CN112086671B - Composite anion exchange membrane doped with guanidino functionalized graphene and preparation method thereof - Google Patents
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Abstract
The invention discloses a composite anion exchange membrane doped with guanidino functionalized graphene and a preparation method thereof, and belongs to the technical field of membranes. The composite anion exchange membrane is an organic-inorganic composite membrane, the inorganic phase is guanidine functional graphene, and the organic phase is a fluorine-containing acrylate polymer with a large number of guanidine functional groups on side chains. The composite anion exchange membrane prepared by the invention has higher ionic conductivity, good chemical stability and thermal stability, excellent dimensional stability and mechanical property, and good alcohol resistance when being used for a direct methanol fuel cell.
Description
Technical Field
The invention belongs to the technical field of membranes, and particularly relates to an organic-inorganic composite anion exchange membrane doped with guanidino functionalized graphene and a preparation method thereof.
Background
An anion exchange membrane is an alkaline electrolyte and is also referred to as an anion permselective membrane because of its selective action on anions. The anion exchange membrane has wide application, is one of key materials in a mixture separation and purification device and an electrochemical component, and plays an important role in the fields of chlor-alkali industry, water treatment industry, heavy metal recovery, hydrometallurgy, electrochemical industry and the like. In recent years, with the development of novel chemical power sources, the application of an anion exchange membrane as a battery diaphragm in the aspects of a liquid flow energy storage battery, an alkaline anion exchange membrane fuel battery, a novel super capacitor and the like is also getting more and more attention and research. As a core material for alkaline anion exchange membrane fuel cells, an ideal anion exchange membrane should meet several requirements: 1) The ionic conductivity is high; 2) Good alkali resistance and heat resistance stability; 3) Good mechanical properties and dimensional stability.
At present, the reported anion exchange membranes generally have the problems of low ionic conductivity, poor alkali resistance, poor heat resistance and the like. And membranes with higher conductivities generally have higher water contents and ion exchange capacities. However, too high a water content results in excessive swelling of the membrane, poor dimensional stability, and reduced mechanical properties and alkali resistance, and too high a methanol permeability results in reduced cell performance when used in a direct methanol fuel cell.
Doping inorganic phase into polymer film is one method of modifying anion exchange film, and common inorganic phase dopant is SiO 2 、TiO 2 、ZrO 2 Carbon nanotubes, montmorillonite, graphene oxide, and the like. The polymer anion exchange membrane is modified by doping proper inorganic particles, so that the water content, conductivity, chemical stability, mechanical property and the like of the membrane are hopeful to be improved. For example, yang et al describe nano TiO 2 Introducing the polymer into a polyvinyl alcohol matrix, uniformly mixing to prepare an organic-inorganic hybrid membrane, and then carrying out crosslinking reaction on the membrane to obtain the crosslinked hybrid membrane, wherein the membrane has good thermal stability, high ionic conductivity and low swelling ratio, and the ionic conductivity can reach 48mS cm at room temperature -1 . Li and the like are mixed directly with ZrO 2 The inorganic nano material is introduced into the aryl polymer to prepare the organic/inorganic anion exchange membrane, so that the comprehensive performance of the hybrid membrane is obviously improved. Liu et al prepared Quaternized Graphene (QGs) by epoxy ring-opening reaction, and introduced QGs into quaternized polyethersulfone to make a composite anion exchange membrane. The introduction of QGs increases the density of the quaternary ammonium salt within the membrane and forms ion exchange channels on the QGs surface, which increases the conductivity of the membrane and may improve other properties of the composite membrane. In the modification method of inorganic-organic hybridization, how to select proper inorganic components as doping materials and interfacial compatibility of organic phase and inorganic phase are all problems to be solved. The compatibility of organic and inorganic particles affects the water molecules and OH - The inorganic phase and the organic phase can be ionized, so that the water absorption of the film can be improved, and the uniform distribution of inorganic particles is facilitated. Since anion exchange membranes operate in alkaline environments, the stability of the ionized groups is also a problem to be solved.
