CN114471179A - Alkali-resistant bipolar membrane with main chain fluorocarbon-phthalocyanine catalytic layer and preparation method thereof - Google Patents
Alkali-resistant bipolar membrane with main chain fluorocarbon-phthalocyanine catalytic layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer and a preparation method thereof, belonging to the field of electrically driven membranes.
Description
Technical Field
The invention relates to a main chain fluorocarbon-phthalocyanine catalytic layer acid-base bipolar membrane and a preparation method thereof, belonging to the technical field of electrically driven membranes.
Background
The bipolar membrane is a composite membrane material formed by compounding an anion exchange membrane layer, a cation exchange membrane layer and an intermediate interface layer (intermediate layer). Under the action of an electric field, water molecules in the middle layer of the bipolar membrane are subjected to water dissociation to generate hydrogen ions and hydroxyl, so that the purpose of acid and alkali production is achieved. The theoretical potential of acid and alkali produced by the water dissociation of the bipolar membrane is 0.828V, and the theoretical voltage of acid and alkali produced by the electrolysis of water is 2.057V. In addition, the water dissociation speed of the bipolar membrane intermediate layer is about 5000 ten thousand times faster than that in the general case. Therefore, the bipolar membrane technology has the characteristics of low energy consumption, high efficiency, no pollution of products and the like, and is widely applied to various fields of acid and alkali production and recovery, ocean chemical industry, pollution treatment, organic synthesis and the like.
Aromatic carbon skeletons such as polyaryletherketone and the like are commonly used bipolar membrane substrate materials at present, and quaternary ammonium functional groups are common functional groups of an anion exchange membrane layer of the bipolar membrane. However, the carbon-oxygen bond in the aromatic carbon skeleton is easily attacked by hydroxyl groups to be degraded. In addition, due to the attack of hydroxide, quaternary ammonium functional groups are destroyed due to Hofmann reaction, affinity substitution reaction and the like, so that the alkali-resistant concentration of the bipolar membrane is generally low. On the other hand, the existing bipolar membrane is formed by compounding an anion exchange membrane layer, a cation exchange membrane layer and an intermediate layer, and due to the difference of physicochemical properties of different layers, the bipolar membrane is easy to peel off in the use process, so that the service life of the bipolar membrane is shortened.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalyst layer and the preparation method thereof, wherein the anion exchange membrane layer and the cation exchange membrane layer in the bipolar membrane both use perfluorocarbons as main chains, so that the defect that carbon-oxygen bonds in the common main chains are easily degraded by being attacked by hydroxide is overcome, and the anion and cation exchange membrane layers have similar physicochemical properties, so that the stripping possibility in the use process is reduced, and the service life of the bipolar membrane is prolonged.
The technical scheme of the invention is as follows:
the invention aims to provide an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer, which comprises a cation exchange membrane layer and an anion exchange membrane layer, wherein the cation exchange membrane layer and the anion exchange membrane layer both use perfluorocarbon as a main chain, and nitrogen heterocycle is used as a cation functional group on the anion exchange membrane layer; wherein, the chemical structural formula of the cation exchange membrane layer is as follows:
the chemical structural formula of the anion exchange membrane layer is as follows:
wherein x is the polymerization degree of a polymer main chain containing a chlorotrifluoroethylene structural unit, n is the polymerization degree of a side chain containing a sulfonic acid group substituent group, m is the polymerization degree of a side chain containing an imidazole substituent group, and n and m are integers which are not zero.
