Anion exchange membrane and method for manufacturing same

Abstract

Disclosed are an anion exchange membrane and a method for manufacturing same. The anion exchange membrane comprises: a porous polymer support; and an electrolyte containing an anion exchange polymer. The electrolyte may be disposed on at least a portion of a porous polymer support surface and pore interiors, and the anion exchange polymer may be a cross-linked product of a composition including a cross-linkable monomer represented by chemical formula 1 and an ionic monomer represented by chemical formula 2. [Chemical formula 1] [Chemical formula 2] In chemical formulae 1 and 2, A, R1, R2, R3, R4, X-, Y-, p, q, and r are as defined in the specification.

Description

Anion exchange membrane and its manufacturing method

[0001] The present disclosure relates to an anion exchange membrane and a method for manufacturing the same.

[0002] An ion exchange membrane is a synthetic resin membrane that selectively allows the passage of cations and anions, with only one side permeating. Cation exchange membranes, possessing negatively charged functional groups, selectively allow cations to pass through, while anion exchange membranes, conversely, possess positively charged functional groups, selectively allow anions to pass through. Ion exchange membranes typically require high permeability selectivity, low electrical resistance, excellent mechanical strength, and high chemical stability.

[0003] These anion exchange membranes can be applied to water treatment systems such as electrodialysis, bipolar membrane electrodialysis, capacitive desalination, and electrodeionization, or to systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries. Systems that apply anion exchange membranes can apply acidic or alkaline raw water to the process, and acids or alkalis may be generated during the process operation of the raw water. Perfluorinated anion exchange membranes can be used as anion exchange membranes, but hydrocarbon anion exchange membranes are applied in actual systems due to their high price. However, hydrocarbon anion exchange membranes have limitations in the application process and conditions due to chemical resistance issues. In addition, anion exchange membranes that include a support have a certain proportion of support fraction within the membrane, so there is a limit to increasing the ion exchange capacity to improve the membrane properties.

[0004] According to one aspect, the electrolyte content in the ion exchange membrane is increased to provide an anion exchange membrane with high ion exchange capacity and excellent appearance.

[0005] According to another aspect, a method for manufacturing the above-described anion exchange membrane is provided.

[0006] According to one aspect,

[0007] porous polymer support; and

[0008] An electrolyte containing an anion exchange polymer;

[0009] The electrolyte is located on at least a portion of the surface and interior of the pores of the porous polymer support,

[0010] The anion exchange polymer is provided as an anion exchange membrane which is a crosslinked product of a composition comprising a crosslinkable monomer represented by the following chemical formula 1 and an ionic monomer represented by the following chemical formula 2:

[0011] [Chemical Formula 1] [Chemical Formula 2]

[0012]

[0013] In chemical formula 1,

[0014] X - is a halogen anion;

[0015] In chemical formula 2,

[0016] A is -O-, , or 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;

[0017] R1 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group;

[0018] R2, R3 are independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group;

[0019] R4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C5 to C30 aryl group;

[0020] p is 0 or 1;

[0021] q is an integer from 0 to 6;

[0022] r is an integer from 0 to 6; and

[0023] Y - is a halogen anion.

[0024] In the above chemical formula 2,

[0025] The above R4 may be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0026] In the above chemical formula 2,

[0027] The above A is -O-;

[0028] The above R4 may be a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C15 aryl group.

[0029] The above ionic monomer is

[0030] (3-acrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium bromide, (3-acrylamidopropyl)trimethylammonium iodide;

[0031] (3-methacryloylamidopropyl)trimethylammonium chloride, (3-methacryloylamidopropyl)trimethylammonium bromide, (3-methacryloylamidopropyl)trimethylammonium iodide;

[0032] (2-acryloyloxyethyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium bromide, (2-acryloyloxyethyl)trimethylammonium iodide;

[0033] (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide;

[0034] 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;

[0035] Benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium bromide, benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium iodide;

[0036] 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;

[0037] 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;

[0038] 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;

[0039] 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;

[0040] 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;

[0041] 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;

[0042] 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;

[0043] 2-(Acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium iodide;

[0044] 2-(Acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide;

[0045] (Vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium bromide, (vinylbenzyl)trimethylammonium iodide; and

[0046] (2-methylvinylbenzyl)trimethylammonium chloride, (2-methylvinylbenzyl)trimethylammonium bromide, (2-methylvinylbenzyl)trimethylammonium iodide;

[0047] The weight ratio of the crosslinking monomer and the ionic monomer may be 1:0.2 to 1:8.