Graphene Oxide (GO) is receiving widespread attention due to its unique two-dimensional layered structure, rich oxygen-containing functional groups, high specific surface area and good mechanical stability. Considering that the oxygen-containing groups in GO have weaker ionic conductivity, the ionic conductivity is reduced after GO is directly introduced into the polymer anion membrane, so that the voltage efficiency of the battery is reduced. In the invention, guanidine groups are firstly introduced into GO for ionization so as to improve the ion conductivity of the GO, and meanwhile, the water absorption of an inorganic phase is also improved, so that the uniform distribution of inorganic particles is facilitated, the compatibility of the inorganic particles with the guanidine group functionalized polymer is enhanced, and the composite ion exchange membrane with excellent comprehensive performance is obtained.
Disclosure of Invention
The invention aims to solve the problems of low ion conductivity, poor alkali resistance, poor heat resistance, poor dimensional stability and the like of the anion exchange membrane in the prior art, and provides a composite anion exchange membrane doped with guanidino functionalized graphene and a preparation method thereof. The anion exchange membrane prepared by the invention has higher ionic conductivity, good chemical stability and thermal stability, excellent dimensional stability and mechanical property and good alcohol resistance.
According to the invention, graphite is used as a raw material, an improved Hummers method is adopted to prepare Graphene Oxide (GO), then the graphene oxide is Ji Gua to obtain the guanidyl functionalized graphene (GGO), and finally GGO is doped into a self-made guanidyl functionalized fluorine-containing anion exchange membrane to obtain the guanidyl functionalized graphene doped composite anion exchange membrane.
The technical scheme of the invention is as follows:
a composite anion exchange membrane doped with guanidine functional graphene comprises an organic phase and an inorganic phase, wherein the inorganic phase is the guanidine functional graphene, the organic phase is a fluorine-containing acrylate polymer with a large number of guanidine functional groups on side chains, active groups of the polymer are tetramethyl benzyl guanidine, and after the composite anion exchange membrane is soaked in a target anion solution, tetramethyl benzyl guanidine compounds on a main chain of the polymer contain target anions. Wherein the target anion is specifically Cl - 、Br - 、HCO 3 - 、I - 、CO 3 2- 、SO 3 H - 、OH - 、SO 4 2- Any one of them.
The preparation method of the composite anion exchange membrane doped with the guanidino functionalized graphene comprises the following steps:
(1) Preparation of guanidino-functionalized graphene
Placing the reactor in an ice-water bath, adding sulfuric acid/phosphoric acid mixed solution (the volume ratio of sulfuric acid to phosphoric acid is 9:1), graphite powder and potassium permanganate, stirring uniformly, reacting for 10-28 hours at 40-80 ℃, cooling to room temperature, adding deionized water and hydrogen peroxide until the reactants become bright yellow solid, washing with dilute hydrochloric acid, repeatedly washing with deionized water to neutrality, and drying to obtain graphene oxide; another reactor is taken, tetramethyl guanidine and graphene oxide are added, and the mass ratio of the tetramethyl guanidine to the graphene oxide is 1:0.1-0.3, sealing and reacting for 16-20 hours at 60-90 ℃, cooling, washing to neutrality, and drying to obtain a product, namely the guanidine-functionalized graphene;
(2) Synthesis of tetramethyl benzyl guanidine
Placing tetramethylguanidine in a reactor, adding benzyl halide such as benzyl chloride, benzyl bromide, and benzyl iodide, reacting at 30-80deg.C for 10-20 hr at molar ratio of tetramethylguanidine to benzyl halide of 10:1-10, filtering, dissolving the obtained filtrate with diethyl ether, washing with distilled water for 4-6 times, and anhydrous Na 2 SO 4 Drying and evaporating to remove the solvent, and obtaining the product, namely tetramethyl benzyl guanidine;
(3) Preparation of chloromethylated fluoropolymers
