CN113097551A - Preparation method of siloxane grafted piperidine type polyphenyl ether anion exchange membrane - Google Patents
Preparation method of siloxane grafted piperidine type polyphenyl ether anion exchange membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a siloxane grafted piperidine type polyphenyl ether anion exchange membrane, which comprises the steps of dripping a liquid bromine solution into a polyphenyl ether solution under the nitrogen atmosphere, heating at 140-160 ℃ for 3-5h, and naturally cooling to room temperature; adding a precipitator, filtering, washing and drying to obtain brominated polyphenylene oxide solid; dissolving in N-methyl pyrrolidone, adding hydroxyl-containing piperidine micromolecules, uniformly mixing, and reacting at 70-80 ℃ for 24-48 h; adding a precipitator, filtering, washing and drying to obtain a piperidyl polyphenylene ether polymer; dissolving in dimethyl sulfoxide, adding organic epoxy siloxane and an epoxy ring-opening catalyst, and reacting at 40-60 ℃ to obtain siloxane-bonded piperidyl polyphenylene ether solution; standing at room temperature for 24-48h for hydrolysis crosslinking reaction to form sol, then drying at 60-80 ℃ for 4-8h, heating to 120-130 ℃ for drying for 6-8h, cooling and demoulding to obtain the siloxane grafted piperidine type polyphenylene ether anion exchange membrane. The preparation process is simple, the experimental process is simple and convenient to operate, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a polyphenyl ether anion exchange membrane.
Background
Anion Exchange Membrane Fuel Cells (AEMFC), as a new energy technology with high efficiency and environmental protection, have been the focus of scientific research due to the advantages of fast oxygen reduction kinetics under alkaline conditions and cost reduction by using non-metallic catalysts. As a key component of the AEMFC, anion exchange membranes play an important role in conducting OH "ions, isolating anode fuel from cathode oxidant, and the like. However, since the anion exchange membrane operates in a strongly alkaline environment for a long time, the cationic groups and the polymer main chain are easily attacked by OH "ions to be degraded, resulting in a decrease in the performance of the membrane. In addition, how to balance various performances (dimensional stability, ionic conductivity, alkali resistance under high temperature and strong alkali conditions and the like) of the anion exchange membrane to meet the actual use requirement of the AEMFC is still a difficult problem to be solved urgently.
For how to improve the alkali stability of the anion-exchange membrane, researchers find that the introduction of a strong electron-donating group can reduce the electron cloud density of a cationic group, thereby reducing the attack of OH-ions on the cationic group and further improving the alkali stability of the cationic group. In addition, as an ion conducting group, piperidine has been a hot spot of current research due to its excellent alkali stability and high ionic conductivity under high temperature conditions. However, due to the influence of the piperidine ring structure and the main side chain structure relationship, the mechanical properties and dimensional stability of the currently prepared piperidine anion-exchange membrane still need to be improved.
Disclosure of Invention
The invention aims to further improve the mechanical property and dimensional stability of the polyphenyl ether anion exchange membrane, and the modified group is introduced into the anion exchange membrane structure, so that the prepared anion exchange membrane has excellent mechanical property, dimensional stability and alkali resistance.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of a siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following steps:
1) under the nitrogen atmosphere, dropwise adding a liquid bromine solution into the polyphenyl ether solution, heating at the temperature of 140-160 ℃ for 3-5h, and naturally cooling to room temperature; adding a precipitator, filtering, washing and drying to obtain brominated polyphenylene oxide solid;
2) dissolving the obtained brominated polyphenylene oxide solid in N-methyl pyrrolidone, adding hydroxyl-containing piperidine micromolecules, uniformly mixing, and reacting at 70-80 ℃ for 24-48 h; adding a precipitator, filtering, washing and drying to obtain a piperidyl polyphenylene ether polymer;
3) dissolving the obtained piperidyl polyphenylene ether polymer in dimethyl sulfoxide, adding organic epoxy siloxane and an epoxy ring-opening catalyst, and reacting at 40-60 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution;
4) and standing the obtained siloxane-bonded piperidyl polyphenylene oxide solution at room temperature for 24-48h for hydrolysis crosslinking reaction to form sol, then drying at 60-80 ℃ for 4-8h, then heating to 120-130 ℃ for drying for 6-8h, cooling and demolding to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
According to the scheme, the number average molecular weight of the polyphenylene ether in the step 1 is 27000-50000. Polyphenylene oxide is used as a high-performance engineering plastic, has excellent thermal stability, alkali resistance, thermal stability and film-forming property, is low in cost and easy to modify, and is an ideal material used as an anion exchange membrane substrate.
