CN106994304B - Homogeneous cation exchange membrane and preparation method thereof - Google Patents
Homogeneous cation exchange membrane and preparation method thereof Download PDFInfo
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Abstract
A homogeneous cation exchange membrane and a preparation method thereof, relating to a functional polymer membrane material. A high-molecular film sensitive to high-energy rays is taken as a base film, after the high-molecular film is cleaned and irradiated by high-energy rays, monomer styrene or alkyl styrene monomers are grafted on two side surfaces of the base film and functionalized, cation exchange groups are introduced into two side surfaces of the film, and then the homogeneous cation exchange film is obtained by a method of re-granulation or co-fusion with the non-irradiated high-molecular film. The prepared homogeneous cation exchange membrane has the characteristics of high exchange capacity, good electrochemical performance, high flexibility and strength and the like, has wide application prospects in national economic departments such as the food industry, the electronic industry, the semiconductor industry, the medical industry, the printing and dyeing industry, the chemical industry and the like, has excellent alcohol resistance, and solves the problem of methanol leakage in the use process of an anode membrane in a direct methanol fuel cell.
Description
Technical Field
The invention relates to a functional polymer membrane material, in particular to a homogeneous cation exchange membrane and a preparation method thereof.
Background
Ion exchange membranes, which are polymer materials that selectively pass ions, have attracted much attention in recent years due to the advantages of environmental protection, no pollution, high efficiency, energy conservation, easy module formation and the like in the preparation and application processes. Ion exchange membrane technology has been widely used in the fields of electrodialysis, diffusion dialysis, chlor-alkali industry, and fuel cells over the past decades. However, the development of the ion exchange membrane is greatly limited due to the problems of high price, poor tolerance, serious membrane pollution and the like. Therefore, the development of a membrane having good chemical stability, low price, low swelling degree and high ion exchange capacity is of great significance to the commercial development and application of cation exchange membranes. Cation exchange membranes have received much attention as compared to anion exchange membranes. Since cation exchange membranes represent a very significant advantage both in membrane separation processes and in energy conversion processes, they have an irreplaceable position.
At present, the most widely used cation exchange membrane is a perfluorosulfonic acid membrane (Nafion) produced by dupont, but the application and development of Nafion membrane are limited by the defects of high price, high fuel permeability, poor oxidation resistance and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a homogeneous cation exchange membrane and a preparation method thereof.
The homogeneous cation exchange membrane is grafted by irradiation and is cast again to form a membrane in the process, so that the influence of damage to the mechanical property of the base membrane after irradiation is overcome, and the chemical structural formula of the homogeneous cation exchange membrane is as follows:
wherein M is a polymer chain of a basement membrane, n is polymerization degree, is an integer and is not zero; r1 and R2 are hydrogen atoms or alkyl groups with less than 4 carbon atoms; r3 is a hydrocarbon group having less than 3 carbon atoms; x+The cation may be one of H +, Li +, Na +, K +, etc.
One of the preparation methods of the homogeneous cation exchange membrane adopts grafting, functionalization, re-granulation and film formation, and comprises the following steps:
1) base film pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays;
2) double-sided simultaneous grafting: putting a base film into a reactor, soaking the base film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer on the base film;
3) sulfonation: soaking the grafted membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a cation exchange membrane;
4) and (3) re-film forming: and re-granulating and forming a film on the sulfonated cation exchange membrane under the conditions of heating and pressurizing, thereby preparing the homogeneous cation exchange membrane.
In step 1), the base film may be selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons, and the like; the high-energy rays can be high-energy electron beams, gamma rays and the like; the total dose of irradiation can be 20-200 kGy.
In the step 2), the monomer in the grafting monomer solution can be selected from a class of organic compounds containing unsaturated alkyl on a benzene ring, the class of organic compounds containing unsaturated alkyl on the benzene ring can be selected from one of styrene, α -methylstyrene, p-methylstyrene and the like, the solvent can be selected from one of toluene, isopropanol, ethanol and the like, the temperature of the constant-temperature water bath kettle can be 40-80 ℃, and the reaction time can be 0.5-24 h.
In the step 3), the sulfonation reaction time is 0.25-6 h.
In the step 4), the heating temperature is 70-200 ℃, and the pressurizing pressure can be 10-20 Mp.