[0048] The total content of the crosslinking monomer and the ionic monomer may be 30 wt% to 85 wt% based on 100 wt% of the entire composition.

[0049] The above composition further comprises a photoinitiator,

[0050] The content of the photoinitiator may be 0.01 wt% to 2 wt% based on 100 wt% of the entire composition.

[0051] The above porous polymer support may be a membrane structure, a non-woven structure, a fabric structure, or a mesh structure.

[0052] The above porous polymer support may include one or more polymers selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyetheretherketone, polyethersulfone, polysulfone, polystyrene, polyaryleneethersulfone, and polyetherketone.

[0053] The porosity of the porous polymer support may be 30% to 80%, and the thickness of the porous polymer support may be 10 ㎛ to 150 ㎛.

[0054] The surface resistance (R) of the above anion exchange membrane according to the following equation 1 m ) may be less than 6 Ω·㎠:

[0055] [Formula 1]

[0056] R m (Ω·㎠) = (R 11 - R 12 ) x S

[0057] Among the foods,

[0058] R m is the surface resistance of the anion exchange membrane,

[0059] R 11 is the line resistance of the anion exchange membrane,

[0060] R 12 is the resistance of 0.5 M NaCl aqueous solution,

[0061] S is the area of ​​the electrode.

[0062] The ion exchange capacity (IEC) of the above anion exchange membrane may be 1.5 meq / g or more.

[0063] The above anion exchange membrane can be used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis.

[0064] Depending on other aspects,

[0065] A step of providing a porous polymer support;

[0066] A step of preparing a composition for forming an anion exchange polymer, comprising a crosslinking monomer represented by the following chemical formula 1, an ionic monomer represented by the following chemical formula 2, a photoinitiator, and a solvent;

[0067] A step of impregnating the porous polymer support with the composition for forming the anion exchange polymer and filling at least a portion of the surface and the interior of the pores of the porous polymer support with the composition;

[0068] A step of pressing a polyester film onto at least one side of a porous polymer support filled with the above composition to produce a laminate in which the polyester film and the porous polymer support are combined;

[0069] A step of irradiating light on the laminate and crosslinking 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 the interior of the pores of the porous polymer support; and

[0070] A method for manufacturing an anion exchange membrane is provided, including a step of manufacturing an anion exchange membrane by peeling off the polyester film from a porous polymer support in which the anion exchange polymer is formed on at least a portion of the surface and the interior of the pores;

[0071] [Chemical Formula 1] [Chemical Formula 2]

[0072]

[0073] In chemical formula 1,

[0074] X - is a halogen anion;

[0075] In chemical formula 2,

[0076] A is -O-, , or 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;

[0077] R1 is hydrogen or a substituted or unsubstituted C1 to C20 alkyl group;

[0078] R2, R3 are independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group;

[0079] R4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C5 to C30 aryl group;

[0080] p is 0 or 1;

[0081] q is an integer from 0 to 6;

[0082] r is an integer from 0 to 6; and

[0083] Y - is a halogen anion.

[0084] In the step of forming the above anion exchange polymer, the light may be ultraviolet rays, and the process may include irradiating the light with a light amount of 2000 mJ / cm2 to 10000 mJ / cm2.

[0085] An anion exchange membrane according to one aspect comprises an electrolyte comprising an anion exchange polymer, which is a crosslinked product of a composition comprising a porous polymer support and a crosslinkable monomer represented by the above chemical formula 1 and an ionic monomer represented by the above chemical formula 2. The electrolyte surrounds at least a portion of the surface of the porous support and the interior of the pores. As a result, the content of the electrolyte in the anion exchange membrane is increased, thereby increasing the ion exchange capacity and improving the performance of the anion exchange membrane.

[0086] Figure 1 is a schematic diagram of an anion exchange membrane according to one embodiment.

[0087] Hereinafter, an anion exchange membrane and a manufacturing method thereof according to an embodiment will be described in more detail.

[0088] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including its definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein. As used herein, the term "comprising" does not exclude other components unless specifically stated to the contrary, but rather includes other components. As used herein, the term "a combination thereof" means a mixture or combination of one or more of the listed components. As used herein, the term "and / or" means any and all combinations of one or more of the associated listed items. As used herein, the term "or" means "and / or." The expressions "at least one" or "one or more" preceding elements herein are intended to supplement the entire list of components and not to supplement individual components described above. When an element is referred to herein as being disposed "on" or "over" another element, the element may be disposed directly on the other element, or there may be intervening elements between the elements. Conversely, when an element is referred to as being disposed "directly on" or "directly over" another element, there may not be intervening elements. As used herein, "~-based resin", "~-based polymer", "~-based polymer", or / and "~-based copolymer" are broad concepts that include all of "~ resin", "~ polymer", "~-based polymer", "~ copolymer", or / and "~ resin, polymer, polymer, or copolymer derivatives."In this specification, the term "a polymer or copolymer crosslinked with these resins" means "a polymer or copolymer crosslinked with the aforementioned resins."