According to the scheme, the concentration of the polyphenyl ether solution in the step 1 is 0.05-0.2 mol/L.
According to the scheme, the precipitating agent in the steps 1 and 2 is methanol.
According to the scheme, the hydroxyl-containing piperidine micromolecules in the step 2 are 4-hydroxyl-1-methylpiperidine or 1-methyl-4-piperidinemethanol.
According to the scheme, the ratio of the piperidine group to the benzyl bromide group in the reaction system in the step 2 is 1: 1.
According to the scheme, the organic epoxy siloxane in the step 3 is 3-glycidyloxypropyltrimethoxysilane or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane.
According to the scheme, the epoxy ring-opening catalyst in the step 3 is boron trifluoride diethyl etherate.
According to the scheme, the molar ratio of the organic epoxy siloxane to the piperidine group in the step 3 is 1 (0.15-0.75).
Compared with the prior art, the invention has the following beneficial effects:
the preparation process is simple, the experimental process is simple and convenient to operate, and the industrial production is easy to realize.
The side chain of the siloxane grafted piperidine type polyphenylene oxide anion exchange membrane prepared by the invention contains a strong electron donating group and a piperidine group with excellent alkali resistance, so that the siloxane grafted piperidine type polyphenylene oxide anion exchange membrane has excellent alkali resistance and overcomes the problem of poor alkali stability of the existing anion exchange membrane in a high-temperature and strong-alkali environment. Tests show that the loss of the ionic conductivity of the anion exchange membrane prepared in 1mol/L potassium hydroxide solution at 80 ℃ is within 20 percent after the anion exchange membrane is soaked for 480 hours. In addition, a Si-O-Si crosslinking network constructed by siloxane hydrolysis crosslinking improves the mechanical property, dimensional stability and thermal stability of the prepared anion exchange membrane, and solves the problem of reduction of the mechanical property and dimensional stability caused by grafting a piperidine group on a polymer framework. Therefore, the prepared anion exchange membrane has all necessary performances of alkali stability, dimensional stability, thermal stability and the like, and has good comprehensive performance.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The preparation method of the siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following specific processes:
1) under the nitrogen atmosphere, dropwise adding a liquid bromine solution into the polyphenyl ether solution, heating at the temperature of 140-160 ℃ for 3-5h, and naturally cooling to room temperature; adding a precipitator, filtering, washing and drying to obtain brominated polyphenylene oxide solid; the number average molecular weight of the polyphenyl ether is 27000-50000; the precipitant is methanol.
2) Dissolving the obtained brominated polyphenylene oxide solid in N-methyl pyrrolidone, adding hydroxyl-containing piperidine micromolecules, uniformly mixing, and reacting at 70-80 ℃ for 24-48 h; adding a precipitator, filtering, washing and drying to obtain a piperidyl polyphenylene ether polymer; the hydroxyl-containing piperidine micromolecules are 4-hydroxyl-1-methylpiperidine or 1-methyl-4-piperidinemethanol; the ratio of piperidine group to benzyl bromide group in the system is 1: 1; the precipitant is methanol.
3) Dissolving the obtained piperidyl polyphenylene ether polymer in dimethyl sulfoxide, adding organic epoxy siloxane and an epoxy ring-opening catalyst, and reacting at 40-60 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution; the organic epoxy siloxane is 3-glycidyloxypropyltrimethoxysilane or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane; the epoxy ring-opening catalyst is boron trifluoride diethyl etherate; the molar ratio of the organic epoxy siloxane to the piperidine group is 1 (0.15-0.75).
