 170 ℃ for reacting for 6h, immediately pouring the reaction solution into deionized water under stirring for precipitation, and filtering. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000101
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 4.0mL of boron tribromide solution diluted by 40mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000102
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, and adding 2.54g of epoxyChloropropane and 2.57g Na2CO3And reacting for 5 hours at a constant temperature of 70 ℃, after the reaction is finished, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), separating out a precipitate, leaching the precipitate for multiple times by using ethanol, removing epichlorohydrin, soaking the precipitate in water again, filtering after 24 hours, and drying the precipitate in vacuum at 70 ℃ to prepare the epoxy group-containing poly (aryl ether sulfone ketone) (PPBESK-EG).
Figure BDA0002488447250000111
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of epoxy group-containing poly (aryl ether sulfone ketone) polymer and 60mL of NMP into a 100mL three-necked bottle, and dissolving the copolymer fully, then adding 20mL of NMP solution dissolved with 19.8g of hydroxyl manganese phthalocyanine and 3.4g of NaHCO3And adding the mixture into a three-neck flask, heating to 50 ℃ under the protection of nitrogen, reacting at constant temperature for 5 hours, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to a side chain.
Figure BDA0002488447250000112
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.85: adding the mixture into NMP solvent in a mass ratio of 0.15, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing the phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (mass ratio of NaHSO)3：H2O: DMAc ═ 1: 8: 3) soaking the other side of the negative surface in deionized water, separating the two liquids with the membrane, introducing nitrogen to remove air in the reactor, sealing, and reacting in a 70 deg.C constant temperature water bath for 70 hr to make the positive surface of the membrane ringThe oxygen group reacts with the sulfonating agent to introduce sulfonic acid group, and the ion exchange capacity of the positive surface is 1.68 mmol/g.
(7) The solution on the positive surface of the reactor is changed into deionized water, and the reaction solution on the negative surface of the membrane is changed into aminating agent solution (mass ratio of ethylene diamine to H)2O: DMAc ═ 1: 8: 2) introducing nitrogen to remove air in the reactor, sealing, putting the reactor into a constant-temperature water bath kettle at 40 ℃ for reaction for 50 hours, and introducing amino into the film on the negative surface of the amination agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 1.91 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Example 4
(1) Preparing methoxy-containing polyarylethersulfone ketone: a three-necked flask was charged with a solution containing 3.2221g (10mmol) of 3,3',5,5' -tetramethoxy-4, 4' -hydroxydiphenyl ether, 3.5041g (10mmol) of bisphenol fluorene, 2.5425g (10mmol) of difluorodiphenyl sulfone, 2.1820g (10mmol) of difluorobenzophenone, 2.07g (15mmol) of anhydrous potassium carbonate, 160mL of toluene, and DMAc200mL in that order in the presence of N2Reacting at 140 ℃ for 3h in the atmosphere, then heating to 170 ℃ for reacting for 6h, immediately pouring the reaction solution into deionized water under stirring for precipitation, and filtering. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000121
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 4.0mL of boron tribromide solution diluted by 40mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000122
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, adding 2.19g of epoxy chloropropane and 2.58g of Na2CO3, reacting at a constant temperature of 70 ℃ for 5h, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)) after the reaction is finished, separating out a precipitate, leaching the precipitate with ethanol for multiple times, removing the epoxy chloropropane, soaking the precipitate in water again, filtering after 24h, and drying the precipitate at 70 ℃ in vacuum to prepare the epoxy-containing agglomerated polyarylethersulfone ketone polymer (PPBESK-EG).
Figure BDA0002488447250000131
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of epoxy group-containing polyarylethersulfone ketone polymer and 60mL of NMP into a 100mL three-necked bottle, and after the copolymer is fully dissolved, dissolving 20mL of NMP solution in which 10.95g of hydroxyl manganese phthalocyanine is dissolved and 1.73g of NaHCO3And adding the mixture into a three-neck flask, heating to 50 ℃ under the protection of nitrogen, reacting at constant temperature for 5 hours, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to a side chain.
