CN111097554A - Strong-alkaline carbon nanotube-graphene composite ion exchange resin material and preparation method thereof - Google Patents
Strong-alkaline carbon nanotube-graphene composite ion exchange resin material and preparation method thereof Download PDFInfo
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- CN111097554A CN111097554A CN201811248614.6A CN201811248614A CN111097554A CN 111097554 A CN111097554 A CN 111097554A CN 201811248614 A CN201811248614 A CN 201811248614A CN 111097554 A CN111097554 A CN 111097554A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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Abstract
The invention relates to a strong-alkaline carbon nanotube-graphene composite ion exchange resin material and a preparation method thereof. The invention comprises the following components in percentage by weight: (a) 75-90 parts of a polymerized monomer; (b) 5-15 parts of a comonomer; (c) 0.1-10 parts of carbon nano tubes; (d) 0.1-10 parts of graphene. The technical scheme well improves the thermal decomposition temperature and the swelling resistance of the composite ion exchange resin, and can be used for industrial production and application of strong-alkaline composite ion exchange resin materials in the future.
Description
Technical Field
The invention relates to a strong-alkaline carbon nanotube-graphene composite ion exchange resin material and a preparation method thereof.
Background
The styrene ion exchange resin is an important solid catalyst and has been widely applied in the industrial catalysis field, such as esterification, alkylation, hydrolysis reaction and the like. With the continuous improvement of application technologies, higher requirements on the performance of the resin, such as high temperature resistance, high pressure resistance, high radiation resistance and the like, are put forward in industrial production and application. In order to solve the problem of poor temperature resistance of styrenic resins, many researchers have proposed the addition of nano-materials into the resins to improve their properties.
Graphene is a polymer made of carbon atoms in sp2The new material with a single-layer sheet structure formed by the hybrid track has excellent physical and chemical properties, such as the elastic modulus of graphene can reach 1TPa, and the strength is 130 GPa. At present, the preparation of high-performance polymer-based nanocomposite by compounding graphene and polymer has become a hotspot of graphene research and application. The carbon nano tube is a one-dimensional tubular structure formed by curling graphene sheets, has ultrahigh mechanical properties, thermal and electrical properties, and occupies an important position in the application research of nano composite materials. As a nano material having excellent properties, a composite material of a carbon nanotube and graphene with an ion exchange resin has also been studied. For example, patent CN 102372830a discloses a method for preparing carbon nanotube composite ion exchange resin by using carbon nanotubes as additive phase; patent CN 104926975a strong-base composite resin material and its preparation method disclose a method for preparing strong-base graphene composite anion exchange resin material by solution intercalation method. The preparation methods usually face the problems that graphene and carbon nanotubes are not uniformly dispersed in a matrix and are easy to agglomerate, so that the improvement of the performance of the composite material is limited, and the application of the composite material is limited.
Both graphene and carbon nanotubes are easily agglomerated inside a polymer matrix due to their own small size effect and surface effect, and the action of strong van der waals force, resulting in uneven dispersion in the matrix; on the other hand, due to the hydrophobic property and chemical inertia of the surfaces of the graphene and the carbon nano tube, the compatibility of the graphene and the carbon nano tube with a polymer matrix is poor, and the interface bonding strength of the composite material is low, so that the nano material cannot well play a role in the material.
Disclosure of Invention
The invention provides a composite resin material with good heat resistance, swelling resistance and nano-filler dispersibility, which can be used in industrial production and application of styrene composite ion exchange resin materials.
The second technical problem to be solved by the present invention is to provide a method for preparing a strong basic carbon nanotube-graphene composite ion exchange resin material corresponding to the first technical problem.
In order to solve one of the above technical problems, the invention adopts the technical scheme that:
the strong-basicity carbon nanotube-graphene composite ion exchange resin material is characterized in that a matrix and graphene are combined in a covalent bond mode, and the matrix and carbon nanotubes are combined in a covalent bond mode.
In the above technical solution, preferably, in the composite ion exchange resin, the matrix and the graphene are bonded in a covalent bond manner, and the matrix and the carbon nanotube are bonded in an ester group manner.