4) And standing the obtained siloxane-bonded piperidyl polyphenylene oxide solution at room temperature for 24-48h for hydrolysis crosslinking reaction to form sol, then drying at 60-80 ℃ for 4-8h, then heating to 120-130 ℃ for drying for 6-8h, cooling and demolding to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
Example 1
The preparation method of the siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following specific steps:
1) the preparation method comprises the steps of putting polyphenyl ether (the number average molecular weight is 27000,0.05mol,6g) into a three-neck flask provided with a reflux condenser and a dropping funnel, adding 100mL of chlorobenzene to obtain a polyphenyl ether solution, introducing nitrogen, dropwise adding 3mL of chlorobenzene (20mL of chlorobenzene for dilution) after completely dissolving, heating to 140 ℃, reacting for 4 hours, naturally cooling to room temperature, adding 200mL of methanol to precipitate a product, washing the precipitate for multiple times, and drying to obtain the brominated polyphenyl ether polymer.
2) Dissolving the brominated polyphenylene oxide obtained in the step 1) in N-methyl pyrrolidone to obtain a brominated polyphenylene oxide solution with the mass fraction of 5%, then adding 4-hydroxy-1-methylpiperidine (0.115g,1mmol), wherein the ratio of piperidine groups to benzyl bromide groups in the solution is 1:1, uniformly mixing, reacting at 80 ℃ for 48h, adding a methanol precipitator for precipitation, washing the precipitate for several times by using methanol, and drying to obtain the piperidyl polyphenylene oxide polymer.
3) Dissolving the piperidyl polyphenylene ether polymer (0.6g,1mmol) obtained in the step 2) in dimethyl sulfoxide to obtain a piperidyl polyphenylene ether solution with the mass fraction of 6%, adding 3-glycidyloxypropyltrimethoxysilane (0.035g,0.15mmol) and 2 drops of boron trifluoride diethyl etherate catalyst to ensure that the molar ratio of epoxy groups in the 3-glycidyloxypropyltrimethoxysilane to hydroxyl groups in the piperidyl polyphenylene ether polymer is 1:0.15, and then reacting at 60 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution.
4) Stirring the siloxane-bonded piperidyl polyphenylene oxide solution obtained in the step 3) for 12 hours, then placing the solution at room temperature for 48 hours to perform a hydrolytic crosslinking reaction to form sol, pouring the sol into a tetrafluoroethylene membrane disc, then drying the sol at 60 ℃ for 8 hours, then heating the sol to 120 ℃ to dry the sol for 8 hours, cooling the sol to room temperature, and then demolding to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
The anion exchange membrane prepared in the example is tested, and the anion exchange membrane prepared in the example has the linear swelling degree of 10.3% at normal temperature, the tensile strength of 19.4MPa, the ion exchange capacity of 1.84mmol/g, the ion conductivity of 0.071S/cm at 80 ℃ under the hydration condition, and the ion conductivity loss of 19.97% after being soaked in 1mol/L potassium hydroxide solution at 80 ℃ for 480 h.
Example 2
The preparation method of the siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following specific steps:
1) the preparation method comprises the steps of putting polyphenyl ether (with the number average molecular weight of 5000,0.05mol and 6g) into a three-neck flask provided with a reflux condenser and a dropping funnel, adding 100mL of chlorobenzene to obtain a polyphenyl ether solution, introducing nitrogen, dropwise adding 3mL of chlorobenzene (20mL of chlorobenzene for dilution) after completely dissolving, heating to 160 ℃, reacting for 3 hours, naturally cooling to room temperature, adding 200mL of methanol to precipitate a product, washing the precipitate for multiple times, and drying to obtain the brominated polyphenyl ether polymer.
2) Dissolving the brominated polyphenylene oxide obtained in the step 1) in N-methyl pyrrolidone to obtain a brominated polyphenylene oxide solution with the mass fraction of 6%, then adding 1-methyl-4-piperidinemethanol (0.129g,1mmol), wherein the ratio of piperidine groups to benzyl bromide groups in the solution is 1:1, uniformly mixing, reacting at 80 ℃ for 48h, adding a methanol precipitator for precipitation, washing the precipitate for several times by using methanol, and drying to obtain the piperidyl polyphenylene oxide polymer.