The second preparation method of the homogeneous cation exchange membrane adopts the grafting and then carries out the co-fusion with the basement membrane which is not irradiated by high temperature, and comprises the following steps:
1) base film pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays;
2) double-sided simultaneous grafting: putting a base film into a reactor, soaking the base film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer on the base film;
3) sulfonation: soaking the grafted membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a cation exchange membrane;
4) co-melting with a basement membrane which is not radiated by high temperature under the heating condition, and then curing on a press to prepare the homogeneous cation exchange membrane.
In step 1), the base film may be selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons, and the like; the high-energy rays can be high-energy electron beams, gamma rays and the like; the total dose of irradiation can be 20-200 kGy.
In the step 2), the monomer in the grafting monomer solution can be selected from a class of organic compounds containing unsaturated alkyl on a benzene ring, the class of organic compounds containing unsaturated alkyl on the benzene ring can be selected from one of styrene, α -methylstyrene, p-methylstyrene and the like, the solvent can be selected from one of toluene, isopropanol, ethanol and the like, the temperature of the constant-temperature water bath kettle can be 40-80 ℃, and the reaction time can be 0.5-24 h.
In the step 3), the sulfonation reaction time may be 0.25 to 6 hours.
The third preparation method of the homogeneous cation exchange membrane adopts the steps of film re-forming after grafting and functionalization, and comprises the following steps:
1) base film pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays;
2) double-sided simultaneous grafting: putting a base film into a reactor, soaking the base film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer on the base film;
3) and (3) re-film forming: and re-granulating and forming a film on the sulfonated cation exchange membrane under the conditions of heating and pressurizing, thereby preparing the cation exchange membrane.
4) Sulfonation: soaking the grafted membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a homogeneous cation exchange membrane;
in step 1), the base film may be selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons, and the like; the high-energy rays can be high-energy electron beams, gamma rays and the like; the total dose of irradiation can be 20-200 kGy.
In the step 2), the monomer in the grafting monomer solution can be selected from a class of organic compounds containing unsaturated alkyl on a benzene ring, the class of organic compounds containing unsaturated alkyl on the benzene ring can be selected from one of styrene, α -methylstyrene, p-methylstyrene and the like, the solvent can be selected from one of toluene, isopropanol, ethanol and the like, the temperature of the constant-temperature water bath kettle can be 40-80 ℃, and the reaction time can be 0.5-24 h.
In the step 3), the heating temperature can be 70-200 ℃, and the pressurizing pressure can be 10-20 Mp.
In the step 4), the sulfonation reaction time may be 0.25 to 6 hours.
The preparation method of the homogeneous cation exchange membrane adopts the steps of co-melting the grafted homogeneous cation exchange membrane with a basement membrane which is not subjected to high-temperature radiation under the heating condition, curing the grafted homogeneous cation exchange membrane on a press to form a membrane, and functionalizing the membrane, and comprises the following steps of:
1) base film pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays;
2) double-sided simultaneous grafting: putting a base film into a reactor, soaking the base film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer on the base film;
3) and (3) re-film forming: and re-granulating and forming a film on the sulfonated cation exchange membrane under the conditions of heating and pressurizing, thereby preparing the cation exchange membrane.
4) Sulfonation: soaking the grafted membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a homogeneous cation exchange membrane;
in step 1), the base film may be selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons, and the like; the high-energy rays can be high-energy electron beams, gamma rays and the like; the total dose of irradiation can be 20-200 kGy.
In the step 2), the monomer in the grafting monomer solution can be selected from a class of organic compounds containing unsaturated alkyl on a benzene ring, the class of organic compounds containing unsaturated alkyl on the benzene ring can be selected from one of styrene, α -methylstyrene, p-methylstyrene and the like, the solvent can be selected from one of toluene, isopropanol, ethanol and the like, the temperature of the constant-temperature water bath kettle can be 40-80 ℃, and the reaction time can be 0.5-24 h.
In the step 3), the heating temperature is 70-200 ℃, and the pressurizing pressure can be 10-20 Mp.
In the step 4), the sulfonation reaction time may be 0.25 to 6 hours.
The homogeneous cation exchange membrane prepared by the invention is used for replacing a perfluorosulfonic acid membrane and is applied to two green and environment-friendly ion exchange membrane processes: diffusion dialysis and direct methanol fuel cells.
