Anion exchange membrane and method for producing the same

Abstract

An anion exchange membrane and a method for producing the same are disclosed. The anion exchange membrane comprises a porous polymer support; and an electrolyte containing an anion exchange polymer; wherein the electrolyte is located on the surface and in part within the pores of the porous polymer support; and the anion exchange polymer is also a crosslinking product of a composition containing a crosslinkable monomer represented by the following chemical formula 1 and an ionic monomer represented by the following chemical formula 2: JPEG2026516927000016.jpg56170 In chemical formulas 1 and 2, A, R1, R2, R3, R4, X - , Y - p, q, and r are as disclosed in the specification, respectively.

Description

[Technical Field]

[0001] The present invention relates to an anion exchange membrane and a method for producing the same. [Background technology]

[0002] An ion exchange membrane is a synthetic resin membrane that selectively allows the passage of either cations or anions. Cation exchange membranes have negatively charged functional groups, allowing selective passage of cations, while anion exchange membranes have positively charged functional groups, allowing selective passage of anions. Generally, ion exchange membranes are required to have high permeability selectivity, low electrical resistance, excellent mechanical strength, and high chemical stability.

[0003] Such anion exchange membranes are applied to water treatment systems such as electrodialysis, bipolar membrane electrodialysis, energy storage desalination, and electrodeionization, or to systems such as fuel cells, water electrolysis, reverse electrodialysis, and oxidation-reduction flow batteries. Systems to which anion exchange membranes are applied can use acidic or alkaline raw water in their processes, and acids or alkalis may be generated during the process operation of the raw water. Here, perfluorinated anion exchange membranes can be used as anion exchange membranes, but because they are expensive, hydrocarbon anion exchange membranes are used in actual systems. However, hydrocarbon anion exchange membranes have limitations in the processes and conditions to which they can be applied due to chemical resistance issues. In addition, anion exchange membranes containing a support have limitations in increasing the ion exchange capacity to improve membrane properties because a certain fraction of the support is present in the membrane. [Overview of the project] [Problems that the invention aims to solve]

[0004] One objective is to increase the electrolyte content within the ion exchange membrane by one aspect, thereby providing an anion exchange membrane with high ion exchange capacity and excellent appearance.

[0005] Another aspect is to provide a method for manufacturing the anion exchange membrane described above.

Means for Solving the Problem

[0006] On one side, a porous polymer support; and an electrolyte containing an anion exchange polymer; are included, the electrolyte is located at least in part on the surface and inside the pores of the porous polymer support, there is provided an anion exchange membrane, wherein the anion exchange polymer is a crosslinked product of a composition containing a crosslinkable monomer represented by the following Chemical Formula 1 and an ionic monomer represented by the following Chemical Formula 2:

Chem.

[0007] Among Chemical Formula 1, X , , , a , <0​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​

[0008] Of the chemical formula 2 mentioned above, R4 is a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0009] Of the chemical formula 2 mentioned above, The aforementioned A is -O-; The aforementioned R4 is a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C15 aryl group.

[0010] The aforementioned ionic monomer is (3-acrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium bromide, (3-acrylamidopropyl)trimethylammonium iodide; (3-Methacryloylamidopropyl)trimethylammonium chloride, (3-Methacryloylamidopropyl)trimethylammonium bromide, (3-Methacryloylamidopropyl)trimethylammonium iodide; (2-Acryloyloxyethyl)trimethylammonium chloride, (2-Acryloyloxyethyl)trimethylammonium bromide, (2-Acryloyloxyethyl)trimethylammonium iodide; (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide; N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium bromide, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium iodide; Benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium bromide, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide; (Vinylbenzyl)trimethylammonium chloride, (Vinylbenzyl)trimethylammonium bromide, (Vinylbenzyl)trimethylammonium iodide; and It contains (2-methylvinylbenzyl)trimethylammonium chloride, (2-methylvinylbenzyl)trimethylammonium bromide, and (2-methylvinylbenzyl)trimethylammonium iodide.

[0011] The weight ratio of the crosslinkable monomer to the ionic monomer is 1:0.2 to 1:8.

[0012] The total content of the crosslinkable monomer and the ionic monomer is 30% to 85% by weight, based on 100% by weight of the entire composition.

[0013] The composition further comprises a photoinitiator, The content of the photoinitiator is 0.01% to 2% by weight, based on 100% by weight of the entire composition.

[0014] The porous polymer support is a membrane structure, a nonwoven fabric structure, a woven fabric structure, or a mesh structure.

[0015] The porous polymer support comprises one or more polymers selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyether ether ketone, polyether sulfone, polysulfone, polystyrene, polyarylene ether sulfone, and polyether ketone.

[0016] The porosity of the porous polymer support is 30% to 80%, and the thickness of the porous polymer support is 10 μm to 150 μm.

[0017] The sheet resistance of the anion exchange membrane according to the following formula 1 (R m ) is 6Ω·cm 2 The following is the case: [Formula 1] R m (Ω·cm 2 ) = (R 11 -R 12 ) × S In the formula, R m is the sheet resistance of the anion exchange membrane, R 11 is the wire resistance of the anion exchange membrane, R 12 is the resistance of a 0.5 M NaCl aqueous solution, S is the area of the electrode.

[0018] The ion exchange capacity (IEC) of the anion exchange membrane is 1.5 meq / g or more.