3) Dissolving the piperidyl polyphenylene ether polymer (0.6g,1mmol) obtained in the step 2) in dimethyl sulfoxide to obtain a piperidyl polyphenylene ether solution with the mass fraction of 8%, adding 3-glycidyloxypropyltrimethoxysilane (0.07g,0.30mmol) and 2 drops of boron trifluoride diethyl etherate catalyst to ensure that the molar ratio of an epoxy group in the 3-glycidyloxypropyltrimethoxysilane to a hydroxyl group in the piperidyl polyphenylene ether polymer is 1:0.3, and then reacting at 40 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution.
4) Stirring the siloxane-bonded piperidyl polyphenylene oxide solution obtained in the step 3) for 24 hours, then placing the solution at room temperature for 24 hours to perform a hydrolytic crosslinking reaction to form sol, pouring the sol into a tetrafluoroethylene membrane disc, then drying the sol at 80 ℃ for 4 hours, then heating the sol to 130 ℃ to dry the sol for 8 hours, cooling the sol to room temperature, and then demolding to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
The anion exchange membrane prepared in the example is tested, and the anion exchange membrane prepared in the example has the linear swelling degree of 10.3% at normal temperature, the tensile strength of 23.7MPa, the ion exchange capacity of 1.69mmol/g, the ion conductivity of 0.057S/cm at 80 ℃ under the hydration condition, and the ion conductivity loss of 18.05% after being soaked in 1mol/L potassium hydroxide solution at 80 ℃ for 480 hours.
Example 3
The preparation method of the siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following specific steps:
1) putting polyphenyl ether (number average molecular weight 35000,0.05mol,6g) into a three-neck flask provided with a reflux condenser and a dropping funnel, adding 100mL of chlorobenzene to obtain a polyphenyl ether solution, introducing nitrogen, dropwise adding 3mL of chlorobenzene (20mL of chlorobenzene for dilution) after completely dissolving, heating to 150 ℃, then reacting for 5 hours, naturally cooling to room temperature, adding 200mL of methanol to precipitate a product, washing the precipitate for multiple times, and drying to obtain the brominated polyphenyl ether polymer.
2) Dissolving the brominated polyphenylene oxide obtained in the step 1) in N-methyl pyrrolidone to obtain a brominated polyphenylene oxide solution with the mass fraction of 8%, then adding 4-hydroxy-1-methylpiperidine (0.115g,1mmol), wherein the ratio of piperidine groups to benzyl bromide groups in the solution is 1:1, uniformly mixing, reacting at 60 ℃ for 36h, adding a methanol precipitator for precipitation, washing the precipitate for several times by using methanol, and drying to obtain the piperidyl polyphenylene oxide polymer.
3) Dissolving the piperidyl polyphenylene ether polymer (0.6g,1mmol) obtained in the step 2) in dimethyl sulfoxide to obtain a piperidyl polyphenylene ether solution with the mass fraction of 6%, adding 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane (0.111g,0.45mmol) and 2 drops of boron trifluoride diethyl etherate catalyst to enable the molar ratio of epoxy groups in the 3-glycidyloxypropyltrimethoxysilane to hydroxyl groups in the piperidyl polyphenylene ether polymer to be 1:0.45, and then reacting at 60 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution.
4) Stirring the siloxane-bonded piperidyl polyphenylene oxide solution obtained in the step 3) for 12 hours, then placing the solution at room temperature for 48 hours to perform a hydrolytic crosslinking reaction to form sol, pouring the sol into a tetrafluoroethylene membrane disc, then drying the sol at 40 ℃ for 8 hours, then heating the sol to 130 ℃ to dry the sol for 6 hours, cooling the sol to room temperature, and then demolding the cooled sol to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
The anion exchange membrane prepared in the example is tested, and the anion exchange membrane prepared in the example has the linear swelling degree of 7.1% at normal temperature, the tensile strength of 26.3MPa, the ion exchange capacity of 1.57mmol/g, the ion conductivity of 0.044S/cm at 80 ℃ under the hydration condition, and the ion conductivity loss of 16.74% after being soaked in 1mol/L potassium hydroxide solution at 80 ℃ for 480 h.