[0089] A typical anion exchange membrane has a structure in which an anion exchange polymer with cationic functional groups is positioned on a support. Anion exchange membranes require high anion selectivity, low electrical resistance, excellent mechanical strength, and chemical stability.

[0090] Known anion exchange membranes include perfluorinated anion exchange membranes and hydrocarbon anion exchange membranes. Among these, hydrocarbon anion exchange membranes are less expensive than perfluorinated anion exchange membranes but lack sufficient chemical resistance. Furthermore, anion exchange membranes utilizing supports typically contain a certain amount of support, limiting their ability to increase ion exchange capacity for purposes such as concentration and desalination.

[0091] The present inventors have solved the above-described problems and provided an anion exchange membrane with excellent appearance by increasing the electrolyte content in the ion exchange membrane.

[0092] An anion exchange membrane according to one embodiment 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 the interior of the pores of the porous polymer support, and the anion exchange polymer may be a crosslinked product of a composition comprising a crosslinkable monomer represented by the following chemical formula 1 and an ionic monomer represented by the following chemical formula 2:

[0093] [Chemical Formula 1] [Chemical Formula 2]

[0094]

[0095] In chemical formula 1,

[0096] X - may be a halogen anion;

[0097] In chemical formula 2,

[0098] A is -O-, , or It can be, and here R a may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group;

[0099] R1 may be hydrogen or a substituted or unsubstituted C1 to C20 alkyl group;

[0100] R2 and R3 can be independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group;

[0101] R4 may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C5 to C30 aryl group;

[0102] p can be 0 or 1;

[0103] q can be an integer from 0 to 6;

[0104] r can be an integer from 0 to 6; and

[0105] Y - may be a halogen anion.

[0106] In the ionic monomer represented by chemical formula 2, the vinyl group is a functional group capable of cross-linking with the cross-linkable monomer represented by chemical formula 1.

[0107] An anion exchange membrane according to one embodiment can have lower surface resistance and superior appearance compared to an anion exchange membrane including an anion exchange polymer manufactured using a crosslinking monomer represented by chemical formula 1 without an ionic monomer.

[0108] For example, in chemical formula 2, R4 can be a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

[0109] For example, in chemical formula 2, A may be -O-; and R4 may be a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C15 aryl group.

[0110] For example, the above ionic monomer

[0111] (3-acrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium bromide, (3-acrylamidopropyl)trimethylammonium iodide;

[0112] (3-methacryloylamidopropyl)trimethylammonium chloride, (3-methacryloylamidopropyl)trimethylammonium bromide, (3-methacryloylamidopropyl)trimethylammonium iodide;

[0113] (2-acryloyloxyethyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium bromide, (2-acryloyloxyethyl)trimethylammonium iodide;

[0114] (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide;

[0115] 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;

[0116] Benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium bromide, benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium iodide;

[0117] 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;

[0118] 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;

[0119] 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;

[0120] 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;

[0121] 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;

[0122] 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;

[0123] 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;

[0124] 2-(Acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium iodide;

[0125] 2-(Acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide;

[0126] (Vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium bromide, (vinylbenzyl)trimethylammonium iodide; and

[0127] (2-methylvinylbenzyl)trimethylammonium chloride, (2-methylvinylbenzyl)trimethylammonium bromide, (2-methylvinylbenzyl)trimethylammonium iodide;

[0128] For example, the ionic monomers may 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-oxoallyl)oxyethyl]ammonium chloride, (vinylbenzyl)trimethylammonium chloride, and (2-methylvinylbenzyl)trimethylammonium chloride.

[0129] The weight ratio of the crosslinking monomer to the ionic monomer may be 1:0.2 to 1:8. For example, the weight ratio of the crosslinking monomer to the ionic monomer may be 1:0.2 to 1:5 or 1:0.5 to 1:5. When the weight ratio of the crosslinking monomer to the ionic monomer is within the above range, the anion exchange performance of the anion exchange membrane may be improved without deteriorating the solubility characteristics of the composition for forming an anion exchange polymer.

