CN112295413A - Preparation method of bipolar membrane - Google Patents
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Abstract
The invention belongs to the technical field of bipolar membranes, and discloses a preparation method of a bipolar membrane, which comprises the following steps: blending at least one of ethylene propylene copolymer, ethylene butene copolymer and ethylene octene copolymer with polypropylene, heating, mixing, granulating, drying, and casting to obtain a raw material film; immersing the raw material film into an irradiation liquid formed by mixing absolute ethyl alcohol, a styrene monomer and a divinylbenzene monomer, and performing constant-temperature irradiation grafting by using 60Co gamma-rays at the temperature of-5-15 ℃ to obtain a base film; respectively introducing anion/cation exchange groups on two sides of a base membrane, soaking the base membrane into sulfuric acid at 75 ℃ by using silver sulfate as a catalyst through a covering protection method, heating and sulfonating, and hydrolyzing to form an anode membrane layer after reaction in a reaction kettle; and adding chloromethyl ether into the other side at 45 ℃ by using tin tetrachloride as a catalyst to perform chloromethylation, then soaking the other side into a mixed aqueous solution of trimethylamine and polyethylene glycol at 40 ℃ to perform quaternary ammonification reaction, and reacting to form a cathode membrane layer to obtain the bipolar membrane.
Description
Technical Field
The invention belongs to the technical field of bipolar membranes, and particularly relates to a preparation method of a bipolar membrane.
Background
The bipolar membrane is a special ion exchange membrane, one side of the membrane is a cation exchange membrane layer, the other side of the membrane is an anion membrane layer, and the middle of the membrane is a water layer; under the action of a direct current electric field, the water of a middle water layer between the anion exchange membrane and the cation exchange membrane of the bipolar membrane is dissociated to generate hydrogen ions and hydroxide ions, and the hydrogen ions and the hydroxide ions are provided through the cation exchange membrane and the anion exchange membrane respectively, so that the hydrogen ions and the hydroxide ions are subjected to a displacement reaction with a salt solution in a raw material solution to form corresponding acid and alkali. Therefore, an electrodialysis apparatus consisting of bipolar membranes can be used for the production of acids and bases from salts.
At present, in view of some preparation methods of bipolar membranes reported in the known literature, there are some disadvantages, such as: chinese patent with application number 201510987546.5 discloses Zn2+-TiO2A modified bipolar membrane of polyethyleneimine/sodium polyacrylate is prepared from polyethyleneimine as negative membrane layer and sodium polyacrylate as positive membrane layer through adding Zn2+-TiO2The powder changes the property of the middle layer, so that the prepared film is tightly combined and is not easy to delaminate; but because the dissociation degree of the sodium carboxylate group contained in the used anode film layer is not high, the ion exchange speed is slow; the active groups contained in the used anion membrane layer are alkalescent and are not beneficial to the rapid exchange and transfer of ions.
Disclosure of Invention
In view of the above, in order to solve the defects in the prior art, the present invention aims to provide a method for preparing a bipolar membrane with high ion exchange capacity and high ion exchange rate.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a bipolar membrane comprises the following steps:
s1, blending one or more of ethylene propylene copolymer, ethylene butene copolymer and ethylene octene copolymer with polypropylene, heating to 120-230 ℃, mixing and granulating, drying, and casting to prepare a raw material film with the thickness of 0.2-0.25 mm;
s2, immersing the raw material membrane into an irradiation liquid formed by mixing absolute ethyl alcohol, a styrene monomer and a divinylbenzene monomer, irradiating and grafting at a constant temperature of-5-15 ℃ by using 60Co gamma-rays, soaking for 12-36 hours by using a polyethylene glycol aqueous solution after grafting, and drying to obtain a base membrane for preparing the ion exchange membrane;
s3, respectively introducing anion/cation exchange groups to two sides of the base membrane, soaking the base membrane into sulfuric acid for heating and sulfonation at 75 ℃ by using a covering protection method and taking silver sulfate as a catalyst, and hydrolyzing to form an anode membrane layer after reaction in a reaction kettle; and (2) adding chloromethyl ether into the other side of the base membrane at 45 ℃ by using tin tetrachloride as a catalyst to perform chloromethylation, then soaking the base membrane into a mixed aqueous solution of trimethylamine and polyethylene glycol at 40 ℃ to perform quaternary ammonification reaction, finally soaking the base membrane into a mixed aqueous solution of dimethylamine and polyethylene glycol at 45 ℃ to perform tertiary ammonification reaction, and reacting to form a cathode membrane layer, thereby obtaining the bipolar membrane.