Example 4
The preparation method of the siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following specific steps:
1) the preparation method comprises the steps of putting polyphenyl ether (the number average molecular weight is 42000,0.05mol and 6g) into a three-neck flask provided with a reflux condenser and a dropping funnel, adding 100mL of chlorobenzene to obtain a polyphenyl ether solution, introducing nitrogen, dropwise adding 3mL of chlorobenzene (20mL of chlorobenzene for dilution) after completely dissolving, heating to 160 ℃, reacting for 3 hours, naturally cooling to room temperature, adding 200mL of methanol to precipitate a product, washing the precipitate for multiple times, and drying to obtain the brominated polyphenyl ether polymer.
2) Dissolving the brominated polyphenylene oxide obtained in the step 1) in N-methyl pyrrolidone to obtain a brominated polyphenylene oxide solution with the mass fraction of 5%, then adding 1-methyl-4-piperidinemethanol (0.129g,1mmol), wherein the ratio of piperidine groups to benzyl bromide groups in the solution is 1:1, uniformly mixing, reacting at 70 ℃ for 48h, adding a methanol precipitator for precipitation, washing the precipitate for several times by using methanol, and drying to obtain the piperidyl polyphenylene oxide polymer.
3) Dissolving the piperidyl polyphenylene ether polymer (0.6g,1mmol) obtained in the step 2) in dimethyl sulfoxide to obtain a piperidyl polyphenylene ether solution with the mass fraction of 6%, adding 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane (0.111g,0.45mmol) and 2 drops of boron trifluoride diethyl etherate catalyst to enable the molar ratio of epoxy groups in the 3-glycidyloxypropyltrimethoxysilane to hydroxyl groups in the piperidyl polyphenylene ether polymer to be 1:0.6, and then reacting at 50 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution.
4) Stirring the siloxane-bonded piperidyl polyphenylene oxide solution obtained in the step 3) for 12 hours, then placing the solution at room temperature for 24 hours to perform a hydrolytic crosslinking reaction to form sol, pouring the sol into a tetrafluoroethylene membrane disc, then drying the sol at 70 ℃ for 6 hours, then heating the sol to 120 ℃ to dry the sol for 8 hours, cooling the sol to room temperature, and then demolding to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
The anion exchange membrane prepared in the example is tested, and the anion exchange membrane prepared in the example has the linear swelling degree of 5.3% at normal temperature, the tensile strength of 24.5MPa, the ion exchange capacity of 1.43mmol/g, the ion conductivity of 0.044S/cm at 80 ℃ under the hydration condition, and the ion conductivity loss of 14.64% after being soaked in 1mol/L potassium hydroxide solution at 80 ℃ for 480 h.
Example 5
The preparation method of the siloxane grafted piperidine type polyphenyl ether anion exchange membrane comprises the following specific steps:
1) putting polyphenyl ether (number average molecular weight 38000,0.05mol,6g) into a three-neck flask provided with a reflux condenser and a dropping funnel, adding 100mL of chlorobenzene to obtain a polyphenyl ether solution, introducing nitrogen, dropwise adding 3mL of chlorobenzene (20mL of chlorobenzene for dilution) after complete dissolution, heating to 140 ℃, then reacting for 4h, naturally cooling to room temperature, adding 200mL of methanol to precipitate a product, washing the precipitate for multiple times, and drying to obtain the brominated polyphenyl ether polymer.
2) Dissolving the brominated polyphenylene oxide obtained in the step 1) in N-methyl pyrrolidone to obtain a brominated polyphenylene oxide solution with the mass fraction of 5%, then adding 4-hydroxy-1-methylpiperidine (0.115g,1mmol), wherein the ratio of piperidine groups to benzyl bromide groups in the solution is 1:1, uniformly mixing, reacting at 70 ℃ for 36h, adding a methanol precipitator for precipitation, washing the precipitate for several times by using methanol, and drying to obtain the piperidyl polyphenylene oxide polymer.
3) Dissolving the piperidyl polyphenylene ether polymer (0.6g,1mmol) obtained in the step 2) in dimethyl sulfoxide to obtain a piperidyl polyphenylene ether solution with the mass fraction of 6%, adding 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane (0.111g,0.45mmol) and 2 drops of boron trifluoride diethyl etherate catalyst to enable the molar ratio of epoxy groups in the 3-glycidyloxypropyltrimethoxysilane to hydroxyl groups in the piperidyl polyphenylene ether polymer to be 1:0.75, and then reacting at 50 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution.