[0130] The total content of the crosslinking monomer and the ionic monomer may be 30 wt% to 85 wt% based on 100 wt% of the total composition. For example, the total content of the crosslinking monomer and the ionic monomer may be 35 wt% to 80 wt% or 40 wt% to 75 wt% based on 100 wt% of the total composition. If the total content of the crosslinking monomer and the ionic monomer is less than 30 wt%, the anion exchange performance of the anion exchange membrane may be reduced, and if it is more than 85 wt%, the solubility of the monomer constituting the anion exchange polymer may be reduced when preparing an electrolyte solution of the composition.

[0131] The composition further comprises a photoinitiator, and the content of the photoinitiator may be 0.01 wt% to 2 wt% based on 100 wt% of the total composition. The photoinitiator may be any photoinitiator usable in the art without limitation, but may be, for example, 2-hydroxy-2-methylpropiophenone. For example, the content of the photoinitiator may be 0.1 wt% to 1 wt% based on 100 wt% of the total composition.

[0132] Figure 1 is a schematic diagram of an anion exchange membrane according to one embodiment.

[0133] Referring to FIG. 1, an anion exchange membrane (40) according to one embodiment has an anion exchange polymer (31) having a cationic functional group positioned on the surface of a porous polymer support (20) and within the pores (21). The anion exchange polymer (31) having a cationic functional group is uniformly distributed on the surface of the porous polymer support (20) and within the pores (21), thereby obtaining a homogeneous anion exchange membrane (40). This anion exchange membrane (40) structure can have low surface resistance and high ionic conductivity. In addition, the porous polymer support (20) can improve mechanical durability and have high dimensional stability.

[0134] The porous polymer support (20) may be in the form of a sponge or a three-dimensional network. The porous polymer support (20) may be a membrane structure, a non-woven structure, a fabric structure, or a mesh structure.

[0135] The porous polymer support (20) may include 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) may include one or more polymers selected from polyethylene, polypropylene, and polyvinyl alcohol.

[0136] The porosity of the porous polymer support (20) may be 30% to 80%. Here, % represents volume %. The pore size of the porous polymer support (20) represents the average diameter when the pores are spherical, and represents the major axis length when the pores are non-spherical. The porosity and pore size of the porous polymer support (20) can be measured using the BET method and / or surface SEM images, and the porosity can be obtained through the area ratio in cross-sectional SEM image analysis. The porosity can also be obtained by calculation using the basis weight and thickness.

[0137] The thickness of the porous polymer support may be 10 μm to 150 μm. For example, the thickness of the porous polymer support may be 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 surface resistance may be reduced and the ion exchange capacity may be increased.

[0138] The surface resistance (R) of the anion exchange membrane (40) according to the following equation 1 m ) may be less than 6 Ω·㎠:

[0139] [Formula 1]

[0140] R m (Ω·㎠) = (R 11 - R 12 ) x S

[0141] Among the foods,

[0142] Rm can be the surface resistance of the anion exchange membrane,

[0143] R 11 may be the line resistance of the anion exchange membrane,

[0144] R 12 can be the resistance of a 0.5 M NaCl aqueous solution,

[0145] S can be the area of ​​the electrode.

[0146] The ion exchange capacity (IEC) of the anion exchange membrane (40) may be 1.5 meq / g or more.

[0147] The anion exchange membrane (40) can be used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis.

[0148] The anion exchange membrane (40) can also be used in energy systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries.

[0149] According to another embodiment, a method for manufacturing an anion exchange membrane comprises the steps of: providing a porous polymer support; preparing a composition for forming an anion exchange polymer, the composition comprising a crosslinking 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 so as to fill at least a portion of a surface of the porous polymer support and an interior of pores with the composition; pressing a polyester film onto at least one surface of the porous polymer support filled with the composition so as to manufacture a laminate in which the polyester film and the porous polymer support are laminated; irradiating the laminate with light and crosslinking the composition so as to form an anion exchange polymer, which is a crosslinked product of the composition, in at least a portion of a surface of the porous polymer support and an interior of pores; And a step of manufacturing an anion exchange membrane by peeling off the polyester film from the porous polymer support in which the anion exchange polymer is formed on at least a part of the surface and the interior of the pores; the above-described anion exchange membrane is manufactured, including:

[0150] [Chemical Formula 1] [Chemical Formula 2]

[0151]

[0152] In chemical formula 1,

[0153] X - may be a halogen anion;

[0154] In chemical formula 2,

[0155] A is -O-, , or and here R a may be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group;

[0156] R1 may be hydrogen or a substituted or unsubstituted C1 to C20 alkyl group;

[0157] R2 and R3 can be independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group;

[0158] R4 may be a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C5 to C30 aryl group;

[0159] p can be 0 or 1;

[0160] q can be an integer from 0 to 6;

[0161] r can be an integer from 0 to 6; and

[0162] Y - may be a halogen anion.