Adding a fluorine-containing acrylic ester monomer, a monomer containing halogenated benzyl functional groups, a solvent and an initiator into a reactor, carrying out reflux reaction for 12-28 h at 50-90 ℃ under the protection of inert gas, and obtaining a fluorine-containing polymer with a large number of halogenated benzyl functional groups on side chains after precipitation, washing and drying of the obtained product; the molar ratio of the fluorine-containing acrylate monomer to the monomer containing the halogenated benzyl functional group is 1:0.1-1.5; the fluorine-containing acrylate monomer is one or more of trifluoroethyl acrylate, hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate and the like;
(4) Preparation of guanidine-functionalized fluoropolymer
Dissolving the polymer obtained in the step (3) in an organic solvent to prepare a polymer solution with the mass percent concentration of 5% -20%, adding the tetramethyl benzyl guanidine obtained in the step (2), and stirring and reacting for 6-16 hours at 20-50 ℃, wherein the molar ratio of the tetramethyl benzyl guanidine to the halogenated benzyl functional group monomer is 1: 1-2.5, wherein the organic solvent for dissolving the polymer is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
(5) Doping and composite film forming of guanidine group functionalized graphene
Adding the polymer solution obtained in the step (4) into the guanidino-functionalized graphene obtained in the step (1), stirring, performing ultrasonic dispersion, casting into a composite anion exchange membrane by using a phase inversion method, and drying for later use, wherein the addition amount of the guanidino-functionalized graphene is 0.1% -1.8% of the mass of the guanidino-functionalized fluorine-containing polymer;
(6) Transformation process
Soaking the composite anion exchange membrane obtained in the step (5) in a target anion solution, wherein the tetramethyl benzyl guanidine compound on the main chain of the polymer contains target anions, and the target anions are specifically Cl - 、Br - 、HCO 3 - 、I - 、CO 3 2- 、SO 3 H - 、OH - 、SO 4 2- Any one of them.
The invention has the remarkable advantages compared with the prior art that:
compared with the traditional method for preparing the anion exchange membrane by chloromethylation and oxalyl chloride, the preparation method avoids the use of virulent and cancerogenic agents such as formaldehyde, chloromethyl ether, chloromethyl alkyl ether and the like, and is environment-friendlyThe reaction conditions are mild. The film prepared by the invention has the conductivity of 56 mS.cm at 30 DEG C -1 And the conductivity of the 500 h membrane is hardly changed when the membrane is soaked in 6 mol/L alkali liquor. The membrane is stable at 220 ℃ and meets the operating temperature requirement of the fuel cell. The film has high dimensional stability in water and good mechanical properties. The membrane had a methanol permeability of only 4.23×10 -8 cm 2 s -1 When used in direct methanol anion membrane fuel cell, the catalyst has good alcohol resistance.
Detailed Description
The technical scheme of the invention is further described below through the embodiment examples.
Example 1
A preparation method of a composite anion exchange membrane doped with guanidino functionalized graphene comprises the following steps:
(1) Preparation of guanidine-functionalized graphite oxide (GGO): placing a single-neck flask in an ice-water bath, adding 75 mL mixed acid (sulfuric acid and phosphoric acid in a volume ratio of 9:1) into the flask, adding 1 g graphite powder, stirring while adding, reacting for 30 minutes while stirring, slowly adding 5 g potassium permanganate, heating to 50 ℃ for reacting for 16 hours, cooling to room temperature, and adding 80 mL deionized water and 20mL H 2 O 2 Further oxidation is carried out until the solid turns to be bright yellow, stirring is carried out for 1 hour, washing is carried out to be neutral by 5% of HCl and deionized water, and a yellow product is obtained after freeze drying, namely Graphene Oxide (GO). Weighing 100 mg GO, pouring the GO into a 50mL three-neck flask, adding 15mL of tetramethylguanidine, sealing, heating in an oil bath at 80 ℃ for reaction for 18 hours, cooling to room temperature, washing with absolute ethyl alcohol to neutrality, and freeze-drying to obtain the guanidino functionalized graphene oxide (GGO).
