CN110862519A - Aryl ether ketone/sulfone polymer, preparation method and application thereof - Google Patents

Aryl ether ketone/sulfone polymer, preparation method and application thereof Download PDF

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CN110862519A
CN110862519A CN201911212624.9A CN201911212624A CN110862519A CN 110862519 A CN110862519 A CN 110862519A CN 201911212624 A CN201911212624 A CN 201911212624A CN 110862519 A CN110862519 A CN 110862519A
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ether ketone
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李胜海
李紫芹
杨宽
张所波
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to the technical field of high molecular materials, in particular to an aryl ether ketone/sulfone polymer, and a preparation method and application thereof. The aryl ether ketone/sulfone polymer has a structure shown in a formula (I); wherein n is more than or equal to 1 and less than or equal to 10000, m is an integer of 1-20, x is 0.1-1, and y is more than or equal to 1 and less than or equal to 3; r1、R2、R3And R4Is independently selected from-CH3or-H; a comprises a keto group or a sulfone group; b is a cationic group containing N or P; c comprises F‑、Cl‑、Br‑、I‑、OH‑、HCO3 ‑、PF6 ‑、NO3 ‑、HSO3 ‑、H2PO4 ‑、COO‑、CO3 2‑、SO4 2‑、HSO3 2‑、HPO4 2‑And PO4 3‑One kind of (1). The anion exchange membrane prepared from the aryl ether ketone/sulfone polymer has excellent mechanical property, high ionic conductivity and excellent alkali stability.

Description

Aryl ether ketone/sulfone polymer, preparation method and application thereof
Technical Field
The invention relates to the technical field of high molecular materials, in particular to an aryl ether ketone/sulfone polymer, and a preparation method and application thereof.
Background
Anion exchange membrane fuel cells (AEMs) are a clean, efficient, and environmentally friendly new energy technology. Compared with proton exchange membrane fuel cells (PEMs), the hydroxide ion exchange membrane fuel cell has higher electrode catalytic activity in a high-pH environment, can select a non-noble metal catalyst to assemble the fuel cell, and realizes low cost and high performance. However, the conventional anion exchange membrane suffers from problems of low conductivity and poor alkali stability. The main chain of the polyaryletherketone/sulfone has the advantages of high chemical stability, good mechanical property and the like, but the traditional post-modification method needs to use toxic chloromethyl ether, and the existence of benzyl quaternary ammonium salt enables the polymer film to be easily degraded under the alkaline condition.
In order to improve the stability of the polyaryletherketone/sulfone anion exchange membrane under alkaline conditions, numerous scholars have designed and prepared a series of polymers with different side chains, such as: introduction of long spacer alkyl chains between imidazole groups and the backbone (Gaohong He, et al, International Journal of hydroenergy 2016, 41, 14982-.
Since George Andrew Olah et al discovered that super acids can be used for carbocation stabilization, a large number of organic reactions using super acids as catalysts have been reported in succession. In recent years, some researchers have realized super acid-catalyzed polymerization, and the polymerization reaction has the advantages of low polymerization temperature, short time, narrow molecular weight distribution, no need of equal-equivalent feeding and the like. However, these polymerization reactions have strict requirements on the reactivity of the monomers and a few types of polymers are currently available.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an aryl ether ketone/sulfone polymer, a preparation method and an application thereof, wherein an anion exchange membrane prepared from the aryl ether ketone/sulfone polymer of the present invention has excellent mechanical properties and a high ionic conductivity.
The invention provides an aryl ether ketone/sulfone polymer, which has a structure shown in a formula (I):
Figure BDA0002298545880000021
wherein n is more than or equal to 1 and less than or equal to 10000, m is an integer of 1-20, x is 0.1-1, and y is more than or equal to 1 and less than or equal to 3;
R1、R2、R3and R4Is independently selected from-CH3or-H;
a comprises a keto group or a sulfone group;
b is a cationic group containing N or P;
c comprises F-、Cl-、Br-、I-、OH-、HCO3 -、PF6 -、NO3 -、HSO3 -、H2PO4 -、COO-、CO3 2-、SO4 2-、HSO3 2-、HPO4 2-And PO4 3-One kind of (1).
Preferably, R1、R2、R3And R4In which there are at most two-CHs3。
Preferably, B has a structure represented by formulas (1) to (11):
Figure BDA0002298545880000022
wherein e is 0 to 11, R5、R6And R7Is independently selected from-CH3-H or phenyl.
The invention also provides a preparation method of the aryl ether ketone/sulfone polymer, which comprises the following steps:
under the conditions of superacid and organic solvent, biphenyl ether monomers with a structure shown in a formula (III) and a substance a are subjected to polymerization reaction, then mixed with alcohols to obtain an aryl ether ketone/sulfone polymer with a structure shown in a formula (II), and the aryl ether ketone/sulfone polymer with a structure shown in a formula (I) is obtained after quaternization reaction: the substance a is an isatin derivative monomer with a structure shown in a formula (IV), or the substance a is a mixture of the isatin derivative monomer with the structure shown in the formula (IV) and isatin;
Figure BDA0002298545880000031
wherein n is more than or equal to 1 and less than or equal to 10000, m is an integer of 1-20, x is 0.1-1, and y is more than or equal to 1 and less than or equal to 3;
R1、R2、R3and R4Is independently selected from-CH3or-H;
a comprises a keto group or a sulfone group;
b is a cationic group containing N or P;
c comprises F-、Cl-、Br-、I-、OH-、HCO3 -、PF6 -、NO3 -、HSO3 -、H2PO4 -、COO-、CO3 2-、SO4 2-、HSO3 2-、HPO4 2-And PO4 3-One kind of (1).
Preferably, the biphenyl ether monomer having the structure represented by formula (iii) is prepared according to the following method:
reacting the substance b with a phenol compound under an alkaline condition to obtain a biphenyl ether monomer with a structure shown in a formula (III); the substance b comprises 4,4 '-dichlorodiphenyl sulfone or 4,4' -difluorobenzophenone.
Preferably, the reaction temperature is 60-180 ℃, and the reaction time is 2-24 h.
Preferably, the isatin derivative monomer having the structure represented by formula (iv) is prepared according to the following method:
under the alkaline condition, isatin reacts with alkane with halogen connected to two ends in a solvent to obtain an isatin derivative monomer with a structure shown in a formula (IV).
Preferably, the reaction temperature is 20-100 ℃, and the reaction time is 2-15 h.