[0019] The anion exchange membrane is used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or a water electrolysis system.

[0020] On the other hand, providing a porous polymer support; manufacturing a composition for forming an anion exchange polymer, which contains a crosslinkable monomer represented by the following Chemical Formula 1, an ionic monomer represented by the following Chemical Formula 2, a photoinitiator, and a solvent; impregnating the porous polymer support with the composition for forming an anion exchange polymer to fill the composition in at least a part of the surface and the pores inside the porous polymer support; pressing a polyester film onto at least one surface of the porous polymer support filled with the composition to manufacture a laminate in which the polyester film and the porous polymer support are laminated; A step of irradiating the laminate with light to cause a crosslinking reaction of the composition, thereby forming an anion exchange polymer, which is a crosslinking product of the composition, on at least a portion of the surface and interior of the pores of the porous polymer support; and A method for producing an anion exchange membrane is provided, comprising the step of peeling off the polyester film from a porous polymer support on which the anion exchange polymer is formed in at least a portion of the surface and interior of the pores; [ka]

[0021] Of the chemical formulas, X - It is a halogen anion; Of the chemical formulas, A is [ka] And here, R a is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R1 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group; R2 and R3 are independently substituted or unsubstituted C1-C20 alkyl groups, or substituted or unsubstituted C5-C40 aryl groups; R4 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C5-C30 aryl group; p is either 0 or 1; q is an integer between 0 and 6; r is an integer from 0 to 6; and Y - It is a halogen anion. In the step of forming the anion exchange polymer, the light is ultraviolet light, and the light is applied at a density of 2000 mJ / cm². 2or 10,000 mJ / cm² 2 This process includes irradiating with a light intensity. [Effects of the Invention]

[0022] The one-sided anion exchange membrane contains an electrolyte comprising an anion exchange polymer, which is a crosslinking product of a composition comprising a porous polymer support, a crosslinkable monomer represented by chemical formula 1, and an ionic monomer represented by chemical formula 2. The electrolyte surrounds at least a portion of the surface and interior of the pores of the porous support. This can increase the ion exchange capacity by increasing the electrolyte content within the anion exchange membrane, thereby improving the performance of the anion exchange membrane. [Brief explanation of the drawing]

[0023] [Figure 1] This is a schematic diagram of an anion exchange membrane based on one actual example. [Modes for carrying out the invention]

[0024] The following provides a more detailed explanation of an anion exchange membrane and its manufacturing method based on a real-world example. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art in which the invention pertains. In case of any conflict, the foregoing, including the definitions, shall prevail. Similar or equivalent methods and materials may be used in carrying out or testing the invention, but preferred methods and materials are described herein. In this specification, the term “including” means that, unless otherwise specified, other components may be included, not excluded. In this specification, the term “combination of these” means a mixture or combination with one or more components described herein. In this specification, the term “and / or” means any combination and all combinations of one or more items described in relation to it. In this specification, the term “or” means “and / or.” In this specification, expressions such as “at least one type” or “one or more” preceding a component may complement the entire list of components, not the individual components described above. In this specification, where one component is said to be “on top of” another component, that component may be directly on top of the other component, or other components may be interposed between the components. On the other hand, when it is said that one component is placed "directly on top of" another component, there may be no intervening component. In this specification, "~-based resin," "~-based polymer," "~-based polymer," or / and "~-based copolymer" is a broad concept that includes all "~-based resin," "~-based polymer," "~-based polymer," "~-copolymer," or / and "derivatives of ~-based resin, polymer, polymer, or copolymer." In this specification, the term "polymer or copolymer crosslinked with these resins" means "polymer or copolymer crosslinked with the aforementioned resins."

[0025] Typical anion exchange membranes have a structure in which an anion exchange polymer with cationic functional groups is positioned on top of a support. Anion exchange membranes require high selective permeability to anions, low electrical resistance, and excellent mechanical strength and chemical stability.

[0026] Anion exchange membranes include perfluorinated anion exchange membranes and hydrocarbon anion exchange membranes. Of these, hydrocarbon anion exchange membranes are less expensive than perfluorinated anion exchange membranes, but their chemical resistance is not sufficient. Furthermore, anion exchange membranes that use a support structure have a certain percentage of support material, which limits the increase in ion exchange capacity needed to improve concentration and desalination performance.

[0027] The present inventors have solved the aforementioned problems and increased the electrolyte content within the ion exchange membrane to provide an anion exchange membrane with excellent appearance.

[0028] An example of an anion exchange membrane comprises a porous polymer support; and an electrolyte containing an anion exchange polymer; wherein the electrolyte is located on at least a portion of the surface and interior of the pores of the porous polymer support; and the anion exchange polymer is a crosslinking product of a composition containing a crosslinkable monomer represented by the following chemical formula 1 and an ionic monomer represented by the following chemical formula 2: [ka]

[0029] Of the chemical formulas, X - It is a halogen anion; Of the chemical formulas, A is [ka] And here, R a is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R1 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group; R2 and R3 are independently substituted or unsubstituted C1-C20 alkyl groups, or substituted or unsubstituted C5-C40 aryl groups; R4 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C5-C30 aryl group; p is either 0 or 1; q is an integer between 0 and 6; r is an integer from 0 to 6; and Y - It is a halogen anion.

[0030] In the ionic monomer represented by chemical formula 2, the vinyl group is a functional group capable of crosslinking with the crosslinkable monomer represented by chemical formula 1.