[0163] First, a porous polymer support is provided.

[0164] The shape, structure, material, porosity, pore size, thickness, etc. of the porous polymer support are the same as described above, so their description is omitted below.

[0165] Before performing the step of immersing the porous polymer support in an anion exchange polymer forming composition, which is an ion exchange resin solution, so that the ion exchange resin solution surrounds the pores and outer surface of the porous polymer support, the method may further include a step of immersing the porous polymer support in a surfactant solution and drying it to make the surface of the porous polymer support hydrophilic.

[0166] 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, and can be omitted if the degree of hydrophilization of the porous polymer support is sufficient or the pores of the substrate are sufficiently large so that the ion exchange resin solution can be filled.

[0167] In the hydrophilization step, 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 may not be sufficiently hydrophilized, which may result in 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 speed and an increase in production costs may occur.

[0168] Through the above-described immersion, the pores of the porous polymer support may be filled with an ion exchange resin solution, resulting in a pore-filled form. Furthermore, the ion exchange resin may be formed to cover the outer surface of the porous polymer support.

[0169] Additionally, in the hydrophilizing step, drying can be performed immediately after immersion, and can be performed 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.

[0170] Meanwhile, the surfactant solution may contain 0.001 to 6 wt% of the surfactant and the remainder of the solvent, or may contain 0.01 to 4 wt% of the surfactant and the remainder of the solvent, or may contain 0.05 to 3 wt% of the surfactant and the remainder of the solvent.

[0171] If the surfactant is included in the surfactant solution in an amount of less than 0.001 wt%, the surface of the porous polymer support may not be hydrophilized, which may cause a problem in which the ion exchange resin solution is not filled into the pores of the substrate. If the surfactant is included in an amount exceeding 6 wt%, the surfactant may be eluted or the ion exchange resin filling amount may be reduced.

[0172] Any known surfactant may be used without limitation, 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), alcoholpolyoxyethyleneether (AE), and alcoholpolyoxyethyleneethersulfonic acid (AES) may be used. For example, dodecylbenzenesulfonic acid may be used as the surfactant.

[0173] When the hydrophobic part of the surfactant is combined with the hydrophobic surface of the hydrophobic porous polymer support through hydrophobic-hydrophobic interaction, the hydrophilic part of the surfactant replaces the surface of the porous polymer support, thereby achieving hydrophilization. Here, not only the outer surface of the porous polymer support but also the entire inner pore surface can be hydrophilized by the surfactant. However, if the degree of hydrophilization of the porous polymer support is sufficient or the pores of the porous polymer support are sufficiently large to be filled with the composition for forming an anion exchange polymer, the surfactant may be omitted.

[0174] Next, a composition for forming an anion exchange polymer is prepared, which is an ion exchange resin solution containing a crosslinking monomer represented by the chemical formula 1, which is an electrolyte monomer having a cationic group, an ionic monomer represented by the chemical formula 2, a photoinitiator, and a solvent.

[0175] By irradiating an ion exchange resin solution with ultraviolet rays, a crosslinking monomer represented by chemical formula 1, which is an electrolyte monomer having a cationic group, and an ionic monomer represented by chemical formula 2 can be crosslinked to form a crosslinked product.

[0176] In this specification, the term “crosslinked product” means a polymer obtained by crosslinking a crosslinkable monomer represented by Chemical Formula 1 and an ionic monomer represented by Chemical Formula 2, and includes all of the initial reaction products, intermediate reaction products, final reaction products, and unreacted products.

[0177] The total content of the crosslinking 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 described above, so their description is omitted below.

[0178] The solvent may be used without limitation as long as it is a solvent usable in the relevant technical field, but may be, for example, a water-soluble solvent such as water, methanol, or ethanol, or may be distilled water. The solvent may be included as the remainder of the composition for forming an anion exchange polymer, excluding the crosslinking monomer represented by Chemical Formula 1, the ionic monomer represented by Chemical Formula 2, and the photoinitiator.

[0179] A polyester film is pressed onto at least one side of a porous polymer support filled with the above composition to produce a laminate in which the polyester film and the porous polymer support are combined.

[0180] A polyester film can be pressed onto the upper or / and lower surface of a porous polymer support by roll calendering. The polyester film can be, for example, a polyethylene terephthalate film.