Preferably, the ratio of the amount of the biphenyl ether monomer having the structure represented by formula (iii) to the amount of the substance a is 1: 1-2;
the superacid comprises HF BF3、HSO3F·SbF5、HSO3Cl、HSO3F、CF3SO3H、SbF5、AsF5、AuF5、TaF5And NbF5One of (1);
the organic solvent comprises one of dichloromethane, carbon disulfide and nitrobenzene;
the volume ratio of the super acid to the organic solvent is 1: 0 to 3;
the alcohol substance comprises methanol or ethanol;
the temperature of the polymerization reaction is 0-140 ℃, and the time is 0.5-72 h.
The invention also provides a preparation method of the anion exchange membrane, which comprises the following steps:
mixing the polymer with a nonpolar solvent, spreading a membrane by a tape casting method, and then performing alkali exchange to obtain an anion exchange membrane;
the polymer is the aryl ether ketone/sulfone polymer with the structure shown in the formula (I) in any one of claims 1 to 3, or the aryl ether ketone/sulfone polymer with the structure shown in the formula (I) prepared by the preparation method in any one of claims 4 to 9.
Preferably, the non-polar solvent comprises N, N-dimethylacetamide;
the concentration of the casting solution after the polymer is mixed with the nonpolar solvent is 5 wt% -10 wt%.
The invention also provides an anion exchange membrane prepared by the preparation method.
The anion exchange membrane prepared from the aryl ether ketone/sulfone polymer has better mechanical property and higher ionic conductivity, has better alkali stability, and can be applied to the fields of fuel cells, flow batteries, water electrolysis, resource recycling and other electrochemical devices relating to anion exchange membranes.
Drawings
FIG. 1 is a NMR spectrum of an aryl ether ketone/sulfone polymer having a structure shown in formula (I) prepared in example 3;
FIG. 2 shows OH of anion exchange membrane prepared in example 3 of the present invention in water-Conductivity test result graph;
FIG. 3 shows the residual OH after the anion exchange membrane prepared in example 3 of the present invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days-Electrical conductivity;
FIG. 4 is a stress-strain curve of the anion exchange membrane prepared in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an aryl ether ketone/sulfone polymer, which has a structure shown in a formula (I):
Figure BDA0002298545880000051
wherein n is more than or equal to 1 and less than or equal to 10000; in certain embodiments of the present invention, n is 167, 130, 147, 175, 124, or 150;
m is an integer of 1-20; in certain embodiments of the present invention, m is 1, 2 or 3;
x is 0.1-1; in certain embodiments of the invention, x is 1;
y is the reciprocal of the number of charges carried by the counter ion, and is more than or equal to 1 and less than or equal to 3; in certain embodiments of the present invention, y ═ 1;
R1、R2、R3and R4Is independently selected from-CH3or-H; in certain embodiments of the invention, the R is1、R2、R3And R4In which there are at most two-CHs3The rest is-H; in certain embodiments of the invention, R1is-H, R2is-H, R3is-H, R4is-H; in certain embodiments of the invention, R1is-H, R2is-CH3，R3is-CH3，R4is-H; in certain embodiments of the invention, R1is-CH3，R2is-H, R3is-H, R4is-CH3；
A comprises a keto group or a sulfone group.
B is a cationic group containing N or P. In some embodiments of the present invention, B has a structure represented by formulas (1) to (11):
Figure BDA0002298545880000052
Figure BDA0002298545880000061
in the formula (10), e is 0 to 11, R5、R6And R7Is independently selected from-CH3-H or phenyl.
C comprises F-、Cl-、Br-、I-、OH-、HCO3 -、PF6 -、NO3 -、HSO3 -、H2PO4 -、COO-、CO3 2-、SO4 2-、HSO3 2-、HPO4 2-And PO4 3-One kind of (1).
The invention also provides a preparation method of the aryl ether ketone/sulfone polymer, which comprises the following steps:
under the conditions of superacid and organic solvent, biphenyl ether monomers with a structure shown in a formula (III) and a substance a are subjected to polymerization reaction, then mixed with alcohols to obtain an aryl ether ketone/sulfone polymer with a structure shown in a formula (II), and the aryl ether ketone/sulfone polymer with a structure shown in a formula (I) is obtained after quaternization reaction: the substance a is an isatin derivative monomer with a structure shown in a formula (IV), or the substance a is a mixture of the isatin derivative monomer with the structure shown in the formula (IV) and isatin:
Figure BDA0002298545880000062
wherein n is more than or equal to 1 and less than or equal to 10000;
m is an integer of 1-20; in certain embodiments of the present invention, m ═ 1;
x is 0.1-1; in certain embodiments of the invention, x is 1;
y is the reciprocal of the number of charges carried by the counter ion, and is more than or equal to 1 and less than or equal to 3;
R1、R2、R3and R4Is independently selected from-CH3or-H. In certain embodiments of the invention, the R is1、R2、R3And R4In which there are at most two-CHs3The remainder was-H.
A comprises a keto group or a sulfone group.
B is a cationic group containing N or P. In some embodiments of the present invention, B has a structure represented by formulas (1) to (11):
Figure BDA0002298545880000071
in the formula (10), e is 0 to 11, R5、R6And R7Is independently selected from-CH3-H or phenyl.
C comprises F-、Cl-、Br-、I-、OH-、HCO3 -、PF6 -、NO3 -、HSO3 -、H2PO4 -、COO-、CO3 2-、SO4 2-、HSO3 2-、HPO4 2-And PO4 3-One kind of (1).
In certain embodiments of the present invention, the biphenyl ether-based monomer having the structure represented by formula (iii) is prepared according to the following method:
reacting the substance b with a phenol compound under an alkaline condition to obtain a biphenyl ether monomer with a structure shown in a formula (III); the substance b comprises 4,4 '-dichlorodiphenyl sulfone or 4,4' -difluorobenzophenone.
In certain embodiments of the present invention, the phenolic compound comprises phenol.
In certain embodiments of the invention, the substance that provides basic conditions is potassium carbonate.
In certain embodiments of the present invention, the molar ratio of the substance b to the phenol compound is 0.5 to 1: 1 to 5. In certain embodiments, the molar ratio of substance b to phenolic compound is 0.92: 1.65. in certain embodiments of the present invention, the molar ratio of the substance b to the potassium carbonate is 0.5-1: 1 to 5. In certain embodiments, the molar ratio of substance b to potassium carbonate is 0.92: 1.65.
in certain embodiments of the present invention, the reaction of the substance b with the phenolic compound is carried out under a nitrogen atmosphere.