The invention also aims to provide a preparation method of the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer, which specifically comprises the following steps:
s1, preparation of cation exchange membrane liquid: dissolving a polymer containing a chlorotrifluoroethylene structural unit in an organic solvent I, introducing nitrogen to remove oxygen, heating, adding the polymer containing the chlorotrifluoroethylene structural unit, sodium styrene sulfonate, CuBr and bipyridine into a reaction system according to a molar ratio of 1 (20-100): 1:2, carrying out constant-temperature sulfonation reaction for 16-48 h at 90-130 ℃ under the protection of nitrogen, filling a reaction solution into a dialysis bag, and dialyzing for 24h in water; drying the solution in the dialysis bag to obtain a polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer (PCTEF-g-PSSNa);
s2, preparation of anion exchange membrane liquid: dissolving a polymer containing a chlorotrifluoroethylene structural unit in an organic solvent II, introducing nitrogen to remove oxygen, heating, mixing according to the molar ratio 1 (20-100): 1:2 of the polymer containing the chlorotrifluoroethylene structural unit, a monomer containing an imidazole group, uBr and bipyridine, reacting for 16-48 h at a constant temperature under the protection of nitrogen, filling a reaction solution into a dialysis bag, and dialyzing for 24h in water; drying the solution in the dialysis bag to obtain polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer (PCTEF-g-PVIm);
s3, preparation of phthalocyanine precursor: adding KH-560 and amino phthalocyanine into a reaction bottle according to a molar ratio of 1:1, adding an organic solvent III, uniformly stirring, and reacting at room temperature for 1-3 h to obtain a phthalocyanine-KH 560 precursor;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: adding the phthalocyanine-KH 560 precursor obtained in the step S3 and a silane coupling agent into a reactor, adding an acid catalyst and distilled water, adjusting the pH of a reaction system to 2.5-3.5, and reacting at 50-60 ℃ for 1-8 h to obtain KH-560 modified phthalocyanine silica sol serving as a bipolar membrane intermediate layer water dissociation catalyst;
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified phthalocyanine silica sol on the cation exchange membrane layer, drying in the air, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer, and drying to obtain the alkali-resistant bipolar membrane of the chain fluorocarbon-phthalocyanine catalyst layer.
Further, the polymer containing a chlorotrifluoroethylene structural unit in steps S1 and S2 is any one of poly (vinylidene fluoride-chlorotrifluoroethylene), poly (vinylidene fluoride-chlorotrifluoroethylene-tetrafluoroethylene), poly (tetrafluoroethylene-chlorotrifluoroethylene), or polychlorotrifluoroethylene.
Further, in the step S1, the organic solvent i is any one or a combination of two of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any ratio.
Further, in the step S2, the imidazole-containing monomer is 2-methyl-1-vinylimidazole, 2, 4-dimethyl-1-vinylimidazole, 2,4, 5-trimethyl-1-vinylimidazole, 5-ethyl-2, 4-dimethyl-1-vinylimidazole, 2-ethyl-4, 5-dimethyl-1-vinylimidazole, 4-ethyl-2, 5-dimethyl-1-vinylimidazole, 2-propyl-4, 5-dimethyl-1-vinylimidazole, 4-propyl-2, 5-dimethyl-1-vinylimidazole, 2-butyl-4, 5-dimethyl-1-vinylimidazole, 4-butyl-2, 5-dimethyl-1-vinylimidazole, 2, 4-diethyl-5-methyl-1-vinylimidazole, 4, 5-diethyl-2-methyl-1-vinylimidazole, 2, 4-dibutyl-5-methyl-1-vinylimidazole and 4, 5-dibutyl-2-methyl-1-vinylimidazole.
Further, in the step S2, the organic solvent ii is any one or a combination of two of tetrahydrofuran, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, and N, N-dimethylformamide in any proportion.
Further, in step S3, the organic solvent iii is any one or a combination of two of anhydrous methanol, anhydrous ethanol, isopropanol, tetrahydrofuran, and acetone at any ratio.
Further, in step S3, the amino phthalocyanine is transition metal-containing amino phthalocyanine, and the transition metal is any one of Fe, Mg, Ba, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, or Zn.
Further, in the step S4, the silane coupling agent is any one of KH540, KH550, KH602 or KH 792; the catalyst is any one of hydrochloric acid, formic acid or acetic acid.