[0031] An anion exchange membrane according to one embodiment exhibits lower sheet resistance and superior appearance compared to an anion exchange membrane containing an anion exchange polymer, which is manufactured using a crosslinkable monomer represented by chemical formula 1 without the use of ionic monomers.

[0032] For example, in chemical formula 2, R4 is a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0033] For example, in chemical formula 2, A is -O-; and R4 is a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C15 aryl group.

[0034] For example, the ionic monomer is (3-acrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium bromide, (3-acrylamidopropyl)trimethylammonium iodide; (3-Methacryloylamidopropyl)trimethylammonium chloride, (3-Methacryloylamidopropyl)trimethylammonium bromide, (3-Methacryloylamidopropyl)trimethylammonium iodide; (2-Acryloyloxyethyl)trimethylammonium chloride, (2-Acryloyloxyethyl)trimethylammonium bromide, (2-Acryloyloxyethyl)trimethylammonium iodide; (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide; N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium bromide, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium iodide; Benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium bromide, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide; (Vinylbenzyl)trimethylammonium chloride, (Vinylbenzyl)trimethylammonium bromide, (Vinylbenzyl)trimethylammonium iodide; and It contains (2-methylvinylbenzyl)trimethylammonium chloride, (2-methylvinylbenzyl)trimethylammonium bromide, and (2-methylvinylbenzyl)trimethylammonium iodide.

[0035] For example, ionic monomers include (3-acrylamidopropyl)trimethylammonium chloride, (3-methacryloylamidopropyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium chloride, (vinylbenzyl)trimethylammonium chloride, and (2-methylvinylbenzyl)trimethylammonium chloride.

[0036] The weight ratio of the crosslinkable monomer to the ionic monomer is 1:0.2 to 1:8. For example, the weight ratio of the crosslinkable monomer to the ionic monomer is 1:0.2 to 1:5, or 1:0.5 to 1:5. If the weight ratio of the crosslinkable monomer to the ionic monomer is within the above range, the anion exchange performance of the anion exchange membrane can be improved without a decrease in the solubility characteristics of the anion exchange polymer forming composition.

[0037] The total content of crosslinkable monomers and ionic monomers is 30% to 85% by weight, based on 100% by weight of the entire composition. For example, the total content of crosslinkable monomers and ionic monomers is 35% to 80% by weight, or 40% to 75% by weight, based on 100% by weight of the entire composition. If the total content of crosslinkable monomers and ionic monomers is less than 30% by weight, the anion exchange performance of the anion exchange membrane will decrease, and if it exceeds 85% by weight, the solubility of the monomers constituting the anion exchange polymer may decrease when producing the electrolyte solution of the composition.

[0038] The composition further comprises a photoinitiator, the content of which is 0.01% to 2% by weight based on 100% by weight of the entire composition. The photoinitiator can be any photoinitiator available in the art, but is not limited to 2-hydroxy-2-methylpropiophenone. For example, the content of which is 0.1% to 1% by weight based on 100% by weight of the entire composition.

[0039] Figure 1 is a schematic diagram of an anion exchange membrane based on one actual example.

[0040] Referring to Figure 1, in one embodiment, the anion exchange membrane 40 has an anion exchange polymer 31 having cationic functional groups located on the surface and inside the pores 21 of the porous polymer support 20. The cationic functional group-containing anion exchange polymer 31 is uniformly distributed on the surface and inside the pores 21 of the porous polymer support 20, thereby obtaining a homogeneous anion exchange membrane 40. Such an anion exchange membrane 40 structure has low sheet resistance and high ionic conductivity. Furthermore, the porous polymer support 20 can improve mechanical durability and has high dimensional stability.

[0041] The porous polymer support 20 is in the shape of a sponge or a three-dimensional network. The porous polymer support 20 is a membrane structure, a nonwoven fabric structure, a woven fabric structure, or a mesh structure.

[0042] The porous polymer support 20 comprises one or more polymers selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyether ether ketone, polyether sulfone, polysulfone, polystyrene, polyarylene ether sulfone, and polyether ketone. For example, the porous polymer support 20 comprises one or more polymers selected from polyethylene, polypropylene, and polyvinyl alcohol.

[0043] The porosity of the porous polymer support 20 is 30% to 80%. Here, % represents volume %. The pore size of the porous polymer support 20 indicates the average diameter when the pores are spherical, and the length of the major axis when the pores are non-spherical. The porosity and pore size of the porous polymer support 20 are measured by the BET method and / or surface SEM imaging, and the porosity is determined by the area ratio in cross-sectional SEM image analysis. The porosity can also be calculated using basis weight and thickness.

[0044] The thickness of the porous polymer support is 10 μm to 150 μm. For example, the thickness of the porous polymer support is 20 μm to 150 μm, 40 μm to 150 μm, or 60 μm to 140 μm. Within the thickness range of the porous polymer support, the sheet resistance decreases and the ion exchange capacity increases.

[0045] The sheet resistance of the anion exchange membrane 40 according to the following formula 1 (R m ) is 6Ω·cm 2 The following is the case: [Formula 1] R m (Ω·cm 2 )=(R 11 -R 12 )×S During the ceremony, R m This is the sheet resistance of the anion exchange membrane, R 11 This is the wire resistance of the anion exchange membrane, R 12 This is the resistance of a 0.5M NaCl aqueous solution. S is the area of ​​the electrode. The ion exchange capacity (IEC) of the anion exchange membrane 40 is 1.5 meq / g or more. The anion exchange membrane 40 is used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems.