In certain embodiments of the present invention, the reacting of the substance b with the phenolic compound further comprises dehydration. Preferably, the reaction material is dehydrated in a mixed reagent of dimethyl sulfoxide (DMSO) and toluene at 145 to 155 ℃, and then the toluene is removed by heating. In certain embodiments of the invention, the temperature of the dehydration is 150 ℃. In certain embodiments, the volume ratio of dimethyl sulfoxide (DMSO) to toluene is 500: 200. in certain embodiments of the invention, the heating temperature to remove toluene is 80 ℃.
In some embodiments of the present invention, the reaction temperature of the substance b and the phenol compound is 20-100 ℃ under the alkaline condition, and the reaction time is 2-15 hours. In certain embodiments, substance b is reacted with the phenolic compound under basic conditions at a temperature of 165 ℃ for a period of 2 hours.
In certain embodiments of the present invention, after reacting the substance b with the phenolic compound under basic conditions, the method further comprises: extracted with chloroform or water, washed with methanol, and then dried. The method of drying is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.
In certain embodiments of the present invention, the isatin derivative monomer having the structure of formula (iv) is prepared according to the following method:
under the alkaline condition, isatin reacts with alkane with halogen connected to two ends in a solvent to obtain an isatin derivative monomer with a structure shown in a formula (IV).
Specifically, the following may be mentioned: mixing isatin and a solvent, adding an alkaline substance, uniformly stirring, adding alkane with halogen at two ends, and reacting to obtain the isatin derivative monomer with the structure shown in the formula (IV). In certain embodiments of the invention, the blending is performed at ambient temperature. The stirring and blending time is not particularly limited, and in some embodiments, the stirring and blending time is 30 min.
In certain embodiments of the present invention, the alkaline substance providing alkaline conditions comprises one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium phosphate, and potassium carbonate.
In certain embodiments of the invention, the alkane having a halogen attached to both ends has the structure of formula (v):
Figure BDA0002298545880000081
wherein m is an integer of 1-20.
In certain embodiments of the invention, the solvent comprises one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), Dimethylsulfoxide (DMSO), and N-methylpyrrolidone (NMP).
In certain embodiments of the invention, the molar ratio of isatin to the alkane having a halogen attached to both ends is 0.1 to 1: 1 to 5. In certain embodiments, the molar ratio of isatin to alkane having a halogen attached at both ends is 0.2: 1.01, 0.2: 0.89 or 0.2: 0.79. in certain embodiments of the present invention, the molar ratio of isatin to basic substance is 0.1 to 1: 0.1 to 5. In certain embodiments, the molar ratio of isatin to basic is 0.2: 0.41.
in some embodiments of the present invention, the isatin is reacted with the alkane having the halogen attached to both ends thereof at a temperature of 20 to 100 ℃ for 2 to 15 hours. In certain embodiments, the isatin is reacted with the alkane having the halogen attached to both ends at room temperature for 5 hours.
In some embodiments of the present invention, the method further comprises, after the reaction of isatin with the alkane having the halogen attached to both ends in the solvent is completed: filtering and distilling under reduced pressure. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used. The reduced pressure distillation is used to remove excess alkane and solvent with halogen attached to both ends. In certain embodiments of the present invention, after the vacuum distillation, the method further comprises: and (5) column chromatography purification. The method for purifying by column chromatography is not particularly limited in the present invention, and a method for purifying by column chromatography known to those skilled in the art may be used. In certain embodiments of the present invention, the mobile phase used for the column chromatography purification is ethyl acetate and petroleum ether, and the volume ratio of ethyl acetate to petroleum ether is 1: 4.
after obtaining a biphenyl ether monomer with a structure shown in a formula (III) and an isatin derivative monomer with a structure shown in a formula (IV), carrying out polymerization reaction on the biphenyl ether monomer with the structure shown in the formula (III) and a substance a under the conditions of super acid and an organic solvent, then mixing the biphenyl ether monomer with the substance a and an alcohol substance to obtain an aryl ether ketone/sulfone polymer with a structure shown in a formula (II), and carrying out quaternization reaction to obtain the aryl ether ketone/sulfone polymer with the structure shown in the formula (I): the substance a is an isatin derivative monomer with a structure shown in a formula (IV), or the substance a is an isatin derivative monomer with a structure shown in a formula (IV) and isatin.
In certain embodiments of the present invention, the ratio of the amount of the biphenyl ether-based monomer having the structure represented by formula (iii) to the amount of the substance a is 1: 1 to 2. In certain embodiments, the ratio of the biphenyl ether-based monomer having the structure represented by formula (iii) to the amount of the substance a is 1: 1.
the superacid is a catalyst. In certain embodiments of the invention, the superacid comprises HF BF3、HSO3F·SbF5、HSO3Cl、HSO3F、CF3SO3H、SbF5、AsF5、AuF5、TaF5And NbF5One kind of (1).
In certain embodiments of the present invention, the organic solvent comprises one of dichloromethane, carbon disulfide, and nitrobenzene.
In certain embodiments of the invention, the volume ratio of the superacid to the organic solvent is 1: 0 to 3. In certain embodiments, the volume ratio of the superacid to the organic solvent is 1: 1. in certain embodiments of the present invention, the ratio of the total volume of the super acid and the organic solvent to the volume of the alcohol is 1-3: 5 to 100. In certain embodiments, the ratio of the total volume of the super acid and the organic solvent to the volume of the alcohol is 3: 50.
in some embodiments of the present invention, the ratio of the total mass of the biphenyl ether monomer having a structure represented by formula (iii) and the substance a to the total volume of the superacid and the organic solvent is 5.5 to 6.5 g: 30 mL. In certain embodiments, the ratio of the total mass of the biphenyl ether-based monomer having the structure represented by formula (iii) and the substance a to the total volume of the superacid and the organic solvent is 6.48 g: 30mL, 5.81 g: 30 mL.
In some embodiments of the present invention, the polymerization temperature is 0 to 140 ℃ and the time is 0.5 to 72 hours. In certain embodiments, the polymerization reaction is at a temperature of 0 ℃ for a period of 2 hours. In certain embodiments of the invention, the polymerization reaction is conducted in a sealed environment in order to prevent water in the air from entering the system.
In certain embodiments of the invention, the alcohol comprises methanol or ethanol.