In the above technical solution, preferably, the carbon nanotube/graphene-styrene derivative compound is a mixture of a carbon nanotube-styrene derivative compound and a graphene-styrene derivative compound, and a mass ratio of the carbon nanotube-styrene derivative compound to the graphene-styrene derivative compound in the mixture is 1: 0.1-20, more preferably 1: 1-10.
In the above technical scheme, preferably, the strongly basic carbon nanotube-graphene composite ion exchange resin material comprises the following components in percentage by weight:
(a) 75-90 parts of a polymerized monomer;
(b) 5-15 parts of a comonomer;
(c) 0.1-10 parts of carbon nano tube/graphene-styrene derivative compound; in the carbon nanotube/graphene-styrene derivative compound, a styrene derivative and graphene are combined in an ester group mode, and the styrene derivative and the carbon nanotube are combined in an ester group mode.
In the above technical solution, preferably, the strongly basic carbon nanotube-graphene composite ion exchange resin is a copolymer obtained by in-situ copolymerization of a polymerization monomer, a comonomer, and a carbon nanotube/graphene-styrene derivative compound.
In the above technical scheme, preferably, 1-7 parts of the carbon nanotube/graphene-styrene derivative compound.
In the above technical solution, preferably, the styrene derivative in the carbon nanotube/graphene-styrene derivative compound is combined with graphene in the form of an ester group, and the structural formula is as follows:
wherein R is1Is any 1 or at least 2 combinations of C1-30 alkyl, C2-30 alkenyl and C2-30 halohydrocarbon, and Graphene or its derivatives.
In the above technical solution, preferably, the styrene derivative in the carbon nanotube/graphene-styrene derivative is combined with the carbon nanotube in the form of an ester group, and the structural formula is as follows:
wherein R is2Is any 1 or at least 2 of alkyl with 1-30 carbon atoms, alkenyl with 2-30 carbon atoms and halogenated hydrocarbon with 2-30 carbon atoms.
In the above technical solution, preferably, R is1、R2Is an alkyl group having 1 to 5 carbon atoms. Such as methyl, ethyl, propyl, butyl, pentyl.
In the above technical solution, preferably, the polymerized monomer is a styrene derivative, more preferably, the polymerized monomer is at least one selected from styrene, p-chloromethylstyrene, 4- (3-chloropropyl) styrene, 4- (3-bromopropyl) styrene, 4- (4-chlorobutyl) styrene, 4- (4-bromobutyl) styrene, 4- (5-chloropentyl) styrene and 4- (5-bromopentyl) styrene, and more preferably, at least one selected from p-chloromethylstyrene and 4- (3-chloropropyl) styrene.
In the above technical solution, the comonomer is preferably at least one selected from ethylene glycol dimethacrylate, diacrylene, divinylbenzene or divinylbenzene methane, and more preferably at least one selected from diacrylene or divinylbenzene.
In the above technical solution, preferably, the carbon nanotube is selected from at least one of a single-walled carbon nanotube, a multi-walled carbon nanotube, a double-walled carbon nanotube, and a carboxylated carbon nanotube, and more preferably, is at least one of a multi-walled carbon nanotube and a carboxylated carbon nanotube.
In the above technical solution, preferably, the graphene is at least one selected from single-layer graphene, multi-layer graphene, graphene oxide, and reduced graphene oxide, and more preferably, is at least one selected from graphene oxide and carboxylated graphene. In order to solve the second technical problem, the preparation method adopted by the invention comprises the following specific steps:
(1) preparing mixed carboxylate of carbon oxide nanotubes and graphene oxide;
(2) adding a phase transfer catalyst and a styrene derivative into the mixed carboxylate of the carbon oxide nanotube and the graphene oxide obtained in the step (1), washing, and filtering to obtain a carbon nanotube/graphene-styrene derivative compound;
(3) mixing the carbon nano tube/graphene-styrene derivative compound prepared in the step (2), a polymerization monomer, a comonomer, an initiator and a polymerization auxiliary agent, carrying out polymerization reaction, washing, filtering, drying, sieving, and collecting the composite resin microspheres;
(4) and performing chloromethylation, amination and transformation on the composite resin microspheres to obtain the strong-alkaline carbon nanotube-graphene composite ion exchange resin material.