Figure BDA0002488447250000141
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.9: adding the mixture into NMP solvent in a mass ratio of 0.10, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (mass ratio H)2SO4：H2O: DMSO ═ 0.5: 8: 3) and soaking the negative surface of the other side in deionized water, separating the two liquids by the membrane, introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a constant-temperature water bath kettle at 60 ℃ for reaction for 50 hours to enable the epoxy group on the positive surface of the membrane to react with a sulfonating agent to introduce sulfonic acid groups, wherein the ion exchange capacity of the positive surface is 1.71 mmol/g.
(7) The solution on the positive surface of the reactor is changed into deionized water, and the reaction solution on the negative surface of the membrane is changed into aminating agent solution (mass ratio of ethylene diamine to H)2O: DMSO ═ 1: 8: 2) introducing nitrogen to remove air in the reactor, sealing, putting the reactor into a constant-temperature water bath kettle at 40 ℃ for reaction for 50 hours, and introducing amino into the film on the negative surface of the amination agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 2.17 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Example 5
(1) Preparing methoxy-containing polyarylethersulfone ketone: a three-necked flask was charged with a solution containing 3.0621g (10mmol) of 3,3',5,5' -tetramethoxy-4, 4' -biphenol, 3.5041g (10mmol) of bisphenol fluorene, 2.5425g (10mmol) of difluorodiphenyl sulfone, 2.1820g (10mmol) of difluorobenzophenone, 2.07g (15mmol) of anhydrous potassium carbonate, 160mL of toluene, and 200mL of DMAc in the stated order in the presence of N2Reacting at 140 ℃ for 3h in the atmosphere, then heating to 170 ℃ for reacting for 6h, immediately pouring the reaction solution into deionized water under stirring for precipitation, and filtering. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000151
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 4.0mL of boron tribromide solution diluted by 40mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000152
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, and then adding 2.14g of epichlorohydrin and 2.50g of Na2CO3And reacting for 5 hours at a constant temperature of 70 ℃, after the reaction is finished, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), separating out a precipitate, leaching the precipitate for multiple times by using ethanol, removing epichlorohydrin, soaking the precipitate in water again, filtering after 24 hours, and drying the precipitate in vacuum at 70 ℃ to prepare the epoxy group-containing poly (aryl ether sulfone ketone) (PPBESK-EG).
Figure BDA0002488447250000161
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of bromomethylated polyarylethersulfone ketone polymer and 60mL of NMP into a 100mL three-necked bottle, and after the copolymer is fully dissolved, adding 20mL of NMP solution in which 10.6g of hydroxyl iron phthalocyanine is dissolved and 1.6g of NaHCO3Adding into three-neck bottle, heating to 50 deg.C under nitrogen protection, reacting at constant temperature for 5 hr, immediately cooling to room temperature with ice water bath, and mixing with distilled water and methanolPrecipitating the product polymer with precipitant, washing with mixed solution for several times, and vacuum drying to obtain polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to its side chain.
Figure BDA0002488447250000171
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.9: 0.1 mass ratio, casting on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing the phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, soaking one side surface of the membrane in a positive surface reaction solution (the mass ratio is KHSO 3: H2O: DMSO is 1: 7: 2), soaking the negative surface of the other side in deionized water, separating the two liquids by the membrane, introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a constant-temperature water bath kettle at 70 ℃ for reaction for 72 hours, and reacting the positive surface epoxy group of the membrane with a sulfonating agent to introduce sulfonic acid groups, wherein the ion exchange capacity of the positive surface is 1.85 mmol/g.