In some embodiments of the present invention, the mixing time with the alcohol is 24-26 hours. In certain embodiments, the time for mixing with the alcohol is 24 hours. The mixing with alcohols is to quench the reaction and separate out polymer solid to obtain the aryl ether ketone/sulfone polymer with the structure shown in the formula (II).
In some embodiments of the present invention, after mixing with the alcohol, the method further comprises: washed with hot methanol and dried in vacuo. The method of washing with hot methanol is not particularly limited in the present invention, and a method of washing with hot methanol, which is well known to those skilled in the art, may be used. The method of vacuum drying is not particularly limited in the present invention, and a vacuum drying method known to those skilled in the art may be used.
After the aryl ether ketone/sulfone polymer with the structure shown in the formula (II) is obtained, the functionalized aryl ether ketone/sulfone polymer with the structure shown in the formula (I) is obtained after quaternization reaction.
In some embodiments of the present invention, a solution of an aryl ether ketone/sulfone polymer having a structure represented by formula (ii) is mixed with a tertiary amine or an aqueous solution of a tertiary amine to perform a quaternization reaction.
In certain embodiments of the present invention, the solvent in the solution of the aryl ether ketone/sulfone polymer having the structure of formula (ii) is N, N-dimethylacetamide. In some embodiments of the present invention, the dosage ratio of the aryl ether ketone/sulfone polymer having the structure represented by formula (ii) to the solvent is 1 to 3 g: 20-100 mL. In some embodiments, the ratio of the amount of the aryl ether ketone/sulfone polymer having the structure represented by formula (II) to the amount of the solvent is 2.53 g: 32mL, 2.4 g: 30 mL.
In certain embodiments of the present invention, the tertiary amine has a structure represented by formulas (12) - (22):
Figure BDA0002298545880000111
wherein e is 0 to 11, R5、R6And R7Is independently selected from-CH3-H or phenyl.
In certain embodiments of the present invention, the concentration of the aqueous solution of the tertiary amine is 28 to 32 wt%. In certain embodiments, the concentration of the aqueous solution of the tertiary amine is 30 wt%.
In certain embodiments of the present invention, the molar ratio of aryl ether ketone/sulfone polymer having the structure of formula (ii) to tertiary amine is 1: 1 to 5. In certain embodiments, the molar ratio of aryl ether ketone/sulfone polymer having the structure of formula (ii) to tertiary amine is 1: 3.
in some embodiments of the present invention, the temperature of the quaternization reaction is 0 to 140 ℃ and the time is 6 to 72 hours. In certain embodiments, the temperature of the quaternization reaction is 75 to 85 ℃ or 80 ℃. In certain embodiments, the quaternization reaction time is 24 to 48 hours, 24 hours, or 48 hours.
In certain embodiments of the invention, the quaternization reaction is carried out under an air atmosphere or under a nitrogen atmosphere.
In certain embodiments of the present invention, after the quaternization reaction, the method further comprises: the reaction product was cooled to room temperature and then placed in ethyl acetate to precipitate the ionomer. In some embodiments of the present invention, after the precipitating the ionic polymer, the method further comprises: washed with ethyl acetate and then dried in vacuo.
The washing step with ethyl acetate is not particularly limited in the present invention, and washing steps well known to those skilled in the art may be employed. The method of vacuum drying is not particularly limited in the present invention, and may be vacuum drying method well known to those skilled in the art, and in some embodiments, the vacuum drying time is 12 hours.
The invention utilizes the super acid catalyzed poly (hydroxyalkylation) reaction to prepare the polymer with the main chain of poly (aryl ether ketone)/sulfone with long side chain bromoalkane, and then the polymer is reacted with different tertiary amines to obtain the cation group-containing poly (aryl ether ketone)/sulfone. The method can accurately control the position and the number of ion exchange groups, and avoids the use of noble metal catalysts; the obtained cation group-containing polyaryletherketone/sulfone has excellent solubility and is beneficial to further functional application; the cationic group of the polymer is far away from the main chain, so that the long-term use of the polymer under alkaline conditions is facilitated; and the introduction of the isatin unit can also improve the conductivity of the membrane.
The invention also provides a preparation method of the anion exchange membrane, which comprises the following steps:
mixing the polymer with a nonpolar solvent, spreading a membrane by a tape casting method, and then performing alkali exchange to obtain an anion exchange membrane;
the polymer is the aryl ether ketone/sulfone polymer with the structure shown in the formula (I) or the aryl ether ketone/sulfone polymer with the structure shown in the formula (I) prepared by the preparation method.
In certain embodiments of the invention, the non-polar solvent comprises N, N-dimethylacetamide.
In certain embodiments of the invention, the concentration of the casting solution after mixing the polymer with the non-polar solvent is 5 wt% to 10 wt%. In certain embodiments, the concentration of the casting solution after mixing the polymer with the non-polar solvent is 8 wt%.
In certain embodiments of the invention, casting the film comprises: and casting the casting solution mixed with the polymer and the nonpolar solvent on a glass plate to form a film.
In some embodiments of the present invention, after the casting, the method further comprises: and drying the solvent.
In certain embodiments of the invention, the base solution used for the base exchange comprises an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide. In certain embodiments, the aqueous solution of sodium hydroxide has a concentration of 1 mol/L. In certain embodiments of the invention, the base exchange comprises: putting the product after drying the solventSoaking in alkali solution. In some embodiments of the present invention, the time of the alkali exchange (soaking) is 24-48 h. In certain embodiments, the time for the base exchange (soaking) is 24h or 48 h. Br in the polymer by base exchange-Substitution to OH-。
In certain embodiments of the invention, after the base exchange is complete, a wash is also included. In some embodiments, the cleaning agent used for cleaning is ultrapure water.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
The invention also provides an anion exchange membrane prepared by the preparation method. The anion exchange membrane prepared from the aryl ether ketone/sulfone polymer has better mechanical property and higher ionic conductivity, has better alkali stability, and can be applied to the fields of fuel cells, flow batteries, water electrolysis, resource recycling and other electrochemical devices relating to anion exchange membranes.
Experimental results show that after the anion exchange membrane provided by the invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24 hours, tested OH-The conductivity is not less than 50.2mS/cm at 80 ℃. After the anion exchange membrane is soaked in 1mol/LNaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained to be more than 90 percent, which shows that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is greater than 26MPa, and the elongation at break is not lower than 12%.