[0046] The anion exchange membrane 40 can also be used in energy systems such as fuel cells, water electrolysis, reverse electrodialysis, and oxidation-reduction flow batteries.

[0047] A method for producing an anion exchange membrane according to another embodiment includes the steps of: providing a porous polymer support; producing an anion exchange polymer-forming composition comprising a crosslinkable monomer represented by the following chemical formula 1, an ionic monomer represented by the following chemical formula 2, a photoinitiator, and a solvent; impregnating the porous polymer support with the anion exchange polymer-forming composition to fill at least a portion of the surface and interior of the pores of the porous polymer support with the composition; pressing a polyester film onto at least one surface of the porous polymer support filled with the composition to produce a laminate in which the polyester film and the porous polymer support are laminated; irradiating the laminate with light to cause a crosslinking reaction of the composition to form an anion exchange polymer, which is a crosslinking product of the composition, on at least a portion of the surface and interior of the pores of the porous polymer support; and peeling the polyester film from the porous polymer support, on which the anion exchange polymer has been formed on at least a portion of the surface and interior of the pores, to produce an anion exchange membrane; thereby producing the anion exchange membrane described above: [ka] Of the chemical formulas, X - It is a halogen anion; Of the chemical formulas, A is [ka] And here, R a is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R1 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group; R2 and R3 are independently substituted or unsubstituted C1-C20 alkyl groups, or substituted or unsubstituted C5-C40 aryl groups; R4 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, or a substituted or unsubstituted C5-C30 aryl group; p is either 0 or 1; q is an integer between 0 and 6; r is an integer from 0 to 6; and Y - It is a halogen anion.

[0048] First, a porous polymer support is provided.

[0049] The shape, structure, material, porosity, pore size, and thickness of the porous polymer support are the same as described above, so the following explanation will be omitted.

[0050] The method further includes the step of immersing the porous polymer support in a surfactant solution and drying it to hydrophilize the surface of the porous polymer support, prior to the step of manufacturing the porous polymer support by immersing it in an anion exchange polymer forming composition, which is an ion exchange resin solution, so that the ion exchange resin solution surrounds the voids and outer surface of the porous polymer support.

[0051] The hydrophilization step can be performed depending on the degree of hydrophilization of the porous polymer support or the structure of the porous polymer support. It may be omitted if the degree of hydrophilization of the porous polymer support is sufficient, or if the voids in the substrate are large enough to be filled with the ion exchange resin solution.

[0052] During the hydrophilization stage, immersion can be performed for 0.1 to 10 minutes, or 0.5 to 8 minutes. If immersion is performed for less than 0.1 minutes, the surface of the porous polymer support will not be sufficiently hydrophilized, resulting in problems such as the ion exchange resin solution not filling the pores of the porous polymer support. If immersion is performed for more than 10 minutes, problems such as a decrease in production rate and an increase in production costs may occur.

[0053] As described above, the ion exchange resin solution may fill the pores of the porous polymer support through immersion, resulting in a form where the pores are filled. Alternatively, the ion exchange resin may encase the outer surface of the porous polymer support.

[0054] Furthermore, during the hydrophilization stage, drying can be performed immediately after immersion, either at a temperature of 40 to 90°C for 1 to 20 minutes, or at a temperature of 40 to 80°C for 1 to 10 minutes.

[0055] On the other hand, the surfactant solution contains 0.001 to 6% by weight of the surfactant and the remainder of the solvent, or 0.01 to 4% by weight of the surfactant and the remainder of the solvent, or 0.05 to 3% by weight of the surfactant and the remainder of the solvent.

[0056] If the surfactant is present in the surfactant solution at a concentration of less than 0.001% by weight, the surface of the porous polymer support may not become hydrophilic, and the ion exchange resin solution may not fill the pores of the substrate. If the concentration exceeds 6% by weight, the surfactant may seep out, or the amount of ion exchange resin filling may decrease.

[0057] Any known surfactant can be used without restriction, but for example, one or more materials selected from dodecylbenzenesulfonic acid (DBSA), alkylbenzenesulfonic acid (ABS), linear alkylbenzenesulfonic acid (LAS), alphasulfonic acid (AS), alphaolefinsulfonic acid (AOS), alcohol polyoxyethylene ether (AE), and alcohol polyoxyethyl ethersulfonic acid (AES) may be used. For example, dodecylbenzenesulfonic acid can be used as the surfactant.

[0058] If the hydrophobic portion of the surfactant is bonded to the surface of the hydrophobic porous polymer support through a hydrophobic-hydrophobic interaction, the hydrophilic portion of the surfactant will hydrophilize the surface of the porous polymer support instead. Here, the surfactant hydrophilizes not only the outer surface of the porous polymer support but also the entire inner pore surface. However, this step may be omitted if the degree of hydrophilization of the porous polymer support is sufficient, or if the pores of the porous polymer support are large enough to be filled with the anion exchange polymer forming composition.

[0059] Next, an anion exchange polymer-forming composition is produced, which is an ion exchange resin solution containing a crosslinkable monomer represented by chemical formula 1, an ionic monomer represented by chemical formula 2, a photoinitiator, and a solvent, all of which are electrolyte monomers having a cation group.