Preferably, in the step S1, the weight percentage of the polypropylene is 20% to 40%, and the total weight percentage of one or more of the ethylene propylene copolymer, the ethylene butene copolymer, and the ethylene octene copolymer is 60% to 80%.
Preferably, the weight percentage of propylene in the ethylene-propylene copolymer is 30-60%, the weight percentage of butene in the ethylene-butene copolymer is 20-40%, and the weight percentage of octene in the ethylene-octene copolymer is 10-40%.
Preferably, in step S2, the irradiation solution is composed of: 10-60% of styrene monomer, 1-20% of divinylbenzene monomer and the balance of absolute ethyl alcohol.
Preferably, in the step S2, the irradiation dose is 4 to 6KGy, and the grafting ratio reaches 60 to 80%.
Preferably, in the step S3, during the heating sulfonation, the concentration of the sulfuric acid is controlled to be 72% -98%, the reaction time of the reaction kettle is controlled to be 11-13 hours, and the hydrolysis time is controlled to be 3-5 hours.
Preferably, in step S3, the reaction time of the reaction kettle is 12 hours, and the hydrolysis time is 4 hours.
Preferably, in step S3, the reaction time during chloromethylation is 13 to 15 hours, the concentration of trimethylamine in the mixed aqueous solution during quaternization is 28%, the concentration of polyethylene glycol in the mixed aqueous solution is 8%, the reaction time is 7 to 9 hours, the concentration of dimethylamine in the mixed aqueous solution during tertiary amination is 15%, the concentration of polyethylene glycol in the mixed aqueous solution is 3%, and the reaction time is 9 to 11 hours.
Preferably, in step S3, the reaction time for chloromethylation is 14 hours, the reaction time for quaternization is 8 hours, and the reaction time for tertiary amination is 10 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the invention, before the bipolar membrane is used for preparing the base membrane, polypropylene and several high molecular materials such as ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-octene copolymer and the like are subjected to a series of pretreatment of mixing, heating and granulating to destroy a polymer crystallization area, thereby greatly improving the impregnation rate of the base membrane and further improving the ion exchange capacity of the bipolar membrane.
(2) In the invention, the cation membrane layer is formed by heating and sulfonating in sulfuric acid, is a sulfonic acid type cation layer and has higher cation exchange capacity; the anion membrane layer is formed by chloromethylation of chloromethyl ether and quaternization of trimethylamine aqueous solution, and has higher anion exchange capacity, so that the bipolar membrane prepared by the invention has higher ion exchange capacity;
as the anode membrane layer and the cathode membrane layer both have higher ion exchange capacity, the bipolar membrane has high content of ion exchange groups, and the high content of ion exchange groups can exchange ions quickly, so that the bipolar membrane prepared by the invention has higher ion exchange rate.
In addition, because dimethylamine and trimethylamine aqueous solution are used as amination agents, more tertiary amine groups can be arranged at the junction of the positive mask and the negative mask, the tertiary amine groups have the characteristic of catalyzing water decomposition, and polyethylene glycol can be added on the basis to improve the bipolar membrane middle layer, so that an intermediate catalysis layer with the effect of accelerating the water dissociation can be formed, and the water dissociation efficiency of the whole bipolar membrane is improved.