The invention has the advantages and benefits that:
1. functional group monomers are grafted to the surface of the base membrane through a radiation grafting technology without adding an initiator, a catalyst and the like, and the prepared cation exchange membrane is very uniform and pure;
2. compared with a method of impregnating a monomer solution through a porous membrane for multiple times and then polymerizing, the cation exchange membrane prepared by the method has simpler steps and better thermal stability and chemical stability;
3. the grafting rate of the membrane can be flexibly controlled by controlling the irradiation dose, the concentration of the grafting monomer, the reaction time, the reaction temperature and the like, and the conductivity, the water content, the ion exchange capacity and the like of the membrane can be controlled by controlling the grafting rate of the membrane.
4. Because the mechanical property of the film is damaged after irradiation, the mechanical property of the film is recovered through the reproduction of the film, and the mechanical strength required by use can be achieved, even surpassed that of the original film;
5. the prepared cation exchange membrane has the conductivity of 0.01-0.04S-cm measured in high-purity water at the temperature of 30 DEG C-1Cation exchange capacity (H)+) 0.5 to 1.5 mmol/g-1The water content of the film is 5-30%; has excellent mechanical performance and good thermal stability and chemical stability.
6. The reagent adopted in the reaction process is low in toxicity, and the use of a strong carcinogenic reagent is avoided, so that the harm to human bodies and the environment is greatly reduced.
Detailed Description
Example 1
(1) Cleaning a basement membrane (polyethylene film), then placing the basement membrane into a vacuum drying oven to be dried to constant weight, then placing the basement membrane into an irradiation bottle, and placing the basement membrane into a cobalt source irradiation chamber to be irradiated until the total dose is 30 kGy.
(2) And placing the irradiated membrane in a reactor, soaking the membrane in 30% styrene toluene solution, introducing nitrogen to remove air in the reactor, sealing, and placing the reactor in a constant-temperature water bath kettle at 60 ℃ for reaction for 2 hours to graft styrene monomers on the membrane. After the reaction is finished, residual monomer solution and homopolymer in the film are removed, and the film is dried for later use.
(3) The grafted membrane is placed into the reactor again to react with a sulfonation reagent (2% chlorosulfonic acid in dichloromethane) at room temperature for 1 h. Then, the membrane is put into 0.1mol/L sodium hydroxide aqueous solution and hydrolyzed for 12 hours at room temperature;
(4) and (3) granulating the sulfonated membrane again, drawing out the membrane again through an open mill, respectively attaching nylon mesh cloth to the upper surface and the lower surface of the membrane after cutting, putting the membrane between two stainless steel plates of a tablet press, and finally sending the membrane into the press. Hot-press forming and cooling the mixture at 90 ℃ and 12Mp in the first section and at 110 ℃ and 18Mp in the second section, and taking out the mixture.
Preferably, the film after step (4) may be subjected to a transformation treatment: and (3) soaking the membrane in a 1mol/L sodium hydroxide aqueous solution for 24h, and replacing the solution for 3 times during the soaking process to obtain the sodium cation exchange membrane.
Through determination, the cation exchange membrane prepared in the example 1 has the conductivity of 0.03S/cm at the temperature of 30 ℃ and the water content of 28 percent; the cation exchange capacity was 1.16 mmol/g.
Example 2
(1) Cleaning a basement membrane (polyethylene film), then placing the basement membrane into a vacuum drying oven to be dried to constant weight, then placing the basement membrane into an irradiation bottle, and placing the basement membrane into a cobalt source irradiation chamber to be irradiated until the total dose is 50 kGy.
(2) And placing the irradiated membrane in a reactor, soaking the membrane in 30% styrene toluene solution, introducing nitrogen to remove air in the reactor, sealing, and placing the reactor in a 80 ℃ constant-temperature water bath kettle for reaction for 1h to graft styrene monomer on the membrane. After the reaction is finished, residual monomer solution and homopolymer in the film are removed, and the film is dried for later use.
(3) The grafted membrane is placed into the reactor again to react with a sulfonation reagent (2% chlorosulfonic acid in dichloromethane) at room temperature for 4 h. Then, the membrane is put into 0.1mol/L sodium hydroxide aqueous solution and hydrolyzed for 10 hours at room temperature;
(4) the sulfonated membrane is used for clamping the non-irradiated polyvinylidene fluoride film in the middle, nylon mesh cloth is respectively attached to the upper surface and the lower surface of the membrane, the membrane is placed between two stainless steel plates of a tablet press, and finally the membrane is sent into a press to be co-melted at 120 ℃ and then subjected to hot-press forming and cooling at the first section of 110 ℃, 11Mp and the second section of 130 ℃ and 20 Mp.