4) Stirring the siloxane-bonded piperidyl polyphenylene oxide solution obtained in the step 3) for 12 hours, then placing the solution at room temperature for 36 hours to perform a hydrolytic crosslinking reaction to form sol, pouring the sol into a tetrafluoroethylene membrane disc, then drying the sol at 70 ℃ for 8 hours, then heating to 130 ℃ to dry for 6 hours, cooling to room temperature, and then demolding to obtain the siloxane-grafted piperidine polyphenylene oxide anion exchange membrane.
The anion exchange membrane prepared in the example is tested, and the anion exchange membrane prepared in the example has the linear swelling degree of 4.3% at normal temperature, the tensile strength of 19.2MPa, the ion exchange capacity of 1.35mmol/g, the ion conductivity of 0.041S/cm under the hydration condition at 80 ℃, and the ion conductivity loss of 13.08% after being soaked in 1mol/L potassium hydroxide solution at 80 ℃ for 480 h.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
Claims (9)
1. A preparation method of a siloxane grafted piperidine type polyphenyl ether anion exchange membrane is characterized by comprising the following steps:
1) under the nitrogen atmosphere, dropwise adding a liquid bromine solution into the polyphenyl ether solution, heating at the temperature of 140-160 ℃ for 3-5h, and naturally cooling to room temperature; adding a precipitator, filtering, washing and drying to obtain brominated polyphenylene oxide solid;
2) dissolving the obtained brominated polyphenylene oxide solid in N-methyl pyrrolidone, adding hydroxyl-containing piperidine micromolecules, uniformly mixing, and reacting at 70-80 ℃ for 24-48 h; adding a precipitator, filtering, washing and drying to obtain a piperidyl polyphenylene ether polymer;
3) dissolving the obtained piperidyl polyphenylene ether polymer in dimethyl sulfoxide, adding organic epoxy siloxane and an epoxy ring-opening catalyst, and reacting at 40-60 ℃ to obtain a siloxane-bonded piperidyl polyphenylene ether solution;
4) and standing the obtained siloxane-bonded piperidyl polyphenylene oxide solution at room temperature for 24-48h for hydrolysis crosslinking reaction to form sol, then drying at 60-80 ℃ for 4-8h, then heating to 120-130 ℃ for drying for 6-8h, cooling and demolding to obtain the siloxane-grafted piperidine type polyphenylene oxide anion exchange membrane.
2. The method for preparing the siloxane-grafted piperidine type polyphenylene ether anion exchange membrane according to claim 1, wherein the polyphenylene ether in step 1 has a number average molecular weight of 27000-50000.
3. The method for preparing a silicone-grafted piperidine type polyphenylene ether anion exchange membrane according to claim 1, wherein the polyphenylene ether solution in the step 1 has a concentration of 0.05 to 0.2 mol/L.
4. The method of preparing a silicone-grafted piperidine-based polyphenylene ether anion exchange membrane according to claim 1 wherein the precipitating agent of steps 1 and 2 is methanol.
5. The method for preparing a silicone-grafted piperidine type polyphenylene ether anion exchange membrane according to claim 1, wherein the hydroxyl group-containing piperidine small molecule in step 2 is 4-hydroxy-1-methylpiperidine or 1-methyl-4-piperidinemethanol.
6. The method for producing a silicone-grafted piperidine type polyphenylene ether anion-exchange membrane according to claim 1, wherein the ratio of the piperidine group to the benzylbromide group in the reaction system in the step 2 is 1: 1.
7. The method for preparing a silicone-grafted piperidine-based polyphenylene ether anion exchange membrane according to claim 1, wherein the organo-epoxysiloxane of step 3 is 3-glycidoxypropyltrimethoxysilane or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane.
8. The method for preparing a silicone-grafted piperidine-based polyphenylene ether anion exchange membrane according to claim 1, wherein the epoxide opening catalyst in step 3 is boron trifluoride ethyl ether.
9. The method for preparing a silicone-grafted piperidine-based polyphenylene ether anion exchange membrane according to claim 1, wherein the molar ratio of the organoepoxysiloxane to the piperidine group in step 3 is 1 (0.15-0.75).
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