Drawings
FIG. 1 is a schematic structural diagram of a bipolar membrane prepared by the preparation method provided by the invention;
FIG. 2 is a schematic diagram of the principle of acid-base preparation of the bipolar membrane prepared by the preparation method provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In the embodiment of the invention, a preparation method of a bipolar membrane is disclosed, which specifically comprises the following steps:
s1, uniformly mixing 30% of polypropylene, 5% of ethylene-propylene copolymer, 60% of ethylene-butylene copolymer and 5% of ethylene-octene copolymer, heating to 200-230 ℃, mixing and granulating, drying, and casting to prepare a raw material film with the thickness of 0.2 mm;
s2, mixing 55% of absolute ethyl alcohol, 40% of styrene monomer and 5% of divinylbenzene monomer to form irradiation liquid, placing the irradiation liquid in a stainless steel barrel, cutting the raw material membrane prepared in the step S1 to form a required size (specifically determined according to actual production requirements), then immersing the cut raw material membrane in the irradiation liquid, sealing the stainless steel barrel, introducing nitrogen, placing the stainless steel barrel in a 5-DEG C thermostat, performing constant-temperature irradiation grafting by using 60Co gamma-rays, wherein the irradiation dose is 5KGy, soaking the raw material membrane in a polyethylene glycol aqueous solution for 30 hours after the irradiation grafting, and drying to obtain a base membrane for preparing the ion exchange membrane;
s3, respectively introducing anion/cation exchange groups on two sides of the base membrane, under the coordination of a covering protection method,
one side of the base film is subjected to the following reaction: adding 80% sulfuric acid as a sulfonating agent into a reaction kettle, adding silver sulfate as a catalyst, immersing a base membrane into the sulfuric acid, heating to 75 ℃, sulfonating one side of the base membrane in the reaction kettle for 12 hours, taking out, soaking in water for hydrolysis for 4 hours, and forming a sulfonic acid type cation membrane layer on one side of the base membrane after drying;
the other side of the base film was subjected to the following reaction: adding chloromethyl ether serving as a chloromethylation reagent into a reaction kettle, adding stannic chloride serving as a catalyst, placing a base membrane into the reaction kettle, heating to 45 ℃, and carrying out a chloromethylation reaction for 14 hours; cooling, separating, taking out to obtain chloromethylated chloromethyl membrane, soaking the chloromethyl membrane in 28% aqueous solution of trimethylamine and 8% polyethylene glycol, heating to 40 deg.c and quaternary ammonifying for 8 hr; taking out, drying, immersing in a mixed aqueous solution of 15% dimethylamine and 3% polyethylene glycol, heating to 45 ℃, and carrying out tertiary amination reaction for 10 hours; taking out and drying to form a negative film layer on the other side of the base film;
in conclusion, the bipolar membrane is prepared.
Example 2
S1, uniformly mixing 35% of polypropylene and 65% of ethylene-butylene copolymer, heating to 150-230 ℃, mixing and granulating, drying, and casting to prepare a raw material film with the thickness of 0.23 mm;
s2, mixing 50% of absolute ethyl alcohol, 38% of styrene monomer and 12% of divinylbenzene monomer to form irradiation liquid, placing the irradiation liquid in a stainless steel barrel, cutting the raw material membrane prepared in the step S1 to form a required size (specifically determined according to actual production requirements), then immersing the cut raw material membrane in the irradiation liquid, sealing the stainless steel barrel, introducing nitrogen, placing the cut raw material membrane in a thermostat at 0 ℃, performing constant-temperature irradiation grafting by using 60Co gamma-rays, wherein the irradiation dose is 4.5KGy, soaking the cut raw material membrane in a polyethylene glycol aqueous solution for 24 hours after the irradiation grafting, and drying to obtain a base membrane for preparing an ion exchange membrane;
s3, respectively introducing anion/cation exchange groups on two sides of the base membrane, under the coordination of a covering protection method,
one side of the base film is subjected to the following reaction: adding 90% sulfuric acid as a sulfonating agent into a reaction kettle, adding silver sulfate as a catalyst, immersing a base membrane into the sulfuric acid, heating to 75 ℃, sulfonating one side of the base membrane in the reaction kettle for 12 hours, taking out, soaking in water for hydrolysis for 4 hours, and forming a sulfonic acid type cation membrane layer on one side of the base membrane after drying;
the other side of the base film was subjected to the following reaction: adding chloromethyl ether serving as a chloromethylation reagent into a reaction kettle, adding stannic chloride serving as a catalyst, placing a base membrane into the reaction kettle, heating to 45 ℃, and carrying out a chloromethylation reaction for 14 hours; cooling, separating, taking out to obtain chloromethylated chloromethyl membrane, soaking the chloromethyl membrane in 28% aqueous solution of trimethylamine and 8% polyethylene glycol, heating to 40 deg.c and quaternary ammonifying for 8 hr; taking out, drying, immersing in a mixed aqueous solution of 15% dimethylamine and 3% polyethylene glycol, heating to 45 ℃, and carrying out tertiary amination reaction for 10 hours; taking out and drying to form a negative film layer on the other side of the base film;
in conclusion, the bipolar membrane is prepared.