In the above technical scheme, preferably, the carbon nanotube is added with an acid solution for reflux oxidation, after the oxidation is completed, the reaction solution is filtered, washed with water and dried to obtain the oxidized carbon nanotube; and mixing and dispersing the carbon oxide nanotube and the graphene oxide, adding an alkali solution, and adjusting the pH value to prepare the mixed carboxylate of the carbon oxide nanotube and the graphene oxide.
In the above technical solution, preferably, the method for preparing the carbon nanotube includes an arc discharge method, a laser ablation method, a chemical vapor deposition method, a solid phase pyrolysis method, a glow discharge method, a gas combustion method, and a polymerization synthesis method, and more preferably, the method is a chemical vapor deposition method.
In the above technical solution, preferably, the preparation method of the graphene oxide dispersion liquid includes a Brodie method, a staudenmier method, a Hummers method or an improved Hummers method, and more preferably, the method is an improved Hummers method;
in the above technical solution, preferably, the acid solution includes concentrated sulfuric acid, concentrated nitric acid, or a mixed acid of the concentrated sulfuric acid and the concentrated nitric acid, and more preferably, the mixed acid of the concentrated sulfuric acid and the concentrated nitric acid (a ratio is 3: 1).
In the above technical solution, preferably, the alkali solution includes 1 or a combination of at least 2 of sodium hydroxide, potassium hydroxide or ammonia water.
In the above technical scheme, preferably, the concentration of the alkali solution is 1-5 mmol/L.
In the above technical scheme, preferably, the pH value of the solution is adjusted to 9-10 after the alkali solution is added.
In the technical scheme, preferably, the concentration of the dispersion liquid of the carbon oxide nanotube and graphene oxide mixed carboxylate is 0.1-10 mg/L.
In the above technical scheme, the weight ratio of the carbon oxide nanotube to the graphene oxide mixed carboxylate is preferably 1: 0.1-20, and more preferably 1: 1-10.
In the above technical solution, preferably, the phase transfer catalyst includes any 1 or a combination of at least 2 of quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, crown ether or cryptate, and more preferably, is quaternary ammonium salt.
In the above technical solution, preferably, in the step (2), the washing is specifically implemented by adding an organic solvent to disperse after the reaction is completed, wherein the organic solvent includes at least one selected from chloroform, ethyl acetate, tetrahydrofuran, butyl acetate, dichloromethane, diethyl ether, chlorobenzene, xylene, toluene, and carbon tetrachloride.
In the above technical scheme, the reaction time of the carbon nanotube, the graphene and the styrene derivative is preferably 0.5 to 12 hours, and more preferably 1 to 3 hours.
In the above technical scheme, the reaction temperature of the carbon nanotube, the graphene and the styrene derivative is preferably 50-200 ℃, and more preferably 60-100 ℃.
In the above technical solution, preferably, the styrene derivative includes at least one of p-chloromethyl styrene, 4- (3-chloropropyl) styrene, 4- (3-bromopropyl) styrene, 4- (4-chlorobutyl) styrene, 4- (4-bromobutyl) styrene, 4- (5-chloropentyl) styrene, or 4- (5-bromopentyl) styrene.
In the above technical solution, preferably, the weight ratio of the carbon oxide nanotube to the graphene oxide mixed carboxylate, the phase transfer catalyst and the styrene derivative is 1: 1-20: 1-20, preferably, the weight ratio of 1: 1-10: 1 to 10.
In the above technical solution, preferably, in step (3), the carbon nanotube/graphene-styrene derivative compound prepared in step (2), a polymerization monomer, a comonomer, and an initiator are mixed and processed to obtain a solution a; preparing a water solution B from a polymerization assistant, pre-polymerizing the solution A, mixing the solution A with the solution B, heating for polymerization reaction, and continuing to cure and form; and after the reaction is finished, pouring out the upper-layer liquid, washing, filtering, drying, sieving and collecting the composite resin microspheres.
In the above technical solution, preferably, the initiator is at least one selected from benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide and cumene hydroperoxide, and more preferably, at least one selected from benzoyl peroxide and azobisisobutyronitrile.
In the above technical solution, preferably, the weight ratio of the carbon nanotube/graphene-styrene derivative compound, the initiator, the comonomer, and the polymerization monomer is 1: 0.01-100: 0.5 to 150: 7.5 to 900.
In the above technical solution, preferably, the polymerization assistant is at least one selected from polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite, and calcium carbonate, and more preferably, is one selected from polyvinyl alcohol and gelatin.