[0181] The thickness of the polyester film may be 10 ㎛ to 150 ㎛, for example, 20 ㎛ to 120 ㎛ or 30 ㎛ to 100 ㎛. If the thickness of the polyester film is less than 10 ㎛, bonding defects such as film wrinkling may occur when bonding with a support filled with an anion exchange polymer. If the thickness of the polyester film is more than 150 ㎛, the thickness of the polyester film may be too thick during the crosslinking reaction described below, so that light may not be sufficiently irradiated to the porous polymer support, and thus the crosslinking reaction may not sufficiently occur.

[0182] The polyester film may have one surface in contact with the porous polymer support untreated or subjected to a release treatment. By using such a film, the bonding between the polyester film and the hydrophilic anion exchange polymer can be prevented, thereby preventing the anion exchange polymer from being removed from the surface of the support. The pressing can be performed at a temperature of 10°C to 35°C, for example, at a temperature of 15°C to 30°C, and at a pressure of about 0 bar to 5 bar. The pressure can be appropriately adjusted in consideration of the thickness of the porous polymer support and the thickness of the polyester film.

[0183] Next, light is irradiated onto the laminate and the composition is crosslinked to form an anion exchange polymer, which is a crosslinking product of the composition, on the surface and inside the pores of the porous polymer support.

[0184] In the step of forming the anion exchange polymer, the light may be ultraviolet light. For example, UVA, UVB, UVC or / and UVV may be used.

[0185] The above process may include performing irradiation with UVC light at a light dose of 2000 mJ / cm2 to 10000 mJ / cm2. For example, the process may be performed with UVC light at a light dose of 2000 mJ / cm2 to 8000 mJ / cm2. When performing light irradiation under these conditions, an ion exchange membrane with improved ion exchange capacity can be manufactured.

[0186] Finally, the polyester film is peeled off from the porous polymer support in which the anion exchange polymer is formed on the surface and inside the pores, thereby manufacturing an anion exchange membrane. The peeling can be accomplished by pulling the polyester film attached to the porous polymer support in the opposite direction using a peeling roll.

[0187] An anion exchange membrane manufactured according to the above manufacturing method may include 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 surrounds the outer surface of the substrate.

[0188] The anion exchange membrane may have 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 may be reduced, which may lead to membrane damage during operation. In addition, desalination and concentration performance may be reduced due to unnecessary salt permeation. If the thickness exceeds 200 μm, the surface resistance may be high, which may lead to high power consumption for operation and desalination and concentration performance may be reduced.

[0189] Additionally, the ion exchange capacity (IEC) of the anion exchange membrane may be 1.5 meq / g or more, or 1.6 meq / g or more.

[0190]

[0191] As used herein, "substitution" is derived by exchanging one or more hydrogens in an unsubstituted mother group with another atom or functional group. Unless otherwise stated, when a functional group is considered to be "substituted," it means that the functional group is substituted with one or more substituents selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 40 carbon atoms. When a functional group is described as being "optionally substituted," it means that the functional group can be substituted with the above-described substituents.

[0192] In this specification, the C1 to C20 alkyl group means, for example, a straight-chain alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, a decyl group, etc.; a branched alkyl group such as an isopropyl group, a tert-butyl group, a neopentyl group, a hexyl group, etc. Among these, it may be a methyl group or an ethyl group considering the ease of procurement of raw materials and the usability of the product. At least one hydrogen atom of the alkyl group may be substituted with a substituent as defined in the above-mentioned "substitution."

[0193] In this specification, a C3 to C30 cycloalkyl group means a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. At least one hydrogen atom in the cycloalkyl group may be substituted with a substituent as defined in the above-mentioned “substitution.”

[0194] In this specification, the aryl group having C5 to C40 means an aromatic system including one or more benzene rings, such as a phenyl group, a naphthyl group, etc. At least one hydrogen atom in the aryl group may be substituted with a substituent as defined in the above-mentioned “substitution.”

[0195] In this specification, the halogen anion is F - , Cl- , Br - , I - Examples include:

[0196]

[0197] Hereinafter, the present invention will be described through the following examples. Please note that the following examples are presented merely to illustrate the invention, and the scope of the present invention is not limited by the following examples.