Preferably, the film after step (4) may be subjected to a transformation treatment: and (3) soaking the membrane in 1mol/L potassium hydroxide aqueous solution for 24h, and replacing the solution for 3 times during the soaking process to obtain the potassium cation exchange membrane.
Through determination, the cation exchange membrane prepared in the example 2 has the conductivity of 0.02S/cm at the temperature of 30 ℃ and the water content of 25 percent; the cation exchange capacity was 1.22 mmol/g.
Example 3
(1) Cleaning a basement membrane (polyvinylidene fluoride film), then placing the basement membrane into a vacuum drying oven to be dried to constant weight, then placing the basement membrane into an irradiation bottle, and placing the basement membrane into a cobalt source irradiation chamber to be irradiated until the total dose is 70 kGy.
(2) And placing the irradiated membrane in a reactor, soaking the membrane in 30% styrene toluene solution, introducing nitrogen to remove air in the reactor, sealing, and placing the reactor in a constant-temperature water bath kettle at 70 ℃ for reaction for 1.5h to graft styrene monomers on the membrane. After the reaction is finished, residual monomer solution and homopolymer in the film are removed, and the film is dried for later use.
(3) Clamping the non-irradiated polyvinylidene fluoride film by the grafted film, respectively attaching nylon mesh cloth on the upper surface and the lower surface of the film, putting the film between two stainless steel plates of a tablet press, finally sending the film into a press, performing procedures of co-melting at 160 ℃, performing procedures of hot-press forming at 110 ℃, 12Mp in the first section and at 130 ℃ and 18Mp in the second section, and cooling the film and taking the film out.
(4) And putting the film subjected to hot press forming into the reactor again, and reacting with a sulfonation reagent (2% chlorosulfonic acid in dichloromethane), wherein the reaction temperature is room temperature, and the reaction time is 4 hours. Then, the membrane is put into 0.1mol/L sodium hydroxide aqueous solution and hydrolyzed for 10 hours at room temperature;
(5) and putting the sulfonated membrane into a hot press again for hot pressing, carrying out hot press molding at 110 ℃ in the first section and at 12Mp at 130 ℃ in the second section by 18Mp programs, cooling and taking out.
Preferably, the film after step (5) may be subjected to a transformation treatment: and (3) soaking the membrane in 1mol/L potassium hydroxide aqueous solution for 24h, and replacing the solution for 3 times during the soaking process to obtain the potassium cation exchange membrane.
Through determination, the cation exchange membrane prepared in the example 3 has the conductivity of 0.03S/cm at the temperature of 30 ℃ and the water content of 23 percent; the cation exchange capacity was 1.27 mmol/g.
Example 4
(1) Cleaning a basement membrane (polyethylene film), then placing the basement membrane into a vacuum drying oven to be dried to constant weight, then placing the basement membrane into an irradiation bottle, and placing the basement membrane into a cobalt source irradiation chamber to be irradiated until the total dose is 20 kGy.
(2) And placing the irradiated membrane in a reactor, soaking the membrane in 30% styrene toluene solution, introducing nitrogen to remove air in the reactor, sealing, and placing the reactor in a constant-temperature water bath kettle at 60 ℃ for reaction for 2 hours to graft styrene monomers on the membrane. After the reaction is finished, residual monomer solution and homopolymer in the film are removed, and the film is dried for later use.
(3) Re-granulating the grafted membrane, re-pulling out the membrane by an open mill, respectively attaching nylon mesh cloth to the upper surface and the lower surface of the membrane after cutting, putting the membrane between two stainless steel plates of a tablet press, finally sending the membrane into a press, and taking out the membrane after hot press forming and cooling through the procedures of the first section at 100 ℃ and 10Mp and the second section at 120 ℃ and 15 Mp;
(4) the recast membrane was placed in a reactor and reacted with a sulfonating agent (4% chlorosulfonic acid in methylene chloride) at room temperature for 1 h. Then, the membrane is put into 1mol/L sodium hydroxide aqueous solution and hydrolyzed for 20 hours at room temperature;
(5) and putting the sulfonated membrane into a hot press again for hot pressing, carrying out hot press molding at 90 ℃ at a first section and at 10Mp at a second section at 125 ℃ at 15Mp, cooling and taking out.
Through determination, the cation exchange membrane prepared in the example 1 has the conductivity of 0.02S/cm at the temperature of 30 ℃ and the water content of 22 percent; the cation exchange capacity was 1.11 mmol/g.