In the above technical scheme, preferably, the concentration of the aqueous solution of the polymerization assistant is 0.5-4%.
In the above technical scheme, preferably, the weight of the polymerization assistant is 5-50% of the weight of the polymerized monomer.
In the above technical scheme, preferably, the prepolymerization temperature is 40-75 ℃.
In the above technical scheme, preferably, the prepolymerization time is 0.5-2.5 h.
In the above technical scheme, preferably, the temperature-rise polymerization temperature is 70-90 ℃.
In the above technical scheme, preferably, the temperature-rising polymerization time is 5-15 h.
In the above technical scheme, preferably, the curing temperature is 90-100 ℃.
In the technical scheme, preferably, the curing time is 5-15 h.
In the above technical scheme, preferably, in the step (4), a swelling agent, an aminating agent and an alkali are added to the composite resin microspheres for a functionalization reaction; after the reaction is finished, washing with water, adding a transformation agent for transformation, and washing with water until the reaction is neutral.
In the above technical solution, preferably, the swelling agent is at least one selected from dichloromethane, 1, 2-dichloroethane, chloroform, and tetrahydrofuran, and more preferably, is one selected from dichloromethane and tetrahydrofuran.
In the above technical solution, preferably, the weight of the swelling agent is 110 to 250% of the weight of the composite resin microsphere, and more preferably, the weight of the swelling agent is 150 to 200%.
In the above technical solution, preferably, the amination reagent is selected from at least one of trimethylamine salt, triethylamine salt, diethylamine salt or tributyl salt, more preferably, is one of trimethylamine salt or triethylamine;
in the above technical solution, preferably, the weight of the amination agent is 70 to 200% of the weight of the composite resin microsphere, and more preferably, 100 to 180%.
In the above technical solution, preferably, the alkali is at least one selected from sodium hydroxide and potassium hydroxide.
In the above technical solution, preferably, the weight of the alkali is 60 to 180% of the weight of the composite resin microsphere, and more preferably, 80 to 150%.
In the above technical solution, preferably, the transformation agent is at least one selected from sodium hydroxide, sodium bicarbonate, sodium formate or sodium acetate, and more preferably, is one selected from sodium hydroxide or sodium bicarbonate.
According to the invention, graphene and the carbon nano tube are grafted to a styrene derivative through a nucleophilic reaction, and then the styrene derivative compound grafted with the functionalized carbon nano tube/graphene is mixed in a pure polymerization monomer, so that the carbon nano tube and the graphene can be well dispersed in the polymerization monomer. The covalently bonded carbon nanotube-graphene/polymer composite material can be obtained through polymerization. Introducing quaternary ammonium groups through amination reaction to obtain the strong-basicity carbon nanotube-graphene composite anion exchange resin material. The method utilizes the chemical bond combination of the functionalized carbon nanotube and the graphene with the organic polymeric monomer, not only effectively solves the problem that the carbon nanotube and the graphene are difficult to be uniformly dispersed in the polymer material, but also realizes the covalent compounding of the graphene, the carbon nanotube and the polymer material, and has simple preparation process.
The method for evaluating the mass fraction of the carbon nanotubes/graphene in the carbon nanotube/graphene-styrene derivative compound and the thermal stability of the strong-alkaline composite resin material comprises the following steps: and (3) evaluating the thermal stability of the resin pellets by a thermal weight loss method, and measuring the thermal decomposition curve of the sample at 50-800 ℃ at a heating rate of 10 ℃/min in air and nitrogen atmosphere.
The swelling agent selected in the anti-swelling property test of the strong-alkaline composite resin material is water, and the evaluation method comprises the following steps: taking swelling agent solutionSoaking and flowing through the resin, keeping the solution submerged in the resin for 24 hours, and recording the volume V1Rinsing the resin with pure water and impregnating the resin for 24 hours, drying the resin at 60 ℃ for 24 hours, and recording the volume V2The swelling degree calculation formula is as follows:
according to the carbon nanotube/graphene-styrene derivative, the carbon nanotube, the graphene and the styrene derivative are bonded in a chemical bond mode, and when the mass ratio of the carbon nanotube to the graphene is 1: and 3, the content of p-methylstyrene in the prepared carbon nanotube/graphene-p-methylstyrene is 18.2%, and the content of p-propylstyrene in the carbon nanotube/graphene-p-propylstyrene compound is 19.7%. The strong-base carbon nanotube-graphene composite ion exchange resin material has the advantages that the carbon nanotubes and the graphene are uniformly dispersed in a polymer matrix in a covalent bond mode, the percolation value is low, the thermal stability and the swelling resistance are good, the thermal decomposition starting temperature can reach 375 ℃, the swelling rate can be as low as 18.1%, and good technical effects are achieved.