[0060] By irradiating an ion exchange resin solution with ultraviolet light, a crosslinkable monomer represented by chemical formula 1 and an ionic monomer represented by chemical formula 2, both of which are electrolyte monomers having a cationic group, are crosslinked to form a crosslinked product.

[0061] In this specification, "crosslinked product" means a polymer obtained by crosslinking and polymerizing a crosslinkable monomer represented by chemical formula 1 and an ionic monomer represented by chemical formula 2, as well as initial reaction products, intermediate reaction products, final reaction products, and unreacted materials.

[0062] The total content of the crosslinkable monomer represented by chemical formula 1, the ionic monomer represented by chemical formula 2, and the type and content of the photoinitiator are the same as those described above, so the following explanation is omitted.

[0063] The solvent can be any solvent available in the art, but may be a water-soluble solvent such as water, methanol, or ethanol, or distilled water. The solvent may be present in the anion exchange polymer-forming composition in the amount remaining after excluding the crosslinkable monomer represented by chemical formula 1, the ionic monomer represented by chemical formula 2, and the photoinitiator.

[0064] A polyester film is pressed onto at least one surface of a porous polymer support filled with the aforementioned composition to produce a laminate in which the polyester film and the porous polymer support are laminated.

[0065] The polyester film is pressed onto the upper and / or lower surface of a porous polymer support by roll carating. The polyester film is, for example, a polyethylene terephthalate film.

[0066] The thickness of the polyester film is 10 μm to 150 μm, for example, 20 μm to 120 μm or 30 μm to 100 μm. If the thickness of the polyester film is less than 10 μm, lamination defects such as wrinkles in the film may occur when laminating with a support filled with anion exchange polymer. If the thickness of the polyester film exceeds 150 μm, the thickness of the polyester film may be excessively large during the crosslinking reaction described later, and light may not be sufficiently irradiated onto the porous polymer support, potentially preventing the crosslinking reaction from occurring sufficiently.

[0067] The polyester film may have one surface in contact with the porous polymer support that is either untreated or treated for mold release. Using such a film prevents bonding between the polyester film and the hydrophilic anion exchange polymer, thus preventing the anion exchange polymer from being removed from the support surface. The bonding can be performed at a temperature of 10°C to 35°C, for example, 15°C to 30°C, at a pressure of approximately 0 bar to 5 bar. The pressure is adjusted appropriately considering the thickness of the porous polymer support and the polyester film.

[0068] Next, the laminate is irradiated with light to cause a crosslinking reaction of the composition, forming an anion exchange polymer, which is a crosslinking product of the composition, on the surface and inside the pores of the porous polymer support.

[0069] In the process of forming the anion exchange polymer, the light used is ultraviolet light. For example, UVA, UVB, UVC, and / or UVV are used.

[0070] Using UVC as the aforementioned light source, 2000 mJ / cm² 2 or 10,000 mJ / cm² 2 The process may include setting the light intensity and performing the irradiation. For example, using UVC as the light, the intensity may be 2000 mJ / cm². 2 or 8000 mJ / cm² 2 This is done with a light intensity of [specified]. When light irradiation is performed under these conditions, an ion exchange membrane with improved ion exchange capacity can be manufactured.

[0071] Finally, the polyester film is peeled off the porous polymer support, on which the anion exchange polymer is formed on the surface and inside the pores, to produce an anion exchange membrane. The peeling is performed by pulling the polyester film attached to the porous polymer support in the opposite direction using a detachment roll.

[0072] The anion exchange membrane produced by the above-described manufacturing method comprises a porous polymer support; and an anion exchange polymer, which is an ion exchange resin that fills the pores of the porous polymer support and encloses the outer surface of the substrate.

[0073] The anion exchange membrane has an average thickness of 10 to 200 μm, for example, 12 to 150 μm. If the average thickness is less than 10 μm, the durability of the anion exchange membrane decreases, there is a risk of membrane damage during operation, and the desalination and concentration performance decreases due to the permeation of unwanted salts. If it exceeds 200 μm, the sheet resistance is high, the power consumption required for operation is large, and the desalination and concentration performance may decrease.

[0074] Furthermore, the ion exchange capacity (IEC) of the anion exchange membrane is 1.5 meq / g or higher, or 1.6 meq / g or higher.

[0075] In the present invention, "substitution" is induced by the exchange of one or more hydrogen atoms in the unsubstituted mother group with other atoms or functional groups. Unless otherwise stated, when a functional group is considered to be "substituted," it means that the functional group is substituted with at least one substituent selected from C1 to C20 alkyl groups, C2 to C20 alkenyl groups, C2 to C20 alkynyl groups, C3 to C30 cycloalkyl groups, C3 to C30 cycloalkenyl groups, and C6 to C40 aryl groups. When a functional group is described as "selectively substituted," it means that the functional group can be substituted with the substituents described above.

[0076] In this specification, C1 to C20 alkyl groups refer to linear alkyl groups such as methyl, ethyl, hexyl, octyl, and decyl groups; branched alkyl groups such as isopropyl, tert-butyl, neopentyl, and hexyl groups; and so on. Of these, methyl or ethyl groups may be used, depending on the ease of preparation of the raw materials and the usefulness of the product. One or more hydrogen atoms in the alkyl group can be substituted with substituents as defined in the "substitution" section above.

[0077] In this specification, C3 to C30 cycloalkyl groups refer to cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. One or more hydrogen atoms in the cycloalkyl group can be substituted with substituents as defined above in "Substitution".