Example 5
(1) Cleaning a base film (polypropylene film), drying the base film in a vacuum drying oven to constant weight, then placing the base film in an irradiation bottle, and placing the base film in a cobalt source irradiation chamber for irradiation until the total dose is 100 kGy.
(2) And placing the irradiated membrane in a reactor, soaking the membrane in 30% styrene toluene solution, introducing nitrogen to remove air in the reactor, sealing, and placing the reactor in a 50 ℃ constant-temperature water bath kettle for reaction for 3 hours to graft styrene monomers on the membrane. After the reaction is finished, residual monomer solution and homopolymer in the film are removed, and the film is dried for later use.
(3) Clamping the non-irradiated polyvinylidene fluoride film by the grafted film, respectively attaching nylon mesh cloth on the upper surface and the lower surface of the film sheet, putting the film sheet between two stainless steel plates of a tablet press, finally feeding the film sheet into a press, and carrying out hot press molding and cooling through the procedures of 135 ℃ at a first section, 14Mp and 160 ℃ at a second section by 20 Mp;
(4) and putting the film subjected to hot press forming into the reactor again, and reacting with a sulfonation reagent (2% chlorosulfonic acid in dichloromethane), wherein the reaction temperature is room temperature, and the reaction time is 4 hours. Then, the membrane is put into 0.1mol/L sodium hydroxide aqueous solution and hydrolyzed for 10 hours at room temperature;
(5) and putting the sulfonated membrane into a hot press again for hot pressing, carrying out hot press molding at 110 ℃ in the first section and at 14Mp in the second section at 130 ℃ and at 20Mp, cooling and taking out.
Preferably, the film after step (5) may be subjected to a transformation treatment: and (3) soaking the membrane in 1mol/L potassium hydroxide aqueous solution for 24h, and replacing the solution for 3 times during the soaking process to obtain the potassium cation exchange membrane.
Through determination, the cation exchange membrane prepared in the example 3 has the conductivity of 0.03S/cm at the temperature of 30 ℃ and the water content of 23 percent; the cation exchange capacity was 1.27 mmol/g.
Claims (5)
1. A homogeneous cation exchange membrane is characterized in that a polymer base membrane forms a base membrane containing free radicals after irradiation, the irradiation product is grafted and sulfonated, and after the grafting or sulfonation step, the base membrane is re-filmed in a mode of re-granulation or co-fusion with the base membrane which is not irradiated; the chemical structural formula of the homogeneous cation exchange membrane is as follows:
wherein M is a polymer chain of a basement membrane, n is polymerization degree, is an integer and is not zero; r1And R2Is a hydrogen atom or an alkyl group having less than 4 carbon atoms; r3Is a hydrogen atom or a hydrocarbon group having less than 3 carbon atoms; x+Is a cation, is H+、Li+、Na+、K+One kind of (1).
2. One of the preparation methods of the homogeneous cation exchange membrane of claim 1, wherein the method of grafting, sulfonating, re-granulating and film forming is adopted, which comprises the following steps:
1) pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays; the base film is selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons; the high-energy rays are high-energy electron beams and gamma rays; the total irradiation dose is 20-200 kGy;
2) the method comprises the steps of simultaneously grafting two surfaces of a substrate film, namely putting the substrate film into a reactor, soaking the substrate film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer, wherein the monomer in the grafting monomer solution is selected from organic compounds containing unsaturated alkyl on a benzene ring, and the organic compounds containing unsaturated alkyl on the benzene ring are selected from one of styrene, α -methyl styrene and p-methyl styrene;
3) sulfonation: soaking the grafted base membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a cation exchange membrane; the sulfonation reaction time is 0.25-6 h;
4) and (3) re-film forming: granulating and forming a film on the sulfonated basement membrane under the conditions of heating and pressurizing, thereby preparing a homogeneous cation exchange membrane; the heating temperature is 70-200 ℃, and the pressurizing pressure is 10-20 MP a.
3. A second method for preparing a homogeneous cation exchange membrane according to claim 1, wherein the method of grafting, sulfonating, co-melting with a base membrane which is not subjected to high temperature radiation, and forming a film again comprises the following steps:
1) pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays; the base film is selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons; the high-energy rays are high-energy electron beams and gamma rays; the total irradiation dose is 20-200 kGy;
2) the method comprises the steps of simultaneously grafting two surfaces of a substrate film, namely putting the substrate film into a reactor, soaking the substrate film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer on the substrate film, wherein the monomer in the grafting monomer solution can be selected from a class of organic compounds containing unsaturated alkyl on a benzene ring, and the class of organic compounds containing unsaturated alkyl on the benzene ring is selected from one of styrene, α -methyl styrene and p-methyl styrene;
3) sulfonation: soaking the grafted base membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a sulfonated grafted membrane; the sulfonation reaction time is 0.25-6 h;
4) and (3) re-film forming: co-melting with a basement membrane which is not radiated by high temperature under the heating condition, and then curing on a press to prepare the homogeneous cation exchange membrane.