Further, in the step S5, the KH-560 modified phthalocyanine silica sol is sprayed on the cation exchange membrane layer by any one of aerosol spraying, electrostatic spraying, dip-and-draw method, and spin coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalyst layer, provided by the invention, has the advantages that the cation exchange membrane layer and the anion exchange membrane layer both take fluorocarbon as the main chain, the defect that a carbon-oxygen bond in an aromatic carbon skeleton is easily attacked by hydroxyl and degraded in the prior art can be overcome, meanwhile, the nitrogen heterocyclic ring is used as a cation functional group of the anion exchange membrane layer to replace a quaternary ammonium salt functional group, on one hand, the situation that the quaternary ammonium salt functional group is damaged due to Hofmann reaction and affinity substitution reaction can be avoided, on the other hand, the electron distribution of the nitrogen heterocyclic ring functional group is more uniform, the alkali resistance is stronger, the alkali resistance of the bipolar membrane can be improved, and the acid-base concentration generated in electrodialysis can be improved.
(2) In the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalyst layer, the anion exchange membrane layer and the cation exchange membrane layer both use fluorocarbon chains as main chains, and the anion exchange membrane layer and the cation exchange membrane layer have similar physicochemical properties, so that the difference of the physicochemical properties of different layers is avoided, the possibility of stripping in the use process is reduced, and the service life of the bipolar membrane is prolonged.
Detailed Description
The invention is further described in connection with the preferred embodiments, and the endpoints of the ranges disclosed herein and any values are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values; for ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified;
the experimental procedures in the following examples are conventional unless otherwise specified.
Example 1
An alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer comprises a cation exchange membrane layer and an anion exchange membrane layer, wherein the cation exchange membrane layer and the anion exchange membrane layer both use perfluorocarbon as a main chain, and nitrogen heterocycles are used as cation functional groups on the anion exchange membrane layer; wherein, the chemical structural formula of the cation exchange membrane layer is as follows:
the chemical structural formula of the anion exchange membrane layer is as follows:
wherein x is the polymerization degree of a polymer main chain containing a chlorotrifluoroethylene structural unit, n is the polymerization degree of a side chain containing a sulfonic acid group substituent group, m is the polymerization degree of a side chain containing an imidazole substituent group, and n and m are integers which are not zero.
Example 2
A preparation method of an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer comprises the following steps:
s1, preparation of cation exchange membrane liquid: weighing 10g of poly (vinylidene fluoride-chlorotrifluoroethylene (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N-methylpyrrolidone, introducing nitrogen to remove oxygen, heating to 120 ℃, adding 126.3g of sodium styrene sulfonate, 4.36g of CuBr and 4.76g of bipyridine, carrying out constant-temperature sulfonation reaction for 24h at 120 ℃ under the protection of nitrogen, pouring the reaction solution into an alcohol/water mixed solvent (V/V ═ 1:1), precipitating to obtain a grafted polymer, filling the grafted polymer into a dialysis bag, dialyzing for 24h with water to remove copper ions, bromine ions and bipyridine and unreacted monomers, collecting the solution in the dialysis bag, concentrating and drying to obtain a polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer (PCTEF-g-PSSNa), wherein the grafting reaction is as follows:
s2, preparation of anion exchange membrane liquid: weighing 10g of poly (vinylidene fluoride-chlorotrifluoroethylene) (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N, N-dimethylformamide, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 74.44g of 2-methyl-1-vinylimidazole, 4.36g of CuBr and 10.56g of pentamethyl diethyl triamine, reacting for 48 hours at constant temperature under the protection of nitrogen, filling reaction liquid into a dialysis bag, dialyzing for 24 hours in water, and removing copper ions, bromide ions, bipyridine and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer (PCTEF-g-PVIm); wherein the grafting reaction is as follows:
s3, preparation of phthalocyanine precursor: weighing 2.36g of KH-560 and 5.77g of copper phthalocyanine, adding into a reaction bottle, adding 35mL of absolute ethanol, stirring uniformly, reacting at room temperature for 3h, and distilling to remove the solvent to obtain a precursor of the iron phthalocyanine-KH 560;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: weighing 8.06g of the iron phthalocyanine-KH 560 precursor obtained in the step S3, adding the precursor and 1.11g of a silane coupling agent KH792 into a reactor, simultaneously adding 18mL of ethanol, 7.5mL of distilled water and 0.6mL of 1.0% hydrochloric acid, adjusting the pH of a reaction system to 3.5, and reacting at 50 ℃ for 1h to obtain KH-560 modified iron phthalocyanine silica sol serving as a bipolar membrane intermediate layer water dissociation catalyst; wherein the reaction is as follows:
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified iron phthalocyanine silica sol on the cation exchange membrane layer by adopting an electrostatic spraying method, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer after drying, soaking the dried cathode surface in a methyl iodide tetrahydrofuran solution for 5 hours, taking out, and washing impurities on the surface of the membrane by using distilled water to obtain the chain fluorocarbon-phthalocyanine catalyst layer bipolar alkali-resistant membrane.