(7) And (3) replacing the solution on the positive side of the reactor with deionized water, replacing the reaction solution on the negative side of the membrane with an aminating agent solution (the mass ratio is ethylenediamine: H2O: DMSO: 1: 9: 3), introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a constant-temperature water bath kettle at 50 ℃ for reaction for 40 hours, and introducing amino groups into the reaction solution on the negative side of the membrane by using the aminating agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 2.28 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Example 6
(1) Preparing methoxy-containing polyarylethersulfone ketone: 2.3421g (10mmol) of 2,3,5, 6-tetramethoxyhydroquinone, 2.2202g (20mmol) of resorcinol, 2.5425g (10mmol) of difluorodiphenyl sulfone, 4.3640g (20mmol) of difluorobenzophenone, 5.52g (40mmol) of anhydrous potassium carbonate, 160mL of toluene and DMAc200mL are sequentially added into a three-neck flask, and the mixture is reacted for 3 hours at 140 ℃ in an N2 atmosphere, then the temperature is raised to 170 ℃ for 6 hours, and the reaction liquid is immediately poured into deionized water for precipitation under stirring and filtered. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000181
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 4.0mL of boron tribromide solution diluted by 40mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000182
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, and then adding 2.27g of epichlorohydrin and 2.60g of Na2CO3And reacting for 5 hours at a constant temperature of 70 ℃, after the reaction is finished, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), separating out a precipitate, leaching the precipitate for multiple times by using ethanol, removing epichlorohydrin, soaking the precipitate in water again, filtering after 24 hours, and drying the precipitate in vacuum at 70 ℃ to prepare the epoxy group-containing poly (aryl ether sulfone ketone) (PPBESK-EG).
Figure BDA0002488447250000191
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of epoxy group-containing polyarylethersulfone ketone polymer and 60mL of NMP into a 100mL three-necked bottle, and after the copolymer is fully dissolved, adding 20mL of NMP solution in which 12.2g of hydroxyl phthalocyanine nickel is dissolved and 1.8g of NaHCO3And adding the mixture into a three-neck flask, heating to 50 ℃ under the protection of nitrogen, reacting at constant temperature for 5 hours, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to a side chain.
Figure BDA0002488447250000201
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.9: adding the mixture into NMP solvent in a mass ratio of 0.1, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (the mass ratio is H)2SO4：H2O: NMP 0.5: 8: 3) and soaking the negative surface of the other side in deionized water, separating the two liquids by the membrane, introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a constant-temperature water bath kettle at 70 ℃ for reaction for 65 hours to enable the epoxy group on the positive surface of the membrane to react with a sulfonating agent to introduce sulfonic acid groups, wherein the ion exchange capacity of the positive surface is 1.75 mmol/g.
(7) The positive surface solution of the reactor is changed into deionized water, and the negative surface reaction solution of the membrane is changed into amination agent solution (the mass ratio is diethylamine: H)2O: DMSO ═ 1: 8: 2) introducing nitrogen to remove air in the reactor, sealing, putting the reactor into a constant-temperature water bath kettle at 50 ℃ for reaction for 40 hours, and introducing amino into the film on the negative surface of the amination agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 1.80 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Example 7
(1) Preparing methoxy-containing polyarylethersulfone ketone: a three-necked flask was charged with 1.7212g (10mmol) of 2, 6-dimethoxyhydroquinone, 2.2820g (10mmol) of bisphenol A, 2.5425g (10mmol) of difluorodiphenyl sulfone, 2.1820g (10mmol) of difluorobenzophenone, 2.07g (15mmol) of anhydrous potassium carbonate, 160mL of toluene, and DMAc200mL in that order under N2Reacting at 140 ℃ for 3h in the atmosphere, then heating to 170 ℃ for reacting for 6h, immediately pouring the reaction solution into deionized water under stirring for precipitation, and filtering. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000211
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 3.0mL of boron tribromide solution diluted by 30mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000212
Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, and then adding 1.68g of epichlorohydrin and 1.92g of Na2CO3And reacting for 5 hours at a constant temperature of 70 ℃, after the reaction is finished, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), separating out a precipitate, leaching the precipitate for multiple times by using ethanol, removing epichlorohydrin, soaking the precipitate in water again, filtering after 24 hours, and drying the precipitate in vacuum at 70 ℃ to prepare the epoxy group-containing poly (aryl ether sulfone ketone) (PPBESK-EG).