[0078] In this specification, a C5 to C40 aryl group means an aromatic system containing one or more benzene rings, such as a phenyl group or a naphthyl group. One or more hydrogen atoms in the aryl group can be substituted with substituents as defined above in "Substitution".

[0079] Examples of halogen anions used herein include F-, Cl-, Br-, and I-.

[0080] The present invention will be described below with reference to the following examples. These examples are provided for illustrative purposes only, and the scope of the present invention is not limited by them. [Examples]

[0081] [Examples] Manufacturing Example 1: Production of Crosslinkable Monomers A solution of 1,4-diazabaicyclo[2,2,2]octane dissolved in methanol was mixed with a solution of 4-vinylbenzyl chloride dissolved in ethyl acetate, so that the molar ratio of vinylbenzyl chloride to 1,4-diazabaicyclo[2,2,2]octane was 2:1. The mixture was stirred at room temperature under an inert atmosphere to produce a mixture. The mixture was filtered and washed with methanol, and then dried under vacuum at room temperature (25°C) to obtain a crosslinkable monomer represented by the following chemical formula 1-1. [ka]

[0082] Example 1: Production of anion exchange membrane A 100 μm thick porous polymer support made of polypropylene (PP) with a porosity of 51% was prepared. The porous polymer support was immersed in a 1% by weight aqueous solution of dodecylbenzenesulfonic acid for 10 minutes, and then dried in a 70°C hot air oven for 10 minutes to make it hydrophilic. The hydrophilized porous polymer support was then immersed in an anion exchange polymer-forming composition, which is an ion exchange resin solution, for 5 minutes to fill the porous polymer support with the ion exchange resin solution.

[0083] At this time, the composition for forming the anion exchange polymer was prepared by mixing 20% ​​by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1, 40% by weight of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer, 0.5% by weight of the 2-hydroxy-2-methylpropiophenone (manufactured by Ciba) photoinitiator, and the remaining amount of distilled water.

[0084] The polypropylene porous polymer support was impregnated with the anion exchange polymer forming composition, filling the surface and pores of the porous polymer support with the composition. The porous polymer support filled with the composition was placed in a pressure roll, and a 50 μm thick polyester film was pressed onto the upper and lower surfaces of the porous polymer support at room temperature (25°C) to produce a laminate in which the polyester film and the porous polymer support were laminated. 3000 mJ / cm³ was applied to the laminate. 2 An anion exchange polymer, which is a crosslinking product of the composition, was formed on the surface and inside the pores of the porous polymer support by irradiation with UVC ultraviolet light. The polyester film was peeled off from the porous polymer support on which the anion exchange polymer had been formed on the surface and inside the pores to produce an anion exchange membrane.

[0085] Example 2: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 40% by weight of (2-acryloyloxyethyl)trimethylammonium chloride was used as the ionic monomer in the composition for forming an anion exchange polymer.

[0086] Example 3: Manufacturing of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 40% by weight of (3-acrylamidopropyl)trimethylammonium chloride was used as the ionic monomer in the composition for forming an anion exchange polymer.

[0087] Example 4: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 40% by weight of 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride was used as the ionic monomer in the composition for forming an anion exchange polymer.

[0088] Example 5: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 40% by weight of (vinylbenzyl)trimethylammonium chloride was used as the ionic monomer in the composition for forming an anion exchange polymer.

[0089] Example 6: Production of anion exchange membrane An anion exchange membrane was manufactured in the same manner as in Example 1, except that a 60 μm thick porous polymer support (porosity: 55%) was used.

[0090] Example 7: Production of anion exchange membrane An anion exchange membrane was manufactured in the same manner as in Example 1, except that a 125 μm thick porous polymer support made of polyvinyl alcohol (PVA) (porosity: 75%) was used.

[0091] Example 8: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 50% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 10% by weight of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0092] Example 9: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 50% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 10% by weight of the (2-acryloyloxyethyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0093] Example 10: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 50% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 10% by weight of the (3-acrylamidopropyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0094] Example 11: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 50% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 10% by weight of the 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0095] Example 12: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 50% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 10% by weight of the (vinylbenzyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0096] Example 13: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 10% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 50% by weight of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0097] Example 14: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 10% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 50% by weight of the (2-acryloyloxyethyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0098] Example 15: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 1, except that 10% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 50% by weight of the (3-acrylamidopropyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0099] Example 16: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 13, except that 10% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 50% by weight of the 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0100] Example 17: Production of anion exchange membrane An anion exchange membrane was prepared in the same manner as in Example 13, except that 10% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 50% by weight of the (vinylbenzyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0101] Comparative Example 1: Manufacturing of anion exchange membranes An anion exchange membrane was prepared in the same manner as in Example 1, except that 60% by weight of only the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 was used in the composition for forming an anion exchange membrane, without the use of ionic monomers.

[0102] Comparative Example 2: Manufacturing of anion exchange membranes An anion exchange membrane was prepared in the same manner as in Example 1, except that 6% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 54% by weight of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0103] Comparative Example 3: Manufacturing of anion exchange membranes An anion exchange membrane was prepared in the same manner as in Example 1, except that 55% by weight of the crosslinkable monomer of chemical formula 1-1 obtained in Production Example 1 and 5.5% by weight of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0104] Evaluation Example 1: Evaluation of the physical properties of ion exchange membranes The anion exchange membranes produced in Examples 1 to 7 and Comparative Examples 1 to 3 were experimentally evaluated for their physical properties using the method described below, and the evaluation results are shown in Table 1 below.