Detailed Description
[ example 1 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:3, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of chloroform, fully shaking, standing to separate an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 62.6g of p-chloromethyl styrene, 5.6g of divinyl benzene, 0.9g of benzoyl peroxide and 0.9g of carbon nano tube/graphene-p-methyl styrene compound are taken, and are subjected to ultrasonic dispersion for 30 minutes and then are kept stand for 1 hour, so that uniform black dispersion liquid is observed, and no precipitate appears. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. After the reaction is finished, the upper layer liquid is poured out, washed by hot water, filtered, dried at 80 ℃, sieved and collected with the composite microspheres A with the particle size ranging from 350 to 600 microns.
Taking the prepared composite microsphere A, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to convert after water washing, and the resin material A is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material A in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material A into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material A.
[ example 2 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:3, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of carbon tetrachloride, fully shaking, standing to separate an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 60.8 g of p-chloromethyl styrene, 5.7 g of divinyl benzene, 0.9g of benzoyl peroxide and 2.6g of carbon nano tube/graphene-p-methyl styrene compound are taken, and are subjected to ultrasonic dispersion for 30 minutes and then are kept stand for 1 hour, so that uniform black dispersion liquid is observed, and no precipitate appears. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres B with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere B, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material B is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material B in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material B into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material B.
[ example 3 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:3, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of chloroform, fully shaking, standing to separate an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-methylstyrene compound.
1.3g of gelatin is dissolved in 130ml of deionized water and uniformly dispersed by ultrasonic. 59.2 g of p-chloromethyl styrene, 5.6g of divinyl benzene, 0.9g of benzoyl peroxide and 4.3 g of carbon nano tube/graphene-p-methyl styrene compound are taken, and are subjected to ultrasonic dispersion for 30 minutes and then are kept stand for 1 hour, so that uniform black dispersion liquid is observed, and no precipitate appears. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres C with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere C, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material C is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material C in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material C into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material C.
[ example 4 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:3, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of ethyl acetate, fully shaking, standing to separate out an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 57.7 g of p-chloromethyl styrene, 5.5g of divinyl benzene, 0.8 g of benzoyl peroxide and 6.0 g of carbon nanotube/graphene-p-methyl styrene compound are taken, and the mixture is subjected to ultrasonic dispersion for 30 minutes and then is kept stand for 1 hour, so that uniform black dispersion liquid is observed, and no precipitate appears. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres D with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere D, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material D is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material D in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material D into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material D.
[ example 5 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:1, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of chloroform, fully shaking, standing to separate an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 59.5 g of p-chloromethyl styrene, 5.6g of divinyl benzene, 0.9g of benzoyl peroxide and 4.0 g of carbon nano tube/graphene-p-methyl styrene compound are taken, and are subjected to ultrasonic dispersion for 30 minutes and then are kept stand for 1 hour, so that uniform black dispersion liquid is observed, and no precipitate appears. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres E with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere E, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material E is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material E in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material E.
[ example 6 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:5, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of chloroform, fully shaking, standing to separate an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 58.8 g of p-chloromethyl styrene, 5.6g of divinylbenzene, 0.9g of azobisisobutyronitrile and 4.7 g of carbon nanotube/graphene-p-methylstyrene compound were ultrasonically dispersed for 30 minutes and then left to stand for 1 hour, and it was found that no precipitate appeared in the uniform black dispersion. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres F with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere F, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material F is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material F in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material F into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material F.
[ example 7 ]
1g of carbon nano tube is taken and added with 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) for reflux oxidation for 20 min. And after the oxidation is finished, filtering the reaction solution, washing for 5 times, and then drying in vacuum at 60 ℃ to obtain the carbon oxide nanotube. The graphene oxide is prepared by a Hummers method.