Example 3
A preparation method of an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer comprises the following steps:
s1, preparation of cation exchange membrane liquid: weighing 10g of poly (vinylidene fluoride-chlorotrifluoroethylene-tetrafluoroethylene) (copolymer contains 25% of chlorotrifluoroethylene), dissolving in 120mL of dimethyl sulfoxide, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 151.6g of sodium styrene sulfonate, 4.36g of CuBr and 10.56g of pentamethyl diethyl triamine, carrying out constant-temperature sulfonation reaction for 48h at 80 ℃ under the protection of nitrogen, pouring reaction liquid into ethanol, precipitating to obtain a graft polymer, filling into a dialysis bag, dialyzing for 24h in water, and removing copper ions, bromine ions, bipyridine and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer (PCTEF-g-PSSNa); wherein the grafting reaction is as shown in example 1:
s2, preparation of anion exchange membrane liquid: weighing 10g of poly (vinylidene fluoride-chlorotrifluoroethylene-tetrafluoroethylene) (copolymer contains 25% of chlorotrifluoroethylene), dissolving in 120mL of tetrahydrofuran, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 74.4g of 5-ethyl-2, 4-dimethyl-1-vinylimidazole, 4.36g of CuBr and 4.76g of bipyridyl, reacting at constant temperature for 16h under the protection of nitrogen, filling reaction liquid into a dialysis bag, dialyzing for 24h in water, and removing copper ions, bromine ions, bipyridyl and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer (PCTEF-g-PVIm); wherein the grafting reaction is as follows:
s3, preparation of phthalocyanine precursor: weighing 2.36g of KH-560 and 5.70g of copper phthalocyanine, adding into a reaction flask, adding 30mL of acetone, stirring uniformly, reacting at room temperature for 1h, and distilling to remove the solvent to obtain a copper phthalocyanine-KH 560 precursor;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: weighing 8.13g of copper phthalocyanine-KH 560 precursor obtained in the step S3, adding the precursor and 1.11g of silane coupling agent KH602 into a reactor, simultaneously adding 18mL of ethanol, 7.5mL of distilled water and 0.6mL of formic acid, adjusting the pH of a reaction system to 2.5, and reacting at 50 ℃ for 2h to obtain KH-560 modified copper phthalocyanine silica sol serving as a bipolar membrane middle layer water dissociation catalyst; wherein the reaction is as follows:
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified copper phthalocyanine silica sol on the cation exchange membrane layer by adopting a spin coating method, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer after drying, soaking the dried negative surface in methyl iodide tetrahydrofuran solution for 5 hours, taking out, and washing impurities on the surface of the membrane by using distilled water to clean the impurities, thereby obtaining the chain fluorocarbon-phthalocyanine catalyst layer bipolar alkali-resistant membrane.