[0105] (1) Sheet resistance (Ω·cm) 2 ) Each anion exchange membrane was cut into 5cm x 5cm pieces to prepare samples. The samples were immersed in a 0.5M NaCl aqueous solution for 24 hours. The samples were then positioned between electrodes for sheet resistance measurement, and the wire resistance (R) of the anion exchange membrane was measured using an LCR meter (E4908A, Agilent). 11 ), the resistance (R) of a 0.5M NaCl aqueous solution 12 The measured resistance value (R) was measured. 11 , R 12 Substitute ) into the following equation 1 to obtain the sheet resistance (R m ) was sought.

[0106] [Formula 1] R m (Ω·cm 2 )=(R 11 -R 12 )×S During the ceremony, R m This is the sheet resistance of the anion exchange membrane, R 11 This is the wire resistance of the anion exchange membrane, R 12 This is the resistance of a 0.5M NaCl aqueous solution. S is the area of ​​the electrode. (2) Ion exchange capacity (IEC, meq / g)

[0107] Each anion exchange membrane was cut to a size of 5 cm x 5 cm to prepare samples. The samples were washed with distilled water, and excess water was removed with tissue paper. After filling a vial with 70 ml of 1 M NaCl solution, the dehydrated samples were placed in the 1 M NaCl solution and immersed for at least 12 hours for primary pretreatment. Next, the samples that had undergone primary pretreatment were washed several times with distilled water, and excess water was removed with tissue paper. After filling a vial with 70 ml of 0.5 M Na2CO3 solution, the dehydrated samples were placed in the 0.5 M Na2CO3 solution and immersed for at least 12 hours for secondary pretreatment. Next, the samples that had undergone secondary pretreatment were removed from the vial, and the remaining solution was titrated with 0.01 M AgNO3 solution, and the volume of AgNO3 solution added during titration was recorded. After washing the samples several times with distilled water, they were dried in an 80°C hot air oven for 15 minutes. After drying was complete, the weight of the dried anion exchange membrane was measured. The measured weight of the dried anion exchange membrane was substituted into Equation 2 below to determine the ion exchange capacity (IEC).

[0108] [Formula 2] IEC (meq / g) = (volume of titration reagent (ml) × 0.01) / weight of dried anion exchange membrane (g)

[0109] (3) Appearance evaluation

[0110] The appearance of each anion exchange membrane was observed with the naked eye and evaluated according to the following criteria. • Good: No cracks or peeling occurred on the surface. • Defect: Cracks or peeling occur on the surface. [Table 1]

[0111] Referring to Table 1, the anion exchange membranes of Examples 1 to 17 have a sheet resistance of 6 Ω·cm. 2 The following results show that the ion exchange capacity is excellent at 1.5 meq / g or more, and the appearance is good. In contrast, the ion exchange membrane of Comparative Example 1, which does not use ionic monomers, has a sheet resistance of 6.3 Ω·cm. 2 The ion exchange membrane of Comparative Example 2, which used the anion exchange polymer forming composition obtained by Production Example 1 with a weight ratio of 1:9 between the crosslinkable monomer and ionic monomer of chemical formula 1-1, had a low ion exchange capacity of 1.4 meq / g, and showed poor appearance due to electrolyte peeling on the surface. The ion exchange membrane of Comparative Example 3, which used the anion exchange polymer forming composition obtained by Production Example 1 with a weight ratio of 1:0.1 between the crosslinkable monomer and ionic monomer of chemical formula 1-1, had a sheet resistance of 6.1 Ω·cm. 2 The price is high, and it is clear that cracks have formed on the surface, resulting in a poor appearance.

[0112] As a result, the anion exchange membranes of Examples 1 to 17 can provide anion exchange membranes with high ion exchange capacity and good appearance.

[0113] The above describes in detail an exemplary example with reference to the attached drawings, but the original idea is not limited to these examples. It is clear that any person with ordinary skill in the art to which this original idea belongs can derive various modifications or alterations within the scope of the technical idea described in the claims, and it goes without saying that these also fall within the technical scope of this original idea. [Explanation of Symbols]

[0114] 20: porous polymer support, 21: Stomata, 30: Anion exchange polymer main chain having a cationic functional group, 31: Anion exchange polymer

Claims

1. A porous polymer support, An electrolyte containing an anion exchange polymer, The electrolyte is located in at least a portion of the surface and interior of the pores of the porous polymer support. The anion exchange polymer is a crosslinked product of a composition containing a crosslinkable monomer represented by the following chemical formula 1 and an ionic monomer represented by the following chemical formula 2, for an anion exchange membrane: 【Chemistry 1】 Of the chemical formulas, X － It is a halogen anion; Of the chemical formulas, A is 【Chemistry 2】 And here, R ａ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R １ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group; R ２ , R ３ These are, independently of each other, substituted or unsubstituted C1 to C20 alkyl groups, or substituted or unsubstituted C5 to C40 aryl groups; R ４ These are substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, or substituted or unsubstituted C6 to C30 aryl groups; p is either 0 or 1; q is an integer between 0 and 6; r is an integer from 0 to 6; and Y － It is a halogen anion.