4. The third method for preparing a homogeneous cation exchange membrane according to claim 1, wherein the sulfonation is performed after re-granulation and film formation after grafting, comprising the steps of:
1) pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays; the base film is selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons; the high-energy rays are high-energy electron beams and gamma rays; the total irradiation dose is 20-200 kGy;
2) the method comprises the steps of simultaneously grafting two surfaces of a substrate film, namely putting the substrate film into a reactor, soaking the substrate film into a grafting monomer solution, and finally putting the reactor into a constant-temperature water bath kettle for reaction to graft a monomer, wherein the monomer in the grafting monomer solution is selected from organic compounds containing unsaturated alkyl on a benzene ring, and the organic compounds containing unsaturated alkyl on the benzene ring are selected from one of styrene, α -methyl styrene and p-methyl styrene;
3) and (3) re-film forming: granulating and forming a film on the grafted base film under the conditions of heating and pressurizing, thereby preparing a uniform grafted film; the heating temperature is 70-200 ℃, and the pressurizing pressure is 10-20 MPa;
4) sulfonation: soaking the grafted membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a homogeneous cation exchange membrane; the sulfonation reaction time is 0.25-6 h.
5. The preparation method of the homogeneous cation exchange membrane of claim 1, which is characterized in that the method of co-melting with a basement membrane which is not irradiated by high temperature under heating condition after grafting, re-forming membrane and then sulfonating is adopted, and the method comprises the following steps:
1) pre-irradiation: cleaning a basement membrane, drying the basement membrane to constant weight, placing the basement membrane in an irradiation chamber, and irradiating the basement membrane by using high-energy rays; the base film is selected from the group consisting of polyhydrocarbons, polyhalogenated hydrocarbons; the high-energy rays are high-energy electron beams and gamma rays; the total irradiation dose is 20-200 kGy;
2) the method comprises the steps of simultaneously grafting two surfaces of a substrate film, namely putting the substrate film into a reactor, soaking the substrate film into a grafting monomer solution, putting the reactor into a constant-temperature water bath kettle for reaction, and grafting a monomer, wherein the monomer in the grafting monomer solution is selected from organic compounds containing unsaturated alkyl on a benzene ring, and the organic compounds containing unsaturated alkyl on the benzene ring are selected from one of styrene, α -methyl styrene and p-methyl styrene;
3) and (3) re-film forming: co-melting the grafted base film with a base film which is not subjected to high-temperature radiation under the heating condition, and then curing on a press to prepare a homogeneous grafted film;
4) sulfonation: soaking the grafted membrane in a sulfonation reagent, hydrolyzing in a sodium hydroxide aqueous solution, washing with deionized water, and finally drying to obtain a homogeneous cation exchange membrane; the sulfonation reaction time is 0.25-6 h.
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| CN103804707A (en) * | 2012-11-09 | 2014-05-21 | 张忠德 | Preparation method of base membrane used for preparation of ion exchange membranes |
| CN104779404A (en) * | 2015-04-09 | 2015-07-15 | 深圳市万越新能源科技有限公司 | Method for preparing homogeneous-phase ion exchange membrane of all-vanadium battery by use of ray irradiation grafting method |
| CN105833737A (en) * | 2016-04-12 | 2016-08-10 | 厦门大学 | Single-sheet type bipolar membrane and preparation method thereof |
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| CN103804707A (en) * | 2012-11-09 | 2014-05-21 | 张忠德 | Preparation method of base membrane used for preparation of ion exchange membranes |
| CN103349915A (en) * | 2013-07-24 | 2013-10-16 | 宜宾海丝特纤维有限责任公司 | Preparation method for cationic exchange membrane suitable for diffusion dialysis recycle of squeeze alkali liquor in viscose fibre production |
| CN104779404A (en) * | 2015-04-09 | 2015-07-15 | 深圳市万越新能源科技有限公司 | Method for preparing homogeneous-phase ion exchange membrane of all-vanadium battery by use of ray irradiation grafting method |
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