(2) Preparation of tetramethyl benzoguanidine: mixing 3g tetramethyl guanidine and 0.4g benzyl chloride in 50mL round bottom flask, stirring at room temperature for 4 hr, reacting in water bath at 60deg.C for 15 hr, filtering the reaction turbid liquid, diluting filtrate with 50mL dichloroethane, washing with deionized water for 4 times, and collecting extractive solution with anhydrous Na 2 SO 4 Drying, filtering, and steamingThe excess solvent was removed by evaporation to give the product tetramethyl benzoguanidine as a brown oil.
(3) Preparation of chloromethylated fluoropolymer: adding hexafluorobutyl methacrylate, trifluoropropyl methacrylate and chloromethyl styrene into a three-neck flask, wherein the molar ratio of the hexafluorobutyl methacrylate to the trifluoropropyl methacrylate to the chloromethyl styrene is as follows: 4:3:4, adding N, N-dimethylformamide as a solvent and azodiisobutyronitrile as an initiator, carrying out reflux reaction for 20 hours at 60 ℃ under the protection of inert gas, precipitating the product with deionized water, washing for multiple times, and drying for later use.
(4) Preparation of guanidine-functionalized fluoropolymer: dissolving chloromethyl fluorine-containing polymer obtained in the last step in dimethylacetamide to prepare 10% polymer solution, adding tetramethyl benzyl guanidine with the molar mass 1.5 times of chloromethyl styrene in the step (3), and stirring and reacting for 12 hours at 25 ℃ for standby.
(5) Doping and composite film forming of guanidine group functionalized graphene: adding the guanidyl functionalized graphene into the polymer solution obtained in the last step, wherein the addition amount of the guanidyl functionalized graphene is 1% of the mass of the guanidyl functionalized fluorine-containing polymer, stirring, performing ultrasonic dispersion, casting into a film by a phase inversion method, and drying for later use.
The prepared film was subjected to 2 mol.L -1 Transferring in NaOH solution to obtain hydroxide type composite anion exchange membrane, and washing the membrane with ultrapure water to neutrality.
The film was tested to have a water content of 15.6% at 25℃and an electrical conductivity of 56.5 mS cm at 30 ℃ -1 The swelling degree was 16%, and the electrical conductivity reached 90 mS cm when the temperature was increased to 80 DEG C -1 The conductivity of the membrane foam was hardly changed by 500. 500 h in 6M NaOH aqueous solution. Tensile strength was 53.8MPa, elongation at break was 15.1%, methanol permeability was 4.23X 10 -8 cm 2 s -1 。
Example 2
A preparation method of a composite anion exchange membrane doped with guanidino functionalized graphene comprises the following steps:
(1) Preparation of guanidine-functionalized graphite oxide (GGO): graphene Oxide (GO) was prepared by the same method as in example 1. Weighing 100 mg GO, pouring the GO into a 50mL three-neck flask, adding 30mL of tetramethylguanidine, sealing, heating in an oil bath at 60 ℃ for reaction for 20 hours, cooling to room temperature, washing with absolute ethyl alcohol to neutrality, and freeze-drying to obtain the guanidino functionalized graphene oxide (GGO).
(2) Preparation of tetramethyl benzoguanidine: mixing 3g tetramethyl guanidine and 0.3g benzyl bromide in 50mL round bottom flask, stirring the mixture at room temperature for 4 hours, then reacting in 40 ℃ water bath for 20 hours, filtering the reaction turbid liquid, taking filtrate, diluting with 50mL methylene dichloride, washing with deionized water for 4 times, finally using anhydrous Na to extract 2 SO 4 Drying, filtration and finally evaporation of the excess solvent using a rotary evaporator gives the product tetramethyl benzoguanamine as a brown oil.
(3) Preparation of chloromethylated fluoropolymer: adding hexafluorobutyl methacrylate and chloromethyl styrene into a three-neck flask, wherein the molar ratio of the hexafluorobutyl methacrylate to the chloromethyl styrene is as follows: 1:1.5, adding N, N-dimethylacetamide as a solvent and azodiisobutyronitrile as an initiator, carrying out reflux reaction for 12 hours at 90 ℃ under the protection of inert gas, precipitating the product with deionized water, washing for multiple times, and drying for later use.