2. Of the chemical formula 2 mentioned above, The aforementioned R ４ The anion exchange membrane according to claim 1, wherein is a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

3. Of the chemical formula 2 mentioned above, The aforementioned A is -O-; Said R ４ is a substituted or unsubstituted C1 to C5 alkyl group or a substituted or unsubstituted C6 to C15 aryl group, and the anion exchange membrane according to Claim 1.

4. The aforementioned ionic monomer is (3-acrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium bromide, (3-acrylamidopropyl)trimethylammonium iodide; (3-methacryloylamidopropyl)trimethylammonium chloride, (3-methacryloylamidopropyl)trimethylammonium bromide, (3-methacryloylamidopropyl)trimethylammonium iodide; (2-Acryloyloxyethyl)trimethylammonium chloride, (2-Acryloyloxyethyl)trimethylammonium bromide, (2-Acryloyloxyethyl)trimethylammonium iodide; (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide; N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium bromide, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium iodide; Benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium bromide, benzyldimethyl[2-(2-methyl-1-oxoaryl)oxyethyl]ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(2-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(3-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(3,5-dimethylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(4-isopropylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(4-(tert-butyl)benzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N-(3,5-di-tert-butylbenzyl)-N,N-dimethylethane-1-ammonium iodide; 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalene-1-ylmethyl)ethane-1-ammonium iodide; 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide; (Vinylbenzyl)trimethylammonium chloride, (Vinylbenzyl)trimethylammonium bromide, (Vinylbenzyl)trimethylammonium iodide; and An anion exchange membrane according to claim 1, comprising (2-methylvinylbenzyl)trimethylammonium chloride, (2-methylvinylbenzyl)trimethylammonium bromide, and (2-methylvinylbenzyl)trimethylammonium iodide.

5. The anion exchange membrane according to claim 1, wherein the weight ratio of the crosslinkable monomer to the ionic monomer is 1:0.2 to 1:

8.

6. The anion exchange membrane according to claim 1, wherein the total content of the crosslinkable monomer and the ionic monomer is 30% to 85% by weight based on 100% by weight of the entire composition.

7. The composition further comprises a photoinitiator, The anion exchange membrane according to claim 1, wherein the content of the photoinitiator is 0.01% to 2% by weight based on 100% by weight of the entire composition.

8. The anion exchange membrane according to claim 1, wherein the porous polymer support is a membrane structure, a nonwoven fabric structure, a woven fabric structure, or a mesh structure.

9. The anion exchange membrane according to claim 1, wherein the porous polymer support comprises one or more polymers selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyetheretherketone, polyethersulfone, polysulfone, polystyrene, polyaryleneethersulfone, and polyetherketone.

10. The anion exchange membrane according to claim 1, wherein the porosity of the porous polymer support is 30% to 80%, and the thickness of the porous polymer support is 10 μm to 150 μm.

11. The sheet resistance (R) of the anion exchange membrane according to the following formula 1. ｍ ) is 6Ω·cm ２ The anion exchange membrane according to claim 1 is as follows: [Formula 1] R ｍ (Ω・cm ２ )=(R １１ -R １２ )×S During the ceremony, R ｍ This is the sheet resistance of the anion exchange membrane, R １ 1 is the wire resistance of the anion exchange membrane, R １２ This is the resistance of a 0.5 M NaCl aqueous solution. S is the area of ​​the electrode.

12. The anion exchange membrane according to claim 1, wherein the ion exchange capacity (IEC) of the anion exchange membrane is 1.5 meq / g or more.

13. The anion exchange membrane according to claim 1, wherein the anion exchange membrane is used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or a water electrolysis system.

14. The steps of providing a porous polymer support and A step of producing a composition for forming an anion exchange polymer, comprising a crosslinkable monomer represented by the following chemical formula 1, an ionic monomer represented by the following chemical formula 2, a photoinitiator, and a solvent; The steps include impregnating the porous polymer support with the anion exchange polymer forming composition to fill at least a portion of the surface and interior of the pores of the porous polymer support with the composition, A step of manufacturing a laminate in which a polyester film and the porous polymer support are laminated, by pressing a polyester film onto at least one surface of a porous polymer support filled with the aforementioned composition, The steps include: irradiating the laminate with light to cause a crosslinking reaction of the composition to form an anion exchange polymer, which is a crosslinking product of the composition, on at least a portion of the surface and interior of the pores of the porous polymer support; A method for producing an anion exchange membrane according to any one of claims 1 to 13, comprising the step of peeling off the polyester film from a porous polymer support on which the anion exchange polymer is formed in at least a portion of the surface and the interior of the pores to produce an anion exchange membrane: 【Transformation 3】 Of the chemical formulas, X － It is a halogen anion; Of the chemical formulas, A is 【Chemistry 4】 And here, R ａ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R １ is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group; R ２ , R ３ These are, independently of each other, substituted or unsubstituted C1 to C20 alkyl groups, or substituted or unsubstituted C5 to C40 aryl groups; R ４ These are substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, or substituted or unsubstituted C5 to C30 aryl groups; p is either 0 or 1; q is an integer between 0 and 6; r is an integer from 0 to 6; and Y － It is a halogen anion.

15. In the step of forming the anion exchange polymer, the light is ultraviolet light. The aforementioned light was applied at a rate of 2000 mJ / cm². ２ or 10,000 mJ / cm ２ A method for producing an anion exchange membrane according to claim 14, comprising the step of irradiating with a light intensity of .

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