Figure BDA0002488447250000221
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of bromomethylated polyarylethersulfone ketone polymer and 60mL of NMP into a 100mL three-neck flask, and after the copolymer is fully dissolved, adding 20mL of NMP solution in which 4.44g of hydroxyl iron phthalocyanine is dissolved and 0.67g of NaHCO3And adding the mixture into a three-neck flask, heating to 50 ℃ under the protection of nitrogen, reacting at constant temperature for 5 hours, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to a side chain.
Figure BDA0002488447250000222
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.8: adding the mixture into NMP solvent in a mass ratio of 0.2, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (mass ratio of NaHSO)3：H2O: DMSO ═ 1: 7: 2) soaking the negative surface of the other side in deionized water, separating the two liquids by the membrane, introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a 70 deg.C constant temperature water bath for reaction for 75h to allow the positive epoxy group of the membrane to react with sulfonating agent to introduce sulfonic acid groupThe cation surface had an ion exchange capacity of 1.62 mmol/g.
(7) The solution on the positive surface of the reactor is changed into deionized water, and the reaction solution on the negative surface of the membrane is changed into aminating agent solution (mass ratio of ethylene diamine to H)2O: DMSO ═ 1: 7: 2) introducing nitrogen to remove air in the reactor, sealing, putting the reactor into a constant-temperature water bath kettle at 50 ℃ for reaction for 40 hours, and introducing amino into the film on the negative surface of the amination agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 1.77 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.
Example 8
(1) Preparing methoxy-containing polyarylethersulfone ketone: a three-necked flask was charged with 2.0312g (10mmol) of 2,3, 5-trimethoxyhydroquinone, 3.3623g (10mmol) of hexafluorobisphenol A, 2.5425g (10mmol) of difluorodiphenyl sulfone, 2.1820g (10mmol) of difluorobenzophenone, 2.07g (15mmol) of anhydrous potassium carbonate, 160mL of toluene, and DMAc200mL in that order in N2Reacting at 140 ℃ for 3h in the atmosphere, then heating to 170 ℃ for reacting for 6h, immediately pouring the reaction solution into deionized water under stirring for precipitation, and filtering. Soaking the precipitate obtained by filtering in deionized water, soaking in running water for 24h, filtering, and drying the precipitate in a vacuum oven at 80 deg.C for 10h to obtain product containing methoxyl polyarylethersulfone ketone.
Figure BDA0002488447250000231
(2) Weighing 5.0g of methoxyl-containing polyarylethersulfone ketone polymer in a 250mL three-neck flask, installing a constant pressure dropping funnel, vacuumizing, and protecting with a nitrogen balloon. And adding 120mL of dried dichloromethane in advance to dissolve the polymer, dropwise adding 3.0mL of boron tribromide solution diluted by 30mL of dichloromethane under the ice bath condition, naturally 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 for multiple times in sequence, and drying for 24 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the hydroxyl-containing polyarylethersulfone ketone polymer.
Figure BDA0002488447250000241
(3) Adding 5.0g of hydroxyl-containing polyarylethersulfone ketone into a three-necked bottle, dissolving with 60mL of N-methylpyrrolidone, and then adding 2.28g of epichlorohydrin and 2.72g of Na2CO3And reacting for 5 hours at a constant temperature of 70 ℃, after the reaction is finished, pouring the reaction solution into a water/ethanol mixed solvent (the volume ratio of the two is 1 (0.5-1)), separating out a precipitate, leaching the precipitate for multiple times by using ethanol, removing epichlorohydrin, soaking the precipitate in water again, filtering after 24 hours, and drying the precipitate in vacuum at 70 ℃ to prepare the epoxy group-containing poly (aryl ether sulfone ketone) (PPBESK-EG).