Mixing the carbon oxide nanotube and graphene oxide powder according to the mass ratio of 1:3, dispersing the mixture into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare mixed carboxylate solution of the carbon oxide nanotube and the graphene oxide, adding 0.2g of tetraoctylammonium bromide and 1.0g of 4- (3-chloropropyl) styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. And cooling to room temperature after complete reaction, adding 100ml of chloroform, fully shaking, standing to separate an organic phase, filtering to remove insoluble substances, washing with ethanol water, and drying to obtain the carbon nanotube/graphene-p-propylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 59.1 g of p-chloromethyl styrene, 5.6g of divinyl benzene, 0.9g of benzoyl peroxide and 4.4 g of carbon nano tube/graphene-p-propyl styrene compound are taken, and are subjected to ultrasonic dispersion for 30 minutes and then are kept stand for 1 hour, so that uniform black dispersion liquid is observed, and no precipitate appears. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours to perform prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5 hours, and finally the temperature is increased to 98 ℃ for reaction for 6 hours. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres G with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere G, adding 60ml of dichloroethane, swelling at 30 ℃ for 2 hours, adding 27.0G of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material G is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material G in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material G into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 minutes; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 minutes; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at the flow rate of 1.7ml/min for 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material G.
[ examples 1 to 7 ] the thermal stability and swelling resistance of the strongly basic carbon nanotube-graphene ion exchange resin composites A to G were as shown in Table 1.
Comparative example 1
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 60.1g of p-chloromethyl styrene, 5.5g of divinylbenzene, 0.9g of benzoyl peroxide initiator, 0.9g of carbon nano tube and 2.6g of graphene are taken, and are subjected to ultrasonic dispersion for 30min and then are kept stand for 1h, so that uniform black dispersion liquid is free from precipitation. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours for prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5h, and finally the temperature is increased to 98 ℃ for reaction for 6 h. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres H with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere H, adding 60ml of dichloroethane, swelling at 30 ℃ for 2H, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6H. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material H is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50mL of the resin material H in 200mL of methanol, washing with 700mL of deionized water, then filling glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5mL/min, and the treatment time is 30 min; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 min; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at a flow rate of 1.7ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube-graphene ion exchange resin composite material H.
The thermal stability and anti-swelling property of the strongly basic carbon nanotube-graphene composite ion exchange resin material H are shown in Table 1
Comparative example 2
59.9g of p-chloromethyl styrene, 5.5g of divinylbenzene and 1.1g of benzoyl peroxide initiator are taken, and the mixture is subjected to ultrasonic dispersion for 30min and then is kept stand for 1h, so that uniform black dispersion liquid is free from precipitation. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours for prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5h, and finally the temperature is increased to 98 ℃ for reaction for 6 h. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres I with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere I, adding 60ml of dichloroethane, swelling at 30 ℃ for 2h, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 h. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to convert after water washing, and the resin material I is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50mL of the resin material I in 200mL of methanol, washing with 700mL of deionized water, then filling glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5mL/min, and the treatment time is 30 min; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 min; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at a flow rate of 1.7ml/min for a treatment time of 200 min; then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strongly basic ion exchange resin I.
The thermal stability and resistance to swelling of the strongly basic ion exchange resin material I are shown in Table 1
Comparative example 3
Graphene oxide is prepared by a Hummers method, the graphene oxide is ultrasonically dispersed into 200ml of 1mg/ml water dispersion, 1mmol/L sodium hydroxide solution is added to adjust the pH value to 10, 0.4g of tetrabutylammonium bromide and 2.0g of p-chloromethyl styrene are added, and the mixture is stirred in an oil bath at the temperature of 98 ℃ for reaction for 3 hours. After the reaction is completed, the mixture is cooled to room temperature, 200ml of trichloromethane is added, the mixture is fully shaken and then is kept stand to separate out an organic phase, and insoluble substances are removed by filtration. And concentrating the mixed solution to 10ml, washing with ethanol water, and drying to obtain the graphene-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 62.5g of p-chloromethyl styrene, 5.8g of divinyl benzene, 0.9g of benzoyl peroxide and 0.81g of graphene-p-methyl styrene compound are taken, ultrasonic dispersion is carried out for 30min, and then standing is carried out for 1h, so that uniform black dispersion liquid has no precipitation. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours for prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5h, and finally the temperature is increased to 98 ℃ for reaction for 6 h. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres J with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere J, adding 60ml of dichloroethane, swelling at 30 ℃ for 2h, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 h. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material J is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material J in 200ml of methanol, washing with 700ml of deionized water, then filling the resin material J into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 min; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 min; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at a flow rate of 1.7ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strongly basic graphene ion exchange resin composite material J.