Example 3
S1, uniformly mixing 30% of polypropylene, 65% of ethylene-butene copolymer and 5% of ethylene-octene copolymer, heating to 180 ℃ and 230 ℃, mixing and granulating, drying, and casting to prepare a raw material film with the thickness of 0.25 mm;
s2, mixing 60% of absolute ethyl alcohol, 25% of styrene monomer and 15% of divinylbenzene monomer to form irradiation liquid, placing the irradiation liquid in a stainless steel barrel, cutting the raw material membrane prepared in the step S1 to form a required size (specifically determined according to actual production requirements), then immersing the cut raw material membrane in the irradiation liquid, sealing the stainless steel barrel, introducing nitrogen, placing the cut raw material membrane in a thermostat at 0 ℃, performing constant-temperature irradiation grafting by using 60Co gamma-rays, wherein the irradiation dose is 5KGy, soaking the cut raw material membrane in a polyethylene glycol aqueous solution for 18 hours after the irradiation grafting, and drying to obtain a base membrane for preparing the ion exchange membrane;
s3, respectively introducing anion/cation exchange groups on two sides of the base membrane, under the coordination of a covering protection method,
one side of the base film is subjected to the following reaction: adding sulfuric acid with the concentration of 97% into a reaction kettle as a sulfonating agent, adding silver sulfate as a catalyst, immersing a base membrane into the sulfuric acid, heating to 75 ℃, sulfonating one side of the base membrane in the reaction kettle for 12 hours, taking out, soaking in water for hydrolysis for 4 hours, and forming a sulfonic acid type cation membrane layer on one side of the base membrane after drying;
the other side of the base film was subjected to the following reaction: adding chloromethyl ether serving as a chloromethylation reagent into a reaction kettle, adding stannic chloride serving as a catalyst, placing a base membrane into the reaction kettle, heating to 45 ℃, and carrying out a chloromethylation reaction for 14 hours; cooling, separating, taking out to obtain chloromethylated chloromethyl membrane, soaking the chloromethyl membrane in 28% aqueous solution of trimethylamine and 8% polyethylene glycol, heating to 40 deg.c and quaternary ammonifying for 8 hr; taking out, drying, immersing in a mixed aqueous solution of 15% dimethylamine and 3% polyethylene glycol, heating to 45 ℃, and carrying out tertiary amination reaction for 10 hours; taking out and drying to form a negative film layer on the other side of the base film;
in conclusion, the bipolar membrane is prepared.
Specifically, in fig. 1, a schematic structural diagram of the bipolar membranes prepared in the 4 embodiments is shown, in which 1 is shown as an anode membrane layer, 2 is shown as a water layer, 3 is shown as a cathode membrane layer, and 4 is shown as an intermediate layer; specifically, as the trimethylamine aqueous solution is adopted as the amination agent, more tertiary amine groups can be arranged at the junction of the positive mask and the negative mask, and the tertiary amine groups have the characteristic of catalyzing water decomposition, and polyethylene glycol can be added on the basis to improve the middle layer of the bipolar membrane, so that the middle catalysis layer 4 with the effect of accelerating the water dissociation can be formed, and the water dissociation efficiency of the whole bipolar membrane is improved.