In order to further illustrate the present invention, the following examples are provided to describe the aryl ether ketone/sulfone polymer, the preparation method and the application thereof in detail, but they should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
A biphenyl ether monomer having a structure represented by the formula (III) (wherein A is a ketone group)，R1is-H, R2is-H, R3is-H, R4is-H) is prepared according to the following method:
into a three-necked flask equipped with a stirrer, a nitrogen supply tube and a water separator were charged 228g (1.65mol) of potassium carbonate, 200g (0.92mol) of 4,4' -difluorobenzophenone and 155g (1.65mol) of phenol. Then, nitrogen purge was performed, dehydration was performed in 500mL of dimethyl sulfoxide (DMSO) and 200mL of toluene at 150 ℃, heating to 80 ℃ to remove toluene, and reaction was performed for 2h at 165 ℃. Extraction with chloroform, washing with methanol and drying gave 221g of 4,4' -bis (phenoxy) benzophenone.
Example 2
An isatin derivative monomer (m ═ 1) having a structure represented by formula (iv) was prepared according to the following method:
30g (0.20mol) of isatin and 120mL of N, N-Dimethylformamide (DMF) were added to a 500mL three-necked flask, and after dissolving the mixture with stirring, 56.39g (0.41mol) of K was added2CO3Then, the mixture was stirred at room temperature for 30 min. Then 121mL (1.01mol) of 1, 4-dibromobutane was added thereto, and the mixture was stirred at room temperature for 5 hours. Filtration and distillation under reduced pressure remove excess 1, 4-dibromobutane. Purifying by column chromatography (volume ratio of mobile phase ethyl acetate to petroleum ether is 1: 4) to obtain pure red solid product with yield of 90.1%.
Example 3
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of 4,4' -bis (phenoxy) benzophenone and 2.82g (0.01mol) of the isatin derivative (m ═ 1) of example 2 were dissolved in 15mL of dichloromethane, and 15mL of cff was slowly added under an ice-water bath (temperature 0 ℃ C.) to the solution3SO3After the reaction is carried out for 2H under sealed condition, the viscous solution is slowly settled in 500mL of methanol to obtain white solid, and the white solid is heated and washed by methanol and dried in vacuum. The yield was 97%.
(2) 2.53g (0.004mol) of the obtained white solid and 32mL of N, N-dimethylacetamide were placed in a 100mL single-neck flask equipped with a magnetic stirrer, and after dissolution, an aqueous solution of a tertiary amine (the tertiary amine has the structure represented by formula (12), 2.36g (0.012mol) of the aqueous solution of the tertiary amine, and the concentration of the aqueous solution of the tertiary amine was 30 wt%) was added, and the mixture was reacted at 80 ℃ for 24 hours, cooled to room temperature, and then settled in ethyl acetate to precipitate an ionomer, and the ethyl acetate was clearWashing for several times, and vacuum drying for 12h to obtain the aryl ether ketone/sulfone polymer (x is 1, m is 1, n is 167, y is 1, R is 1) with the structure shown in formula (I)1is-H, R2is-H, R3is-H, R4is-H, A is a keto group, B is formula (1)), and the yield is 95%.
In this example, the result of nmr analysis of an aryl ether ketone/sulfone polymer having a structure shown in formula (I) is shown in fig. 1. FIG. 1 shows the NMR spectrum of the aryl ether ketone/sulfone polymer of formula (I) prepared in example 3. As can be seen from FIG. 1, the aryl ether ketone/sulfone polymer having the structure shown in formula (I) can be successfully prepared.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 24 hours by using 1mol/L NaOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane was soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then OH-The change in conductivity with temperature is shown in fig. 2. FIG. 2 shows OH of anion exchange membrane prepared in example 3 of the present invention in water-Conductivity test result chart. As can be seen from FIG. 2, at 80 ℃ its OH-The conductivity of the conductive material reaches 94.8 mS/cm. After the anion exchange membrane prepared in the embodiment 3 of the invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the residual OH-The results of the conductivity measurements are shown in figure 3. FIG. 3 shows the residual OH after the anion exchange membrane prepared in example 3 of the present invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days-Electrical conductivity. As can be seen from fig. 3, the conductivity of the anion-exchange membrane hardly changed, and the retention rate of the conductivity was maintained at 96% or more, indicating that the membrane had good alkali resistance. FIG. 4 is a stress-strain curve of the anion exchange membrane prepared in example 3 of the present invention. As can be seen from FIG. 4, the anion-exchange membrane has good tensile strength and toughness, the tensile strength is 31.8MPa, and the elongation at break is 18%.
Example 4
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of 4,4' -bis (phenoxy) benzophenone, 1.41g (0.005mol) of the isatin derivative (m ═ 1) of example 2, and 0.74g (0.005mol) of isatin were dissolved in 15mL of dichloromethane, and 15mL of cff was slowly added under ice-water bath3SO3After the H sealing reaction for 2H, the viscous solution is slowly settled in methanol to obtain a white solid, and the white solid is heated and washed by methanol and dried in vacuum. The yield was 90%.
(2) In a 100mL single-neck flask equipped with a magnetic stirrer, 2.4g (0.004mol) of the obtained white solid and 30mL of N, N-dimethylacetamide were added, after dissolution, a tertiary amine (tertiary amine having a structure represented by formula (14) and 0.12g (0.012mol)) was added, and the mixture was reacted at 80 ℃ for 48 hours, cooled to room temperature, and then settled in ethyl acetate to precipitate an ionomer, and after washing with ethyl acetate several times, vacuum-dried for 12 hours to obtain a polyaryletherketone/sulfone polymer having a structure represented by formula (I) (x is 0.5, m is 1, N is 150, y is 1, R is 1, and R is a polyaryletherketone/sulfone polymer having a structure represented by formula (I) (x is 0.5, m is 1, N is1is-H, R2is-H, R3is-H, R4When it is-H, A is a keto group, B is formula (3)), the yield was 98%.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 48 hours by using 1mol/L KOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then tested OH-The conductivity was 22.5mS/cm at 30 ℃ and 50.2mS/cm at 80 ℃. After the anion-exchange membrane prepared in the embodiment 4 of the invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion-exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained to be more than 96%, which indicates that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is 28.2MPa, and the elongation at break is 16%.