(4) Preparation of guanidine-functionalized fluoropolymer: dissolving the chloromethylated fluorine-containing polymer obtained in the last step in dimethylformamide to prepare a polymer solution with the concentration of 5%, adding tetramethyl benzyl guanidine with the same molar mass as chloromethyl styrene in the step (3), and stirring and reacting for 6 hours at 50 ℃ for later use.
(5) Doping and composite film forming of guanidine group functionalized graphene: adding the guanidino-functionalized graphene into the polymer solution obtained in the last step, wherein the addition amount of the guanidino-functionalized graphene is 0.8% of the mass of the guanidino-functionalized fluorine-containing polymer, stirring, performing ultrasonic dispersion, casting into a film by a phase inversion method, and drying for later use.
The prepared film was subjected to 2 mol.L -1 Transferring in NaOH solution to obtain hydroxide type anion exchange membrane, and washing the membrane with ultrapure water to neutrality.
The film was tested to have a water content of 14.3% at 25℃and an electrical conductivity of 46. mS cm at 30 ℃ -1 The swelling degree was 15.3%, and the electrical conductivity reached 89 mS cm when the temperature was increased to 80 DEG C -1 The conductivity of the membrane foam was hardly changed by 500. 500 h in 6M NaOH aqueous solution. Tensile strength was 47.2MPa, elongation at break was 14.6%, methanol permeability was 6.3X10 -8 cm 2 s -1 。
Example 3
A preparation method of a composite anion exchange membrane doped with guanidino functionalized graphene comprises the following steps:
(1) Preparation of guanidine-functionalized graphite oxide (GGO): graphene Oxide (GO) was prepared by the same method as in example 1. Weighing 100 mg GO, pouring the GO into a 50mL three-neck flask, adding 20mL of tetramethylguanidine, sealing, heating in an oil bath at 90 ℃ for reaction for 16 hours, cooling to room temperature, washing with absolute ethyl alcohol to neutrality, and freeze-drying to obtain the guanidino functionalized graphene oxide (GGO).
(2) Preparation of tetramethyl benzoguanidine: mixing 3g tetramethyl guanidine and 3g benzyl chloride in 50mL round bottom flask, stirring the mixture at room temperature for 4 hours, then reacting in 40 ℃ water bath for 12 hours, filtering the reaction turbid liquid, taking filtrate, diluting with 50mL methylene chloride, washing with deionized water for 4 times, and finally using anhydrous Na to extract 2 SO 4 Drying, filtration and finally evaporation of the excess solvent using a rotary evaporator gives the product tetramethyl benzoguanidine as a brown oil.
(3) Preparation of chloromethylated fluoropolymer: adding tetrafluoropropyl methacrylate and chloromethyl styrene into a three-neck flask, wherein the molar ratio of the tetrafluoropropyl methacrylate to the chloromethyl styrene is as follows: 1:1, adding N, N-dimethylacetamide as a solvent, azodiisobutyronitrile as an initiator, carrying out reflux reaction for 28 hours at 50 ℃ under the protection of inert gas, precipitating the product with deionized water, washing for multiple times, and drying for later use.
(4) Preparation of guanidine-functionalized fluoropolymer: dissolving chloromethyl fluorine-containing polymer obtained in the last step in N-methyl pyrrolidone to prepare 10% polymer solution, adding tetramethyl benzyl guanidine with the molar mass of 2.5 times of chloromethyl styrene in the step (3), and stirring and reacting for 20 hours at 20 ℃ for later use.
(5) Doping and composite film forming of guanidine group functionalized graphene: adding the guanidino-functionalized graphene into the polymer solution obtained in the last step, wherein the addition amount of the guanidino-functionalized graphene is 0.3% of the mass of the guanidino-functionalized fluorine-containing polymer, stirring, performing ultrasonic dispersion, casting into a film by a phase inversion method, and drying for later use.