Further, when the bipolar membranes prepared in the above 4 embodiments are used for acid-base preparation, the principle is shown in fig. 2, in which 5 is an anode, 6 is a cathode, 7 is a cation exchange membrane, 8 is an anion exchange membrane, 9 is a salt chamber one, and 10 is a salt chamber two; specifically, the negative film layer 3 carries a positively charged functional group, allowing passage of negatively charged ions; the positive membrane layer 1 is provided with a negative charge functional group and allows ions with positive charges to pass through, and the middle part is a catalyst layer 4 which can catalyze water to be dissociated into H+And OH-Ions, H generated from the middle layer water layer 2 under the action of DC electric field of the anode 5 and the cathode 6+And OH-Ions respectively pass through the positive membrane layer 1 and the negative membrane layer 3 and are transferred into main body solutions of a salt chamber I9 and a salt chamber II 10 on two sides of the membrane; thus, in combination with anion exchange membrane 7 and cation exchange membrane 8, salts can be converted to the corresponding acids and bases.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of the bipolar membrane is characterized by comprising the following steps:
s1, blending one or more of ethylene propylene copolymer, ethylene butene copolymer and ethylene octene copolymer with polypropylene, heating to 120-230 ℃, mixing and granulating, drying, and casting to prepare a raw material film with the thickness of 0.2-0.25 mm;
s2, immersing the raw material membrane into an irradiation liquid formed by mixing absolute ethyl alcohol, a styrene monomer and a divinylbenzene monomer, irradiating and grafting at a constant temperature of-5-15 ℃ by using 60Co gamma-rays, soaking for 12-36 hours by using a polyethylene glycol aqueous solution after grafting, and drying to obtain a base membrane for preparing the ion exchange membrane;
s3, respectively introducing anion/cation exchange groups to two sides of the base membrane, soaking the base membrane into sulfuric acid for heating and sulfonation at 75 ℃ by using a covering protection method and taking silver sulfate as a catalyst, and hydrolyzing to form an anode membrane layer after reaction in a reaction kettle; and (2) adding chloromethyl ether into the other side of the base membrane at 45 ℃ by using tin tetrachloride as a catalyst to perform chloromethylation, then soaking the base membrane into a mixed aqueous solution of trimethylamine and polyethylene glycol at 40 ℃ to perform quaternary ammonification reaction, finally soaking the base membrane into a mixed aqueous solution of dimethylamine and polyethylene glycol at 45 ℃ to perform tertiary ammonification reaction, and reacting to form a cathode membrane layer, thereby obtaining the bipolar membrane.
2. The preparation method of the bipolar membrane according to claim 1, wherein: in the step S1, the weight percentage of the polypropylene is 20% to 40%, and the total weight percentage of one or more of the ethylene propylene copolymer, the ethylene butene copolymer, and the ethylene octene copolymer is 60% to 80%.
3. The preparation method of the bipolar membrane according to claim 2, characterized in that: the weight percentage of propylene in the ethylene-propylene copolymer is 30-60%, the weight percentage of butene in the ethylene-butene copolymer is 20-40%, and the weight percentage of octene in the ethylene-octene copolymer is 10-40%.
4. The bipolar membrane preparation method according to claim 1, wherein in step S2, the composition of the irradiation liquid is as follows: 10-60% of styrene monomer, 1-20% of divinylbenzene monomer and the balance of absolute ethyl alcohol.
5. The bipolar membrane preparation method according to claim 1 or 4, wherein: in the step S2, the irradiation dose is 4-6KGy, and the grafting rate reaches 60-80%.
6. The preparation method of the bipolar membrane according to claim 1, wherein: in the step S3, the concentration of sulfuric acid is controlled to be 72-98%, the reaction time of a reaction kettle is controlled to be 11-13 hours, and the hydrolysis time is controlled to be 3-5 hours during heating sulfonation.
7. The preparation method of the bipolar membrane according to claim 6, wherein: in the step S3, the reaction time of the reaction kettle is 12 hours, and the hydrolysis time is 4 hours.
8. The bipolar membrane preparation method according to claim 1, 6 or 7, wherein: in step S3, the reaction time during chloromethylation is 13 to 15 hours, the concentration of trimethylamine in the mixed aqueous solution during quaternization is 28%, the concentration of polyethylene glycol in the mixed aqueous solution is 8%, the reaction time is 7 to 9 hours, the concentration of dimethylamine in the mixed aqueous solution during tertiary amination is 15%, the concentration of polyethylene glycol in the mixed aqueous solution is 3%, and the reaction time is 9 to 11 hours.
9. The preparation method of the bipolar membrane according to claim 8, wherein: in step S3, the reaction time during chloromethylation is 14 hours, the reaction time during quaternization is 8 hours, and the reaction time during tertiary amination is 10 hours.
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