Example 5
A biphenyl ether mono-having a structure represented by the formula (III)A compound of formula (wherein A is a keto group, R1is-H, R2is-CH3，R3is-CH3，R4is-H) is prepared according to the following method:
into a three-necked flask equipped with a stirrer, a nitrogen supply tube and a water separator were charged 228g (1.65mol) of potassium carbonate, 200g (0.92mol) of 4,4' -difluorobenzophenone and 201g (1.65mol) of 2, 5-dimethylphenol. Then, nitrogen purge was performed, dehydration was performed in 500mL of dimethyl sulfoxide (DMSO) and 200mL of toluene at 150 ℃, heating to 80 ℃ to remove toluene, and reaction was performed for 2h at 165 ℃. Extraction with chloroform, washing with methanol and drying gave 255g of bis (4- (2, 5-dimethylphenoxy) phenyl) methanone.
Example 6
A biphenyl ether monomer having a structure represented by the formula (III) (wherein A is a ketone group, R1is-CH3，R2is-CH3，R3is-H, R4is-H) is prepared according to the following method:
into a three-necked flask equipped with a stirrer, a nitrogen supply tube and a water separator were charged 228g (1.65mol) of potassium carbonate, 200g (0.92mol) of 4,4' -difluorobenzophenone and 201g (1.65mol) of 2, 6-dimethylphenol. Then, nitrogen purge was performed, dehydration was performed in 500mL of dimethyl sulfoxide (DMSO) and 200mL of toluene at 150 ℃, heating was performed to remove toluene, and reaction was performed for 2h at 165 ℃. Extraction with chloroform, washing with methanol and drying gave 255g of bis (4- (2, 6-dimethylphenoxy) phenyl) methanone.
Example 7
A biphenyl ether monomer with a structure shown as a formula (III) (wherein, A is sulfuryl, R1is-H, R2is-H, R3is-H, R4is-H) is prepared according to the following method:
into a three-necked flask equipped with a stirrer, a nitrogen supply tube and a water separator were charged 228g (1.65mol) of potassium carbonate, 263g (0.92mol) of 4,4' -dichlorodiphenylsulfone and 155g (1.65mol) of phenol. Then, nitrogen purge was performed, dehydration was performed in 500mL of dimethyl sulfoxide (DMSO) and 200mL of toluene at 150 ℃, heating was performed to remove toluene, and reaction was performed for 2h at 165 ℃. Extraction with chloroform, washing with methanol and drying gave 243g of 4,4' -bis (phenoxy) diphenylmethanesulphone.
Example 8
An isatin derivative monomer (m ═ 2) having a structure represented by formula (iv) was prepared according to the following method:
30g (0.20mol) of isatin and 120mL of N, N-Dimethylformamide (DMF) were added to a 500mL three-necked flask, and after dissolving the mixture with stirring, 56.39g (0.41mol) of K was added2CO3Then, the mixture was stirred at room temperature for 30 min. Then 121mL of 0.89mol) of 1, 5-dibromopentane was added thereto, and the mixture was stirred at room temperature for 5 hours. Filtration and distillation under reduced pressure remove excess 1, 5-dibromopentane. Purifying by column chromatography (the volume ratio of mobile phase ethyl acetate to petroleum ether is 1: 4) to obtain a pure red solid product with a yield of 92%.
Example 9
An isatin derivative monomer (m ═ 3) having a structure represented by formula (iv) was prepared according to the following method:
30g (0.20mol) of isatin and 120mL of N, N-Dimethylformamide (DMF) were added to a 500mL three-necked flask, and after dissolving the mixture with stirring, 56.39g (0.41mol) of K was added2CO3Then, the mixture was stirred at room temperature for 30 min. Then, 121mL (0.79mol) of 1, 6-dibromohexane was added thereto, and the mixture was stirred at room temperature for 5 hours. Filtration and distillation under reduced pressure remove excess 1, 6-dibromohexane. Purifying by column chromatography (volume ratio of mobile phase ethyl acetate to petroleum ether is 1: 4) to obtain pure red solid product with yield of 89.5%.
Example 10
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of 4,4' -bis (phenoxy) benzophenone and 2.82g (0.01mol) of the isatin derivative (m ═ 2) of example 8 were dissolved in 15mL of nitrobenzene, and 15mL of cff was slowly added under ice-water bath3SO3After the H sealing reaction for 2H, the viscous solution is slowly settled in methanol to obtain a white solid, and the white solid is heated and washed by methanol and dried in vacuum. The yield was 85%.
(2) 2.53g of the obtained white solid and 32mL of N, N-dimethylacetamide were added to a 100mL single-neck flask equipped with a magnetic stirrer, and after dissolution, an aqueous solution of a tertiary amine (the tertiary amine has the structure represented by formula (13), 2.36g of the tertiary amine, and the concentration of the aqueous solution of the tertiary amine was 30 wt%) was added to the mixture, and the mixture was reacted at 80 ℃ for 24 hours, cooled to room temperature, and then settled in ethyl acetate to be precipitatedThe ionic polymer is taken out, washed by ethyl acetate for several times and dried for 12h in vacuum, and the polyaryletherketone/sulfone polymer with the structure shown in the formula (I) is obtained (x is 1, m is 2, n is 130, y is 1, R is1is-H, R2is-H, R3is-H, R4When it is-H, A is a keto group, and B is formula (2)), the yield was 96%.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 24 hours by using 1mol/L NaOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then tested OH-The conductivity was 45.1mS/cm at 30 ℃ and 95.2mS/cm at 80 ℃. After the anion-exchange membrane prepared in the embodiment 10 of the invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion-exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained to be more than 90%, which indicates that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is 32.1MPa, and the elongation at break is 20%.
Example 11
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of 4,4' -bis (phenoxy) benzophenone and 2.82g (0.01mol) of the isatin derivative (m ═ 3) of example 9 were dissolved in 15mL of dichloromethane, and 15mL of cff was slowly added under ice-water bath3SO3After the reaction is carried out for 2H under sealed condition, the viscous solution is slowly settled in 500mL of methanol to obtain white solid, and the white solid is heated and washed by methanol and dried in vacuum. The yield was 95%.
(2) 2.53g (0.004mol) of the obtained white solid and 32mL of N, N-dimethylacetamide were placed in a 100mL single-neck flask equipped with a magnetic stirrer, and after dissolution, tertiary amine (tertiary amine having the structure represented by formula (15) and 0.12g (0.012mol)) was added and reacted at 80 ℃ for 24 hours, the mixture was cooled to room temperature, settled in ethyl acetate to precipitate an ionomer, and after washing with ethyl acetate several times, vacuum-dried for 12 hours to obtain a complex represented by formula (I)A structural aryl ether ketone/sulfone polymer (x is 1, m is 3, n is 147, y is 1, R1is-H, R2is-H, R3is-H, R4When it was-H, A was a keto group, and B was formula (3)), the yield was 93%.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 24 hours by using 1mol/L NaOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then tested OH-The conductivity was 22.5mS/cm at 30 ℃ and 50.2mS/cm at 80 ℃. After the anion-exchange membrane prepared in the embodiment 11 of the present invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion-exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained to be more than 93%, which indicates that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is 20.5MPa, and the elongation at break is 23%.