Example 4
A preparation method of an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer comprises the following steps:
s1, preparation of cation exchange membrane liquid: weighing 10g of poly (tetrafluoroethylene-chlorotrifluoroethylene) (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N, N-dimethylacetamide, introducing nitrogen to remove oxygen, heating to 130 ℃, adding 126.3g of sodium styrene sulfonate, 4.36g of CuBr and 10.56g of pentamethyldiethyltriamine, carrying out constant-temperature sulfonation reaction for 16h at 80 ℃ under the protection of nitrogen, dialyzing the reaction solution in a dialysis bag for 24h in water, and removing copper ions, bromine ions, bipyridine and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer (PCTEF-g-PSSNa); wherein the grafting reaction is as shown in example 1:
s2, preparation of anion exchange membrane liquid: weighing 10g of poly (tetrafluoroethylene-chlorotrifluoroethylene) (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N-methylpyrrolidone, introducing nitrogen to remove oxygen, heating to 85 ℃, adding 70.4g of 2, 4-dimethyl-1-vinylimidazole, 4.36g of CuBr and 4.76g of bipyridyl, reacting at constant temperature for 18h under the protection of nitrogen, filling reaction liquid into a dialysis bag, dialyzing for 24h in water, and removing copper ions, bromide ions, bipyridyl and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer (PCTEF-g-PVIm); wherein the grafting reaction is as follows:
s3, preparation of phthalocyanine precursor: weighing 2.36g of KH-560 and 5.73g of cobalt phthalocyanine, adding into a reaction bottle, adding 35mL of tetrahydrofuran, stirring uniformly, reacting at room temperature for 2h, and distilling to remove the solvent to obtain a cobalt phthalocyanine-KH 560 precursor;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: weighing 8.09g of cobalt phthalocyanine-KH 560 precursor obtained in the step S3, adding the precursor and 1.11g of silane coupling agent KH540 into a reactor, simultaneously adding 18mL of ethanol, 7.5mL of distilled water and 0.6mL of acetic acid, adjusting the pH of a reaction system to 3.0, and reacting at 50 ℃ for 3 hours to obtain KH-560 modified cobalt phthalocyanine silica sol serving as a bipolar membrane intermediate layer water dissociation catalyst; wherein the reaction is as follows:
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified cobalt phthalocyanine silica sol on the cation exchange membrane layer by adopting a dipping-pulling method, drying, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer, drying, soaking the shade surface in an iodomethane tetrahydrofuran solution for 5 hours, taking out, and washing impurities on the surface of the membrane by using distilled water to obtain the alkali-resistant bipolar membrane with the chain fluorocarbon-phthalocyanine catalytic layer.
Example 5
A preparation method of an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer comprises the following steps:
s1, preparation of cation exchange membrane liquid: weighing 10g of polychlorotrifluoroethylene (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N, N-dimethylformamide, introducing nitrogen to remove oxygen, heating to 110 ℃, adding 140.0 g of sodium styrene sulfonate, 4.36g of CuBr and 10.76g of pentamethyldiethyltriamine, carrying out constant-temperature sulfonation reaction for 40h at 110 ℃ under the protection of nitrogen, dialyzing the reaction solution in a dialysis bag for 24h in water, and removing copper ions, bromine ions, bipyridine and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer (PCTEF-g-PSSNa); wherein the grafting reaction is as shown in example 1:
s2, preparation of anion exchange membrane liquid: weighing 10g of polychlorotrifluoroethylene (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N, N-dimethylacetamide, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 89.68g of 2-ethyl-4, 5-dimethyl-1-vinylimidazole, 4.36g of CuBr and 10.56g of pentamethyldiethyltriamine, reacting at constant temperature for 24h under the protection of nitrogen, filling the reaction solution into a dialysis bag, and dialyzing for 24h in water to remove copper ions, bromine ions, bipyridine and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer (PCTEF-g-PVIm); wherein the grafting reaction is as follows:
s3, preparation of phthalocyanine precursor: weighing 2.36g of KH-560 and 5.70g of cobalt phthalocyanine, adding into a reaction bottle, adding 35mL of isopropanol, stirring uniformly, reacting at room temperature for 3h, and distilling to remove the solvent to obtain a cobalt phthalocyanine-KH 560 precursor;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: weighing 8.09g of cobalt phthalocyanine-KH 560 precursor obtained in the step S3, adding the precursor and 1.11g of silane coupling agent KH550 into a reactor, simultaneously adding 18mL of ethanol, 7.5mL of distilled water and 0.6mL of 1.0% hydrochloric acid, adjusting the pH value of a reaction system to 3.0, and reacting at 50 ℃ for 1h to obtain KH-560 modified cobalt phthalocyanine silica sol serving as a bipolar membrane intermediate layer water dissociation catalyst; wherein the reaction is as follows:
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified cobalt phthalocyanine silica sol on the cation exchange membrane layer by adopting an aerosol spraying method, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer after drying, soaking the dried cathode surface in a methyl iodide tetrahydrofuran solution for 5 hours, taking out, and washing impurities on the surface of the membrane by using distilled water to obtain the alkali-resistant bipolar membrane of the chain fluorocarbon-phthalocyanine catalyst layer.
Example 6
A preparation method of an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer comprises the following steps:
s1, preparation of cation exchange membrane liquid: weighing 10g of poly (vinylidene fluoride-chlorotrifluoroethylene) (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of N-methylpyrrolidone, introducing nitrogen to remove oxygen, heating to 130 ℃, adding 126.3g of sodium styrene sulfonate, 4.36g of CuBr and 4.76g of bipyridyl, carrying out constant-temperature sulfonation reaction for 20h at 130 ℃ under the protection of nitrogen, pouring reaction liquid into ethanol, precipitating to obtain a graft polymer, putting the precipitate into a dialysis bag, dialyzing for 24h in water, and removing copper ions, bromine ions, bipyridyl and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer (PCTEF-g-PSSNa); wherein the grafting reaction is as shown in example 1:
s2, preparation of anion exchange membrane liquid: weighing 10g of poly (vinylidene fluoride-chlorotrifluoroethylene) (copolymer containing 25% of chlorotrifluoroethylene), dissolving in 120mL of dimethyl sulfoxide, introducing nitrogen to remove oxygen, heating to 80 ℃, adding 89.68g of 5-ethyl-2, 4-dimethyl-1-vinyl imidazole, 4.36g of CuBr and 10.56g of pentamethyl diethyl triamine, reacting for 18h at constant temperature under the protection of nitrogen, filling reaction liquid into a dialysis bag, dialyzing for 24h in water, and removing copper ions, bromine ions, bipyridine and unreacted monomers; collecting the solution in the dialysis bag, concentrating and drying to obtain polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer (PCTEF-g-PVIm); wherein the grafting reaction is as follows:
s3, preparation of phthalocyanine precursor: weighing 2.36g of KH-560 and 5.70g of iron phthalocyanine, adding into a reaction bottle, adding 30mL of anhydrous methanol, stirring uniformly, reacting at room temperature for 2h, and distilling to remove the solvent to obtain an iron phthalocyanine-KH 560 precursor;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: weighing 8.06g of the iron phthalocyanine-KH 560 precursor obtained in the step S3, adding the precursor and 0.90g of a silane coupling agent KH540 into a reactor, simultaneously adding 18mL of ethanol, 7.5mL of distilled water and 0.6mL of 1.0% hydrochloric acid, adjusting the pH value of a reaction system to 3.5, and reacting at 50 ℃ for 1h to obtain KH-560 modified iron phthalocyanine silica sol serving as a bipolar membrane intermediate layer water dissociation catalyst; wherein the reaction is as follows:
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified cobalt phthalocyanine silica sol on the cation exchange membrane layer by adopting an electrostatic spraying method, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer after drying, soaking the dried cathode surface in iodomethane tetrahydrofuran solution for 5 hours, taking out, and washing impurities on the surface of the membrane by using distilled water to obtain the alkali-resistant bipolar membrane of the chain fluorocarbon-phthalocyanine catalyst layer.