[0198]

[0199] [Example]

[0200]

[0201] Manufacturing Example 1: Manufacturing of crosslinkable monomer

[0202] To a solution of 1,4-diazabicyclo[2,2,2]octane dissolved in methanol, a solution of 4-vinylbenzyl chloride dissolved in ethyl acetate was added such that the molar ratio of vinylbenzyl chloride to 1,4-diazabicyclo[2,2,2]octane was 2:1, and the mixture was stirred at room temperature under an inert atmosphere to prepare a mixture. The mixture was filtered, washed with methanol, and dried under vacuum at room temperature (25°C) to obtain a crosslinkable monomer represented by the following chemical formula 1-1.

[0203] <Chemical Formula 1-1>

[0204]

[0205]

[0206] Example 1: Preparation of anion exchange membrane

[0207] A 100 ㎛ thick polypropylene (PP) porous polymer support (porosity: 51%) was prepared. The porous polymer support was immersed in a 1 wt% aqueous solution of dodecylbenzenesulfonic acid for 10 minutes and then dried in a 70°C hot air oven for 10 minutes to render it hydrophilic. The hydrophilized porous polymer support was immersed in a composition for forming an anion exchange polymer, which is an ion exchange resin solution, for 5 minutes to fill the porous polymer support with the ion exchange resin solution.

[0208] At this time, the composition for forming an anion exchange polymer was prepared by mixing 20 wt% of the crosslinkable monomer of chemical formula 1-1 obtained according to Preparation Example 1, 40 wt% of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer, 0.5 wt% of 2-hydroxy-2-methylpropiophenone (manufactured by Ciba) photoinitiator, and the remainder of distilled water.

[0209] The composition for forming the anion exchange polymer was impregnated with the polypropylene porous polymer support, and the composition was filled on the surface and inside the pores of the porous polymer support. The porous polymer support filled with the composition was put into a pressing roll, and a polyester film having a thickness of 50 ㎛ was pressed onto the upper and lower surfaces of the porous polymer support at room temperature (25 ℃) to produce a laminate in which the polyester film and the porous polymer support were laminated. The laminate was irradiated with UVC ultraviolet rays at a dose of 3000 mJ / cm2 to form an anion exchange polymer, which is a crosslinked product of the composition, on the surface and inside the pores of the porous polymer support. The polyester film was peeled off from the porous polymer support in which the anion exchange polymer was formed on the surface and inside the pores, to produce an anion exchange membrane.

[0210] Example 2: Preparation of anion exchange membrane

[0211] An anion exchange membrane was prepared in the same manner as in Example 1, except that 40 wt% of (2-acryloyloxyethyl)trimethylammonium chloride was used as an ionic monomer in the composition for forming an anion exchange polymer.

[0212] Example 3: Preparation of anion exchange membrane

[0213] An anion exchange membrane was prepared in the same manner as in Example 1, except that 40 wt% of (3-acrylamidopropyl)trimethylammonium chloride was used as an ionic monomer in the composition for forming an anion exchange polymer.

[0214] Example 4: Preparation of anion exchange membrane

[0215] An anion exchange membrane was prepared in the same manner as in Example 1, except that 40 wt% of 2-(acryloyloxy)-N,N-dimethyl-N-(4-methylbenzyl)ethane-1-ammonium chloride was used as an ionic monomer in the composition for forming an anion exchange polymer.

[0216] Example 5: Preparation of anion exchange membrane

[0217] An anion exchange membrane was prepared in the same manner as in Example 1, except that 40 wt% of (vinylbenzyl)trimethylammonium chloride was used as an ionic monomer in the composition for forming an anion exchange polymer.

[0218] Example 6: Preparation of anion exchange membrane

[0219] An anion exchange membrane was manufactured in the same manner as in Example 1, except that a polypropylene (PP) porous polymer support (porosity: 55%) with a thickness of 60 μm was used.

[0220] Example 7: Preparation of anion exchange membrane

[0221] An anion exchange membrane was manufactured in the same manner as in Example 1, except that a polyvinyl alcohol (PVA) porous polymer support (porosity: 75%) with a thickness of 125 μm was used.

[0222] Example 8: Preparation of anion exchange membrane

[0223] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 50 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 10 wt% of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0224] Example 9: Preparation of anion exchange membrane

[0225] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 50 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 10 wt% of the (2-acryloyloxyethyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0226] Example 10: Preparation of anion exchange membrane

[0227] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 50 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 10 wt% of the (3-acrylamidopropyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0228] Example 11: Preparation of anion exchange membrane

[0229] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 50 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 10 wt% 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.