Example 12
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of bis (4- (2, 5-dimethylphenoxy) phenyl) methanone, 2.82g (0.01mol) of the isatin derivative (m ═ 2) of example 8 were dissolved in 15mL of dichloromethane, and 15mL of cff was slowly added under ice-water bath3SO3After the reaction is carried out for 10H in a sealed manner, the viscous solution is slowly settled in 500mL of methanol to obtain a white solid, and the white solid is heated, washed and dried in vacuum through methanol. The yield was 90%.
(2) In a 100mL single-neck flask equipped with a magnetic stirrer, 2.53g (0.004mol) of the obtained white solid and 32mL of N, N-dimethylacetamide were added, after dissolution, a tertiary amine (tertiary amine having a structure represented by formula (16) and 0.14g (0.012mol)) was added, and the mixture was reacted at 80 ℃ for 24 hours, cooled to room temperature, and then settled in ethyl acetate to precipitate an ionomer, and after washing with ethyl acetate several times, vacuum-dried for 12 hours to obtain an aryl ether ketone/sulfone polymer having a structure represented by formula (I) (x is 1, m is 2, N is 130, y is 1, R is 2, N is 130, R is 1, R is1For the purpose ofH，R2is-CH3，R3is-CH3，R4When it is-H, A is a keto group, and B is formula (5)), the yield was 96%.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 24 hours by using 1mol/L NaOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then tested OH-The conductivity was 40.5mS/cm at 30 ℃ and 90.2mS/cm at 80 ℃. After the anion-exchange membrane prepared in the embodiment 12 of the invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion-exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained to be more than 97%, which indicates that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is 25.3MPa, and the elongation at break is 16%.
Example 13
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of 4,4' -bis (phenoxy) diphenylmethanesulphone and 2.82g (0.01mol) of the isatin derivative (m ═ 1) of example 2 were dissolved in 15mL of dichloromethane, and 15mL of cff was slowly added under ice-water bath3SO3And after sealing reaction for 20H, slowly settling the viscous solution in methanol to obtain a white solid, heating and washing the white solid by methanol, and drying the white solid in vacuum. The yield was 92%.
(2) In a 100mL single-neck flask equipped with a magnetic stirrer, 2.53g (0.004mol) of the obtained white solid and 32mL of N, N-dimethylacetamide were added, after dissolution, an aqueous solution of a tertiary amine (the tertiary amine has the structure represented by formula (14), 2.36g (0.012mol) of the tertiary amine, and the concentration of the aqueous solution of the tertiary amine was 30 wt%) was added, the mixture was reacted at 80 ℃ for 48 hours, cooled to room temperature, and then settled in ethyl acetate to precipitate an ionic polymer, and after washing with ethyl acetate several times, vacuum drying was performed for 12 hours to obtain an aryl ether ketone/sulfone polymer having the structure represented by formula (I) (x is 1, m is 1, N is 175, y is 1, R is 1, and R is 1)1is-H, R2is-H, R3is-H, R4is-H, A is a keto group, B is formula (8)), yield 95%.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 48 hours by using 1mol/L KOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then tested OH-The conductivity was 25.4mS/cm at 30 ℃ and 55.3mS/cm at 80 ℃. After the anion-exchange membrane prepared in example 13 of the present invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion-exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained at 99% or more, indicating that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is 34.2MPa, and the elongation at break is 18%.
Example 14
(1) In a 75mL pressure bottle, 3.66g (0.01mol) of bis (4- (2, 6-dimethylphenoxy) phenyl) methanone was placed. 2.82g (0.01mol) of the isatin derivative (m ═ 2) of example 8 was dissolved in 15mL of dichloromethane, and 15mL of cff was slowly added thereto in an ice-water bath3SO3And after the H sealing reaction is carried out for 10 hours, slowly settling the viscous solution in methanol to obtain a white solid, heating and washing the white solid by the methanol, and drying the white solid in vacuum. The yield was 93%.
(2) In a 100mL single-neck flask equipped with a magnetic stirrer, 2.53g (0.004mol) of the obtained white solid and 32mL of N, N-dimethylacetamide were added, after dissolution, a tertiary amine (tertiary amine having a structure represented by formula (17) and tertiary amine 0.12g (0.012mol)) was added, and the mixture was reacted at 80 ℃ for 24 hours, cooled to room temperature, and then settled in ethyl acetate to precipitate an ionic polymer, which was washed with ethyl acetate several times and then dried in vacuum for 12 hours to obtain an aryl ether ketone/sulfone polymer having a structure represented by formula (I) (x is 1, m is 2, N is 124, y is 1, R is 21is-CH3，R2is-H, R3is-H, R4is-CH3A is a keto group, B is formula (3)) The yield was 98%.
(3) Taking 1g of the polymer obtained in the step (2), preparing 8 wt% of casting solution by using N, N-dimethylacetamide in a 100mL single-neck flask, casting the casting solution on a glass plate to form a film, drying the solvent, soaking the film for 24 hours by using 1mol/L NaOH aqueous solution, and adding Br-Substitution to OH-And washing with ultrapure water to obtain the anion exchange membrane for testing and experiments.
In this example, the obtained anion exchange membrane is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24h, and then tested OH-The conductivity was 41.6mS/cm at 30 ℃ and 98.5mS/cm at 80 ℃. After the anion-exchange membrane prepared in example 14 of the present invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion-exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained at 95% or more, indicating that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is 26.3MPa, and the elongation at break is 12%.