The prepared film was subjected to 2 mol.L -1 Transferring in NaOH solution to obtain hydroxide type anion exchange membrane, and washing the membrane with ultrapure water to neutrality.
The film was tested to have a water content of 14.3% at 25℃and an electrical conductivity of 36.5 mS cm at 30 ℃ -1 The swelling degree was 17.3%, and when the temperature was increased to 80℃the electrical conductivity reached 78 mS cm -1 The conductivity of the membrane foam was hardly changed by 500. 500 h in 6M NaOH aqueous solution. Tensile strength was 52.2MPa, elongation at break was 13.7%, methanol permeability was 7.1X10 -8 cm 2 s -1 。
Example 4
A preparation method of a composite anion exchange membrane doped with guanidino functionalized graphene comprises the following steps:
(1) Preparation of guanidine-functionalized graphite oxide (GGO): graphene Oxide (GO) was prepared by the same method as in example 1. Weighing 100 mg GO, pouring the GO into a 50mL three-neck flask, adding 30mL of tetramethylguanidine, sealing, heating in an oil bath at 60 ℃ for reaction for 20 hours, cooling to room temperature, washing with absolute ethyl alcohol to neutrality, and freeze-drying to obtain the guanidino functionalized graphene oxide (GGO).
(2) Preparation of tetramethyl benzoguanidine: tetramethyl benzoguanamine was prepared in the same manner as in example 1. Mixing 3g tetramethyl guanidine and 0.4g benzyl chloride in a 50mL round bottom flask under stirring, stirring the mixture at room temperature for 4 hours, then reacting in a water bath at 60 ℃ for 15 hours, filtering the reaction turbid liquid, diluting the filtrate with 50mL dichloroethane, washing with deionized water for 4 times,the extract is treated with anhydrous Na 2 SO 4 Drying, filtration and finally removal of excess solvent by evaporation using a rotary evaporator gives the product tetramethyl benzoguanamine as a brown oil.
(3) Preparation of chloromethylated fluoropolymer: adding hexafluorobutyl methacrylate and chloromethyl styrene into a three-neck flask, wherein the molar ratio of the hexafluorobutyl methacrylate to the chloromethyl styrene is as follows: 1:0.8, adding N, N-dimethylformamide as a solvent, taking azodiisobutyronitrile as an initiator, carrying out reflux reaction for 18 hours at 80 ℃ under the protection of inert gas, precipitating the product with deionized water, washing for multiple times, and drying for later use.
(4) Preparation of guanidine-functionalized fluoropolymer: dissolving chloromethyl fluorine-containing polymer obtained in the last step in N, N-dimethylacetamide to prepare 10% polymer solution, adding tetramethyl benzyl guanidine with the molar mass 1.8 times of chloromethyl styrene in the step (3), and stirring and reacting for 15 hours at 35 ℃ for later use.
(5) Doping and composite film forming of guanidine group functionalized graphene: adding the guanidyl functionalized graphene into the polymer solution obtained in the last step, wherein the addition amount of the guanidyl functionalized graphene is 1.5% of the mass of the guanidyl functionalized fluorine-containing polymer, stirring, performing ultrasonic dispersion, casting into a film by a phase inversion method, and drying for later use.
The prepared film was subjected to 2 mol.L -1 NaSO 4 Performing transfer treatment on the solution to obtain SO 4 2- The anion exchange membrane is finally washed to neutrality with ultrapure water.
The water content of the membrane at 25℃was 18.3% and the ion exchange capacity at 30℃was 3.8 mmol g -1 The swelling degree was 16.2%. The membrane was immersed in a 6M NaOH aqueous solution at 500 a h a little change in ion exchange capacity occurred. The tensile strength was 41.3MPa, and the elongation at break was 11.8%.