Figure BDA0002488447250000242
(4) Synthesizing a bipolar membrane middle layer water catalyst-side chain bonded phthalocyanine substituent Pc-PPBESK polymer: adding 5.0g of bromomethylated polyarylethersulfone ketone polymer and 60mL of NMP into a 100mL three-neck flask, and after the copolymer is fully dissolved, adding 20mL of NMP solution in which 4.44g of hydroxyl iron phthalocyanine is dissolved and 0.67g of NaHCO3And adding the mixture into a three-neck flask, heating to 50 ℃ under the protection of nitrogen, reacting at constant temperature for 5 hours, immediately cooling the system to room temperature by using an ice water bath after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain the polymer (Pc-PPBESK) with phthalocyanine (Pc) bonded to a side chain.
Figure BDA0002488447250000251
(5) Mixing PPBESK-EG polymer and Pc-PPBESK polymer according to the weight ratio of 9.8: adding the mixture into NMP solvent in a mass ratio of 0.2, casting the mixture on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polyarylethersulfone ketone-based membrane material containing phthalocyanine and epoxy group side groups.
(6) Placing a polyarylethersulfone ketone base membrane containing phthalocyanine and epoxy group side groups in a reactor, and soaking one side surface of the membrane in a positive reaction solution (mass ratio H)2SO4：H2O: DMSO ═ 1: 7: 3) and soaking the negative surface of the other side in deionized water, separating the two liquids by the membrane, introducing nitrogen to remove air in the reactor, sealing, placing the reactor in a constant-temperature water bath kettle at 50 ℃ for reaction for 75 hours to enable the epoxy group on the positive surface of the membrane to react with a sulfonating agent to introduce sulfonic acid groups, wherein the ion exchange capacity of the positive surface is 1.69 mmol/g.
(7) The positive side solution of the reactor is changed into deionized water, and the negative side reaction solution of the membrane is changed into amination agent solution (mass ratio of diethyl triamine: H)2O: DMSO ═ 1: 7: 3) introducing nitrogen to remove air in the reactor, sealing, putting the reactor into a constant-temperature water bath kettle at 60 ℃ for reaction for 40 hours, and introducing amino groups into the film on the negative surface of the amination agent.
(8) Immersing the negative surface of the reacted membrane in a 50% methyl iodide/ethanol solution, reacting for 48h at 0 ℃, and carrying out quaternization on the negative surface of the membrane, wherein the ion exchange capacity of the negative surface is 1.93 mmol/g.
(9) And (3) reacting the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and the epoxy group side group to introduce anion and cation exchange groups, thereby obtaining the monolithic polyarylethersulfone ketone bipolar membrane containing the phthalocyanine water dissociation catalytic group.

Claims (10)

1. A preparation method of a monolithic polyarylethersulfone ketone bipolar membrane containing phthalocyanine water dissociation catalytic groups is characterized by comprising the following steps:
(1) base film material: placing x mol of bisphenol containing methoxyl, y mol of bisphenol not containing methoxyl, e mol of dihalobenzophenone, (x + y-e) mol of dihalodiphenylsulfone and (1.2-3) (x + y) mol of catalyst I in organic solvent I, and reacting 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 polyarylethersulfone ketone; x, y, e are not 0, and x + y > e;
(2) dissolving a methoxyl group-containing polyarylethersulfone ketone polymer in an organic solvent II, fully dissolving, then installing a constant-pressure dropping funnel, vacuumizing, then, under the protection of nitrogen, dropwise adding a boron tribromide solution under the ice bath condition, after dropwise adding is finished within 1-6 h, heating to room temperature, continuing to react for 12h, stopping the reaction, filtering, sequentially washing with dichloromethane, methanol and water for multiple times to obtain a hydroxyl group-containing polyarylethersulfone ketone polymer, and drying for 24h at 80 ℃ in a vacuum drying oven for later use;
(3) dissolving a hydroxyl-containing polyarylethersulfone ketone polymer 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 an epoxy group-containing polyarylethersulfone ketone polymer, filtering, soaking the precipitate in running water for 24h, removing the organic solvent, unreacted epoxy chloropropane and the catalyst, filtering and drying to obtain a base membrane material of the epoxy group-containing substituent polyarylethersulfone ketone polymer (PPBESK-EG);