Experimental results show that after the anion exchange membrane provided by the invention is soaked in 1mol/L NaOH aqueous solution at 60 ℃ for 24 hours, tested OH-The conductivity is not less than 50.2mS/cm at 80 ℃. After the anion exchange membrane is soaked in 1mol/LNaOH aqueous solution at 60 ℃ for 25 days, the conductivity of the anion exchange membrane is almost unchanged, and the retention rate of the conductivity is maintained to be more than 90 percent, which shows that the membrane has good alkali resistance. The anion exchange membrane has good tensile strength and toughness, the tensile strength is greater than 26MPa, and the elongation at break is not lower than 12%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (12)

1. An aryl ether ketone/sulfone polymer has a structure shown as a formula (I):
Figure FDA0002298545870000011
wherein n is more than or equal to 1 and less than or equal to 10000, m is an integer of 1-20, x is 0.1-1, and y is more than or equal to 1 and less than or equal to 3;
R1、R2、R3and R4Is independently selected from-CH3or-H;
a comprises a keto group or a sulfone group;
b is a cationic group containing N or P;
c comprises F-、Cl-、Br-、I-、OH-、HCO3 -、PF6 -、NO3 -、HSO3 -、H2PO4 -、COO-、CO3 2-、SO4 2-、HSO3 2-、HPO4 2-And PO4 3-One kind of (1).
2. The aryl ether ketone/sulfone-based polymer according to claim 1, wherein R is R1、R2、R3And R4In which there are at most two-CHs3。
3. The aryl ether ketone/sulfone polymer according to claim 1, wherein B has a structure represented by formulae (1) to (11):
Figure FDA0002298545870000012
wherein e is 0 to 11, R5、R6And R7Is independently selected from-CH3-H or phenyl.
4. A preparation method of aryl ether ketone/sulfone polymer comprises the following steps:
under the conditions of superacid and organic solvent, biphenyl ether monomers with a structure shown in a formula (III) and a substance a are subjected to polymerization reaction, then mixed with alcohols to obtain an aryl ether ketone/sulfone polymer with a structure shown in a formula (II), and the aryl ether ketone/sulfone polymer with a structure shown in a formula (I) is obtained after quaternization reaction: the substance a is an isatin derivative monomer with a structure shown in a formula (IV), or the substance a is a mixture of the isatin derivative monomer with the structure shown in the formula (IV) and isatin;
Figure FDA0002298545870000021
wherein n is more than or equal to 1 and less than or equal to 10000, m is an integer of 1-20, x is 0.1-1, and y is more than or equal to 1 and less than or equal to 3;
R1、R2、R3and R4Is independently selected from-CH3or-H;
a comprises a keto group or a sulfone group;
b is a cationic group containing N or P;
c comprises F-、Cl-、Br-、I-、OH-、HCO3 -、PF6 -、NO3 -、HSO3 -、H2PO4 -、COO-、CO3 2-、SO4 2-、HSO3 2-、HPO4 2-And PO4 3-One kind of (1).
5. The production method according to claim 4, wherein the biphenyl ether-based monomer having the structure represented by formula (III) is produced by the following method:
reacting the substance b with a phenol compound under an alkaline condition to obtain a biphenyl ether monomer with a structure shown in a formula (III); the substance b comprises 4,4 '-dichlorodiphenyl sulfone or 4,4' -difluorobenzophenone.
6. The preparation method according to claim 5, wherein the reaction temperature is 60-180 ℃ and the reaction time is 2-24 h.
7. The method according to claim 4, wherein the isatin derivative monomer having the structure represented by the formula (IV) is prepared according to the following method:
under the alkaline condition, isatin reacts with alkane with halogen connected to two ends in a solvent to obtain an isatin derivative monomer with a structure shown in a formula (IV).
8. The preparation method according to claim 7, wherein the reaction temperature is 20-100 ℃ and the reaction time is 2-15 h.
9. The production method according to claim 4, wherein the ratio of the biphenyl ether monomer having the structure represented by formula (III) to the amount of the substance a is 1: 1-2;
the superacid comprises HF BF3、HSO3F·SbF5、HSO3Cl、HSO3F、CF3SO3H、SbF5、AsF5、AuF5、TaF5And NbF5One of (1);
the organic solvent comprises one of dichloromethane, carbon disulfide and nitrobenzene;
the volume ratio of the super acid to the organic solvent is 1: 0 to 3;
the alcohol substance comprises methanol or ethanol;
the temperature of the polymerization reaction is 0-140 ℃, and the time is 0.5-72 h.
10. A method for preparing an anion exchange membrane, comprising the steps of:
mixing the polymer with a nonpolar solvent, spreading a membrane by a tape casting method, and then performing alkali exchange to obtain an anion exchange membrane;
the polymer is the aryl ether ketone/sulfone polymer with the structure shown in the formula (I) in any one of claims 1 to 3, or the aryl ether ketone/sulfone polymer with the structure shown in the formula (I) prepared by the preparation method in any one of claims 4 to 9.
11. The method of claim 10, wherein the non-polar solvent comprises N, N-dimethylacetamide;
the concentration of the casting solution after the polymer is mixed with the nonpolar solvent is 5 wt% -10 wt%.
12. The anion exchange membrane prepared by the preparation method of any one of claims 10 to 11.
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Citations (5)

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US5084530A (en) * 1988-08-22 1992-01-28 Amoco Corporation Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers
CN1752123A (en) * 2005-09-09 2006-03-29 中国科学院长春应用化学研究所 Sulfonated polyphenyl type proton transfer film material and synthetic method thereof
WO2017015336A1 (en) * 2015-07-20 2017-01-26 Massachusetts Institute Of Technology Functionalized triptycene polymers and their uses
CN109880138A (en) * 2019-03-01 2019-06-14 大连理工大学 A kind of poly- isatin aromatic hydrocarbons and its anion-exchange membrane, preparation method and application of high-performance belt length side chain ammonium salt
CN110229335A (en) * 2019-06-26 2019-09-13 中国科学院长春应用化学研究所 A kind of fluorine-containing polysulfones and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084530A (en) * 1988-08-22 1992-01-28 Amoco Corporation Poly(aryl ether sulfone)-poly(aryl ether ketone) block copolymers
CN1752123A (en) * 2005-09-09 2006-03-29 中国科学院长春应用化学研究所 Sulfonated polyphenyl type proton transfer film material and synthetic method thereof
WO2017015336A1 (en) * 2015-07-20 2017-01-26 Massachusetts Institute Of Technology Functionalized triptycene polymers and their uses
CN109880138A (en) * 2019-03-01 2019-06-14 大连理工大学 A kind of poly- isatin aromatic hydrocarbons and its anion-exchange membrane, preparation method and application of high-performance belt length side chain ammonium salt
CN110229335A (en) * 2019-06-26 2019-09-13 中国科学院长春应用化学研究所 A kind of fluorine-containing polysulfones and preparation method thereof

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