Example 5
A preparation method of a composite anion exchange membrane doped with guanidino functionalized graphene comprises the following steps:
(1) Preparation of guanidine-functionalized graphite oxide (GGO): graphene Oxide (GO) was prepared by the same method as in example 1. Weighing 100 mg GO, pouring the GO into a 50mL three-neck flask, adding 30mL of tetramethylguanidine, sealing, heating in an oil bath at 60 ℃ for reaction for 20 hours, cooling to room temperature, washing with absolute ethyl alcohol to neutrality, and freeze-drying to obtain the guanidino functionalized graphene oxide (GGO).
(2) Preparation of tetramethyl benzoguanidine: tetramethyl benzoguanamine was prepared in the same manner as in example 1. Mixing 3g tetramethyl guanidine and 0.4g benzyl chloride in 50mL round bottom flask, stirring at room temperature for 4 hr, reacting in water bath at 60deg.C for 15 hr, filtering the reaction turbid liquid, diluting filtrate with 50mL dichloroethane, washing with deionized water for 4 times, and collecting extractive solution with anhydrous Na 2 SO 4 Drying, filtration and finally removal of excess solvent by evaporation using a rotary evaporator gives the product tetramethyl benzoguanamine as a brown oil.
(3) Preparation of chloromethylated fluoropolymer: as in example 2.
(4) Preparation of guanidine-functionalized fluoropolymer: as in example 2.
(5) Doping and composite film forming of guanidine group functionalized graphene: adding guanidino-functionalized graphene into the polymer solution obtained in the last step, wherein the addition amount of the guanidino-functionalized graphene is 0.6% of the mass of the guanidino-functionalized fluorine-containing polymer, stirring, performing ultrasonic dispersion, casting into a film by a phase inversion method, and drying for later use.
The prepared film was subjected to 2 mol.L -1 Na 2 CO 3 Performing transfer treatment on the solution to obtain CO 3 2- The anion exchange membrane is finally washed to neutrality with ultrapure water.
The water content of the membrane at 25℃was 13.3% and the ion exchange capacity at 30℃was 3.45 mmol g -1 The swelling degree was 11.2%. The membrane was immersed in a 6M NaOH aqueous solution at 500 a h a little change in ion exchange capacity occurred. The tensile strength was 42.8MPa, and the elongation at break was 12.3%.
Claims (10)
1. The preparation method of the composite anion exchange membrane doped with the guanidino functionalized graphene is characterized by comprising the following steps of:
(1) Preparation of guanidino functionalized graphene: taking a reactor, adding tetramethyl guanidine and graphene oxide, heating, sealing, carrying out guanidino functionalization reaction for a period of time, cooling, washing to be neutral, and drying to obtain a product, namely the guanidino functionalized graphene;
(2) Synthesis of tetramethyl benzoguanidine: putting tetramethyl guanidine into a reactor, adding benzyl halide, stirring at room temperature, reacting for a period of time, filtering the mixture, dissolving the obtained filtrate with diethyl ether, washing with water for a plurality of times, drying, evaporating to remove the solvent, and obtaining the product of tetramethyl benzyl guanidine;
(3) Preparation of chloromethylated fluoropolymer: adding a fluorine-containing acrylate monomer, a monomer containing halogenated benzyl functional groups, a solvent and an initiator into a reactor, carrying out reflux reaction for a period of time at a certain temperature under the protection of inert gas, and obtaining a fluorine-containing acrylate polymer with halogenated benzyl functional groups on side chains after precipitation, washing and drying of the obtained product;
(4) Preparation of guanidine-functionalized fluoropolymer: dissolving the fluorine-containing acrylic ester polymer obtained in the step (3) in an organic solvent to prepare a polymer solution, adding the tetramethyl benzyl guanidine obtained in the step (2), and stirring and reacting for a period of time at a certain temperature to obtain a guanidino functional fluorine-containing polymer solution;
(5) Doping of guanidine group functionalized graphene and film forming of composite film: adding the polymer solution obtained in the step (4) into the guanidyl functionalized graphene obtained in the step (1), stirring, performing ultrasonic dispersion, casting into a composite anion exchange membrane by using a phase inversion method, and drying for later use;
(6) Transformation treatment: and (3) soaking the composite anion exchange membrane obtained in the step (5) in a target anion solution, wherein the tetramethyl benzyl guanidine compound on the side chain of the polymer contains target anions.