Comparative example 4
And (2) adding 200ml of acid solution (the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3:1) into 1g of carbon nano tube, refluxing and oxidizing for 20min, filtering reaction liquid after oxidation is finished, washing for 5 times by water, and drying in vacuum at 60 ℃ to obtain the oxidized carbon nano tube. Dispersing the carbon oxide nano tube into 100ml of dispersion liquid with the concentration of 1mg/ml by ultrasonic or stirring, adding alkali solution with the concentration of 1mmol/L, adjusting the pH value to 9 to prepare carboxylate of the carbon oxide nano tube, adding 0.2g of tetraoctyl ammonium bromide and 1.0g of p-chloromethyl styrene, and carrying out oil bath stirring reaction at 98 ℃ for 3 hours. After the reaction is completed, the mixture is cooled to room temperature, 100ml of trichloromethane is added, the mixture is fully shaken and then is kept stand to separate out an organic phase, and insoluble substances are removed by filtration. And concentrating the mixed solution to 10ml, washing with ethanol water, washing with distilled water, and vacuum drying to obtain the carbon nanotube-p-methylstyrene compound.
1.3g of polyvinyl alcohol is dissolved in 130ml of deionized water solution and uniformly dispersed by ultrasonic. 62.6g of p-chloromethyl styrene, 5.6g of divinyl benzene, 0.9g of benzoyl peroxide initiator and 0.9g of carbon nanotube-p-methyl styrene compound are taken, and the mixture is subjected to ultrasonic dispersion for 30min and then is kept stand for 1h, so that uniform black dispersion liquid is not precipitated. The prepared dispersion was poured into a three-necked flask and stirred at 60 ℃ for 2 hours for prepolymerization. Slowly adding the prepared polyvinyl alcohol aqueous solution, gradually heating to 80 ℃, and reacting for 5 hours; then the temperature is increased to 90 ℃ for reaction for 5h, and finally the temperature is increased to 98 ℃ for reaction for 6 h. And (3) after the reaction is finished, pouring out the upper-layer liquid, washing with hot water, filtering, drying at 80 ℃, sieving, and collecting the composite microspheres K with the particle size within the range of 350-600 microns.
Taking the prepared composite microsphere K, adding 60ml of dichloroethane, swelling at 30 ℃ for 2h, adding 27.0g of trimethylamine hydrochloride and 200ml of 6mol/L sodium hydroxide solution, and reacting at 30 ℃ for 6 h. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, sodium hydroxide is added to carry out transformation after water washing, and the resin material K is obtained after water washing to be neutral.
The post-treatment process is as follows: soaking 50ml of the resin material K in 200ml of methanol, washing with 700ml of deionized water, then filling into glass beads with sand cores, washing the resin with the deionized water, wherein the flow rate of the deionized water is 5ml/min, and the treatment time is 30 min; washing the resin with 0.75mol/L HCl solution at a flow rate of 2ml/min for 90 min; washing the resin with deionized water until the eluate is neutral; washing the resin with 0.3mol/L sodium hydroxide solution at a flow rate of 1.7ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing at room temperature of 25 ℃ to obtain the strong-basicity carbon nanotube composite ion exchange resin material K.
TABLE 1
Claims (10)
1. The strong-basicity carbon nanotube-graphene composite ion exchange resin material is characterized in that a matrix is combined with carbon nanotubes and graphene in a covalent bond mode.
2. The strongly basic carbon nanotube-graphene composite ion exchange resin material according to claim 1, wherein the composite ion exchange resin comprises the following components in percentage by weight:
(a) 75-90 parts of a polymerized monomer;
(b) 5-15 parts of a comonomer;
(c) 0.1-10 parts of carbon nano tube/graphene-styrene derivative compound; in the carbon nanotube/graphene-styrene derivative compound, a styrene derivative and graphene are combined in an ester group mode, and the styrene derivative and the carbon nanotube are combined in an ester group mode.