Example 7
The difference from the above embodiment is that:
the monomer having an imidazole group in step S2 may be 2,4, 5-trimethyl-1-vinylimidazole, 4-ethyl-2, 5-dimethyl-1-vinylimidazole, 2-propyl-4, 5-dimethyl-1-vinylimidazole, 4-propyl-2, 5-dimethyl-1-vinylimidazole, 2-butyl-4, 5-dimethyl-1-vinylimidazole, 4-butyl-2, 5-dimethyl-1-vinylimidazole, 2, 4-diethyl-5-methyl-1-vinylimidazole, 4, 5-diethyl-2-methyl-1-vinylimidazole, 2, 4-dibutyl-5-methyl-1-vinyl imidazole, 4, 5-dibutyl-2-methyl-1-vinyl imidazole in any one.
In step S3, the aminophthalocyanine is transition metal-containing aminophthalocyanine, and any one of Mg, Ba, Sc, Ti, V, Cr, Mn, Ni, and Zn may be selected in addition to iron phthalocyanine, cobalt phthalocyanine, and copper phthalocyanine.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present patent.
Claims (10)
1. The alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalyst layer is characterized in that: the membrane comprises a cation exchange membrane layer and an anion exchange membrane layer, wherein the cation exchange membrane layer and the anion exchange membrane layer both use perfluorocarbon as a main chain, and nitrogen heterocycles are used as cation functional groups on the anion exchange membrane layer; wherein, the chemical structural formula of the cation exchange membrane layer is as follows:
the chemical structural formula of the anion exchange membrane layer is as follows:
wherein x is the polymerization degree of a polymer main chain containing a chlorotrifluoroethylene structural unit, n is the polymerization degree of a side chain containing a sulfonic acid group substituent group, m is the polymerization degree of a side chain containing an imidazole substituent group, and n and m are integers which are not zero.
2. A preparation method of an alkali-resistant bipolar membrane with a main chain fluorocarbon-phthalocyanine catalyst layer is characterized by comprising the following steps:
s1, preparation of cation exchange membrane liquid: dissolving a polymer containing a chlorotrifluoroethylene structural unit in an organic solvent I, introducing nitrogen to remove oxygen, heating, adding the polymer containing the chlorotrifluoroethylene structural unit, sodium styrene sulfonate, CuBr and bipyridine into a reaction system according to a molar ratio of 1 (20-100): 1:2, carrying out constant-temperature sulfonation reaction for 16-48 h at 90-130 ℃ under the protection of nitrogen, filling a reaction solution into a dialysis bag, and dialyzing for 24h in water; drying the solution in the dialysis bag to prepare the polytrifluorochloroethylene grafted sodium styrene sulfonate side chain copolymer;
s2, preparation of anion exchange membrane liquid: dissolving a polymer containing a chlorotrifluoroethylene structural unit in an organic solvent II, introducing nitrogen to remove oxygen, heating, mixing according to the molar ratio 1 (20-100): 1:2 of the polymer containing the chlorotrifluoroethylene structural unit, a monomer containing an imidazole group, uBr and bipyridine, reacting for 16-48 h at a constant temperature under the protection of nitrogen, filling a reaction solution into a dialysis bag, and dialyzing for 24h in water; drying the solution in the dialysis bag to prepare a polytrifluorochloroethylene grafted vinyl imidazole side chain copolymer;
s3, preparation of phthalocyanine precursor: adding KH-560 and amino phthalocyanine into a reaction bottle according to a molar ratio of 1:1, adding an organic solvent III, uniformly stirring, and reacting at room temperature for 1-3 h to obtain a phthalocyanine-KH 560 precursor;
s4, preparation of bipolar membrane intermediate layer water dissociation catalyst: adding the phthalocyanine-KH 560 precursor obtained in the step S3 and a silane coupling agent into a reactor, adding an acid catalyst and distilled water, adjusting the pH of a reaction system to 2.5-3.5, and reacting at 50-60 ℃ for 1-8 h to obtain KH-560 modified phthalocyanine silica sol serving as a bipolar membrane intermediate layer water dissociation catalyst;
s5, preparing a bipolar membrane: and (2) casting the polychlorotrifluoroethylene grafted sodium styrene sulfonate side chain copolymer solution prepared in the step (S1) on a cleaned glass plate, drying to prepare a cation exchange membrane layer, spraying KH-560 modified phthalocyanine silica sol on the cation exchange membrane layer, drying in the air, casting the polychlorotrifluoroethylene grafted vinyl imidazole side chain copolymer obtained in the step (S2) on the cation exchange membrane layer, and drying to obtain the alkali-resistant bipolar membrane of the chain fluorocarbon-phthalocyanine catalyst layer.
3. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: the polymer containing the chlorotrifluoroethylene structural unit in the steps S1 and S2 is any one of poly (vinylidene fluoride-chlorotrifluoroethylene), poly (vinylidene fluoride-chlorotrifluoroethylene-tetrafluoroethylene), poly (tetrafluoroethylene-chlorotrifluoroethylene) or polychlorotrifluoroethylene.
4. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: in the step S1, the organic solvent I is any one or a combination of two of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any proportion.
5. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: in step S2, the imidazole-containing monomer is selected from the group consisting of 2-methyl-1-vinylimidazole, 2, 4-dimethyl-1-vinylimidazole, 2,4, 5-trimethyl-1-vinylimidazole, 5-ethyl-2, 4-dimethyl-1-vinylimidazole, 2-ethyl-4, 5-dimethyl-1-vinylimidazole, 4-ethyl-2, 5-dimethyl-1-vinylimidazole, 2-propyl-4, 5-dimethyl-1-vinylimidazole, 4-propyl-2, 5-dimethyl-1-vinylimidazole, 2-butyl-4, 5-dimethyl-1-vinylimidazole, 4-butyl-2, 5-dimethyl-1-vinylimidazole, 2, 4-diethyl-5-methyl-1-vinylimidazole, 4, 5-diethyl-2-methyl-1-vinylimidazole, 2, 4-dibutyl-5-methyl-1-vinylimidazole or 4, 5-dibutyl-2-methyl-1-vinylimidazole.
6. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: in the step S2, the organic solvent II is one or a combination of two of tetrahydrofuran, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any proportion.
7. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: in the step S3, the organic solvent iii is any one of or a combination of two of anhydrous methanol, anhydrous ethanol, isopropanol, tetrahydrofuran and acetone at any ratio.
8. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: in step S3, the amino phthalocyanine is transition metal-containing amino phthalocyanine, and the transition metal is any one of Fe, Mg, Ba, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, or Zn.
9. The method for preparing alkali-resistant bipolar membrane with main chain fluorocarbon-phthalocyanine catalytic layer according to claim 2, wherein: the silane coupling agent in the step S4 is any one of KH540, KH550, KH602 or KH 792; the catalyst is any one of hydrochloric acid, formic acid or acetic acid.
10. The method for preparing the alkali-resistant bipolar membrane with the main chain fluorocarbon-phthalocyanine catalytic layer as claimed in claim 2, wherein: in the step S5, the KH-560 modified phthalocyanine silica sol is sprayed on the cation exchange membrane layer by any one of aerosol spraying, electrostatic spraying, dipping-pulling method, and spin coating.
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| US4253900A (en) * | 1977-02-28 | 1981-03-03 | Allied Chemical Corporation | Method of making novel two component bipolar ion exchange membranes |
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| US4253900A (en) * | 1977-02-28 | 1981-03-03 | Allied Chemical Corporation | Method of making novel two component bipolar ion exchange membranes |
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