(4) dissolving a bromomethylated polyarylethersulfone ketone polymer in an organic solvent IV, and taking 1 mol of bromomethyl in a molecular chain of the bromomethylated polyarylethersulfone ketone polymer as a basis, wherein (0.2-1.02) mol of phthalocyanine containing hydroxyl substituents and (0.2-1.02) NaHCO3Adding the mixture into a reaction system according to the molar ratio, heating to 30-80 ℃ under the protection of nitrogen, reacting at a constant temperature for 3-10 h, cooling to room temperature after the reaction is finished, precipitating a product polymer by using a mixed solution of distilled water and methanol as a precipitator, washing the product polymer for multiple times by using the mixed solution, and drying in vacuum to obtain a polymer (Pc-PPBESK) with phthalocyanine bonded on the polyarylethersulfone ketone side group;
(5) PPBESK-EG and Pc-PPBESK polymers were polymerized in 10: (0.1-1.0) putting the mixture into an organic solvent V solvent in a mass ratio, after the polymer is completely dissolved, casting the mixture on a glass plate, and drying to obtain a polyarylethersulfone ketone base film containing phthalocyanine and epoxy group side groups;
(6) the two sides of the polyarylethersulfone ketone base membrane containing the phthalocyanine and epoxy group side groups respectively react to introduce ion exchange groups: vertically placing 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, then placing the reactor into a constant-temperature water bath kettle for reaction, and respectively reacting two side surfaces of the membrane to introduce different ion exchange groups;
(7) quaternization: and (3) reacting the anion membrane subjected to amination with a methyl iodide solution to carry out quaternization, washing with deionized water to obtain an anion exchange layer, and thus obtaining the phthalocyanine water dissociation catalytic group-containing monolithic polyarylethersulfone ketone bipolar membrane.
2. The method for preparing the bipolar membrane of polyarylethersulfone ketone containing monolithic body with phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein in step (1), the bisphenol is any one or a combination of two of hydroquinone, resorcinol, bisphenol fluorene, bisphenol a, hexafluorobisphenol a, biphenol and dihydroxy diphenyl ether at any ratio;
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.
3. The method for preparing the bipolar membrane of the monolithic poly (aryl ether sulfone ketone) containing phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein in step (1), the organic solvent I is any one or a combination of two of toluene, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone in any proportion;
the catalyst I is anhydrous potassium carbonate or anhydrous sodium carbonate.
4. The preparation method of the monolithic poly (aryl ether sulfone ketone) bipolar membrane containing phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein 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 phthalocyanine is hydroxyl phthalocyanine, amino phthalocyanine or metal phthalocyanine, and the metal is any one of Mg, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
5. The preparation method of the monolithic poly (aryl ether sulfone ketone) bipolar membrane containing phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein 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.
6. The method for preparing the bipolar membrane of polyarylethersulfone ketone containing monolithic phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein in step (4), the organic solvent iv is any one or a combination of two of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone in any proportion.
7. The method for preparing the bipolar membrane of polyarylethersulfone ketone containing monolithic phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein in step (5), the organic solvent v is any one or a combination of two of dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone in any proportion.
8. The preparation method of the monolithic poly (aryl ether sulfone ketone) bipolar membrane containing phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein in step (6):
the sulfonation reagent in the positive 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 cathode 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.
9. The preparation method of the monolithic poly (aryl ether sulfone ketone) bipolar membrane containing phthalocyanine water dissociation catalytic group as claimed in claim 1, wherein in step (6):
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 method for preparing the bipolar membrane of polyarylethersulfone ketone containing monolithic phthalocyanine water dissociation catalytic group of claim 1, wherein in the 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.
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