2. The method for preparing a composite anion exchange membrane doped with guanidino functionalized graphene according to claim 1, wherein in the step (1), the method for preparing graphene oxide is as follows: placing the reactor in an ice-water bath, adding sulfuric acid/phosphoric acid mixed solution, graphite powder and potassium permanganate, stirring uniformly, stirring at 40-80 ℃ for reaction for 10-28 hours, cooling to room temperature, adding water and hydrogen peroxide until the reactant becomes a bright yellow solid, washing with dilute hydrochloric acid, repeatedly washing with water to be neutral, and drying to obtain graphene oxide.
3. The preparation method of the composite anion exchange membrane doped with the guanidino functionalized graphene, which is disclosed in claim 1, is characterized in that in the step (1), the mass ratio of tetramethylguanidine to graphene oxide is 1:0.1-0.3, the temperature of the guanidino functionalized reaction is 60-90 ℃, and the reaction time is 16-20 hours.
4. The preparation method of the composite anion exchange membrane doped with guanidino functionalized graphene according to claim 1, wherein in the step (2), the benzyl halide is one of benzyl chloride, benzyl bromide and benzyl iodide, the mass ratio of tetramethylguanidine to benzyl halide is 10:1-10, the reaction temperature is 30-80 ℃, and the reaction time is 10-20 h.
5. The method for preparing a composite anion exchange membrane doped with guanidino functionalized graphene according to claim 1, wherein in the step (3), the molar ratio of the fluorine-containing acrylate monomer to the monomer containing halogenated benzyl functional group is: 1:0.1-1.5; the fluorine-containing acrylate monomer is one or a mixture of more of trifluoroethyl acrylate, hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate and dodecafluoroheptyl methacrylate; the temperature of the reflux reaction is 50-90 ℃ and the time is 12-28 h.
6. The method for preparing the composite anion exchange membrane doped with the guanidino functionalized graphene according to claim 1, wherein in the step (4), the temperature of the stirring reaction is 20-50 ℃ and the time is 6-16 hours; the organic solvent for dissolving the polymer is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
7. The preparation method of the composite anion exchange membrane doped with the guanidino functionalized graphene according to claim 1, wherein in the step (4), the addition amount of the tetramethylbenzyl guanidine is calculated according to the content of the monomer containing the halogenated benzyl functional group in the step (3), and the molar ratio of the tetramethylbenzyl guanidine to the monomer containing the halogenated benzyl functional group is 1:1-2.5.
8. The preparation method of the composite anion exchange membrane doped with the guanidyl functionalized graphene, which is disclosed in claim 1, is characterized in that in the step (5), the addition amount of the guanidyl functionalized graphene is 0.1% -1.8% of the mass of the guanidyl functionalized fluorine-containing polymer.
9. The method for preparing the composite anion exchange membrane doped with the guanidino functionalized graphene according to claim 1, wherein the prepared composite anion exchange membrane is subjected to transformation treatment to enable tetramethyl benzyl guanidine compound on a polymer side chain to contain target anions, wherein the target anions are Cl - 、Br - 、HCO 3 - 、I - 、CO 3 2- 、SO 3 H - 、OH - 、SO 4 2- Any one of them.
10. The composite anion exchange membrane doped with guanidino-functionalized graphene obtained by the preparation method according to any one of claims 1 to 9.
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| CN102122720A (en) * | 2011-01-25 | 2011-07-13 | 厦门大学 | Fluorine-containing acrylate polymer anion exchange membrane and preparation method thereof |
| CN104861188A (en) * | 2015-04-28 | 2015-08-26 | 大连理工大学 | Crosslinking type polymer anionic membrane and preparation method thereof |
| WO2017136542A1 (en) * | 2016-02-02 | 2017-08-10 | Ohio University | Ionic liquid-functionalized graphene oxide-based nanocomposite anion exchange membranes |
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