3. The strongly basic carbon nanotube-graphene composite ion exchange resin material according to claim 1, wherein the polymerized monomer comprises at least one selected from styrene, p-chloromethyl styrene, 4- (3-chloropropyl) styrene, 4- (3-bromopropyl) styrene, 4- (4-chlorobutyl) styrene, 4- (4-bromobutyl) styrene, 4- (5-chloropentyl) styrene, or 4- (5-bromopentyl) styrene.
4. The strongly basic carbon nanotube-graphene composite ion exchange resin material according to claim 1, wherein the comonomer comprises at least one selected from ethylene glycol dimethacrylate, diacrylene, divinylbenzene or divinylphenylmethane.
5. The strongly basic carbon nanotube-graphene composite ion exchange resin material according to claim 1, wherein the carbon nanotubes comprise at least one selected from single-walled carbon nanotubes, multi-walled carbon nanotubes, double-walled carbon nanotubes, and carboxylated carbon nanotubes; the graphene includes at least one selected from single-layer graphene, multi-layer graphene, graphene oxide, or reduced graphene oxide.
6. A preparation method of a strong-alkaline carbon nanotube-graphene composite ion exchange resin material comprises the following steps:
(1) preparing mixed carboxylate of carbon oxide nanotubes and graphene oxide;
(2) adding a phase transfer catalyst and a styrene derivative into the mixed carboxylate of the carbon nanotube oxide and the graphene oxide obtained in the step (1), washing and filtering to obtain a carbon nanotube/graphene-styrene derivative (3), mixing the carbon nanotube/graphene-styrene derivative obtained in the step (2), a polymerization monomer, a comonomer, an initiator and a polymerization aid, carrying out polymerization reaction, washing, filtering, drying and sieving, and collecting the composite resin microspheres;
(4) and performing chloromethylation, amination and transformation on the composite resin microspheres to obtain the strong-alkaline carbon nanotube-graphene composite ion exchange resin material.
7. The method for preparing the strongly basic carbon nanotube-graphene composite ion exchange resin material according to claim 6, wherein the carbon nanotube is subjected to acid oxidation to obtain an oxidized carbon nanotube, an alkali solution is added, the pH value of the solution is adjusted, and then the solution is filtered, separated and dried to obtain a carboxylate of the carbon nanotube, and the preparation method of the carbon nanotube comprises at least one of an arc discharge method, a laser ablation method, a chemical vapor deposition method, a solid phase pyrolysis method, a glow discharge method, a gas combustion method or a polymerization synthesis method; dispersing graphene, and then adding an alkaline solution to prepare a carboxylate of the graphene, wherein the graphene is graphene oxide, and the preparation method of the graphene oxide comprises at least one of a Brodie method, a Staudenmaier method, a Hummers method or an improved Hummers method; the alkali solution comprises at least one of sodium hydroxide, potassium hydroxide, or ammonia.
8. The method according to claim 6, wherein the phase transfer catalyst comprises at least one of quaternary ammonium salt, quaternary phosphonium salt, tertiary amine, crown ether or cryptate ether.
9. The method of claim 6, wherein the styrene derivative is at least one selected from p-chloromethylstyrene, 4- (3-chloropropyl) styrene, 4- (3-bromopropyl) styrene, 4- (4-chlorobutyl) styrene, 4- (4-bromobutyl) styrene, 4- (5-chloropentyl) styrene, and 4- (5-bromopentyl) styrene.
10. The method for preparing the strongly basic carbon nanotube-graphene composite ion exchange resin material according to claim 6, wherein the polymerization auxiliary agent is at least one selected from polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite and calcium carbonate; the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide and cumene hydroperoxide; the polymerized monomer comprises at least one selected from styrene, p-chloromethyl styrene, 4- (3-chloropropyl) styrene, 4- (3-bromopropyl) styrene, 4- (4-chlorobutyl) styrene, 4- (4-bromobutyl) styrene, 4- (5-chloropentyl) styrene or 4- (5-bromopentyl) styrene; the comonomer includes at least one selected from the group consisting of ethylene glycol dimethacrylate, diacrylene, divinylbenzene or divinylphenylmethane.
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