[0230] Example 12: Preparation of anion exchange membrane

[0231] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 50 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 10 wt% of the (vinylbenzyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0232] Example 13: Preparation of anion exchange membrane

[0233] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 10 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 50 wt% of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0234] Example 14: Preparation of anion exchange membrane

[0235] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 10 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 50 wt% of the (2-acryloyloxyethyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0236] Example 15: Preparation of anion exchange membrane

[0237] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 10 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 50 wt% of the (3-acrylamidopropyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0238] Example 16: Preparation of anion exchange membrane

[0239] An anion exchange membrane was manufactured in the same manner as in Example 13, except that 10 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 50 wt% 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.

[0240] Example 17: Preparation of anion exchange membrane

[0241] An anion exchange membrane was manufactured in the same manner as in Example 13, except that 10 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 50 wt% of the (vinylbenzyl)trimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0242] Comparative Example 1: Preparation of anion exchange membrane

[0243] An anion exchange membrane was manufactured in the same manner as in Example 1, except that only 60 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 was used without an ionic monomer in the composition for forming an anion exchange membrane.

[0244] Comparative Example 2: Preparation of anion exchange membrane

[0245] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 6 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 54 wt% of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0246] Comparative Example 3: Preparation of anion exchange membrane

[0247] An anion exchange membrane was manufactured in the same manner as in Example 1, except that 55 wt% of the crosslinking monomer of Chemical Formula 1-1 obtained according to Preparation Example 1 and 5.5 wt% of the N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride ionic monomer were used in the composition for forming an anion exchange polymer.

[0248]

[0249] Evaluation Example 1: Evaluation of the physical properties of an ion exchange membrane

[0250] The anion exchange membranes manufactured in Examples 1 to 7 and Comparative Examples 1 to 3 were tested using the following method to evaluate their physical properties, and the evaluation results are shown in Table 1 below.

[0251] (1) Surface resistance (Ω·㎠)

[0252] Each anion exchange membrane was cut into 5 cm X 5 cm sizes to prepare samples. The samples were immersed in a 0.5 M NaCl aqueous solution for 24 hours. The samples were placed between electrodes for measuring surface resistance, and the line resistance (R) of the anion exchange membrane was measured using an LCR meter (E4908A, Agilent). 11 ), resistance (R) of 0.5 M NaCl aqueous solution 12 ) was measured. The measured resistance value (R 11 , R 12 ) into Equation 1 to obtain the surface resistance (R m ) was obtained.

[0253] [Formula 1]

[0254] R m (Ω·㎠) = (R 11 - R 12 ) x S

[0255] Among the foods,

[0256] R m is the surface resistance of the anion exchange membrane,

[0257] R 11 is the line resistance of the anion exchange membrane,

[0258] R 12 is the resistance of 0.5 M NaCl aqueous solution,

[0259] S is the area of ​​the electrode.

[0260] (2) Ion Exchange Capacity (IEC, meq / g)

[0261] Each anion exchange membrane was cut into 5 cm X 5 cm sizes to prepare samples. The samples were washed with distilled water and excess moisture was removed with a tissue. After filling a vial with 70 ml of a 1 M NaCl solution, the sample from which moisture had been removed was placed in the 1 M NaCl solution and immersed for more than 12 hours to perform the first pretreatment. Then, the sample from which moisture had been removed was washed several times with distilled water and excess moisture was removed with a tissue. After filling a vial with 70 ml of a 0.5 M Na2CO3 solution, the sample from which moisture had been removed was placed in the 0.5 M Na2CO3 solution and immersed for more than 12 hours to perform the second pretreatment. Then, the sample from which the second pretreatment had been completed was taken out of the vial, and the remaining solution was titrated with a 0.01 M AgNO3 solution, and the volume of the AgNO3 solution added during the titration was recorded. The sample was washed several times with distilled water and then 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 obtain the ion exchange capacity (IEC).

[0262] [Formula 2]

[0263] IEC (meq / g) = (volume of titrant (ml) x 0.01) / weight of dried anion exchange membrane (g)

[0264] (3) Appearance evaluation

[0265] For each anion exchange membrane, the appearance was visually observed and evaluated using the following criteria.

[0266] ·Good: No cracks or peeling on the surface

[0267] ·Defective: Cracks or peeling on the surface

[0268] ClassificationPorous support materialPorous support porosity (%)Porous support thickness (㎛)Sheet resistance (Ω ㎠)Ion exchange capacity (meq / g)Appearance EvaluationExample 1PP511004.22.3Good example 2PP511004.02.2Good example 3PP511003.92.2Good example 4PP511004.32.1Good example 5PP511003.82.3Good example 6PP55602.12.9Good example 7PVA751252.03.4Good example 8PP511005.52.7Good example 9PP511005.22.8Good example 10PP511005.02.7Good embodiment 11PP511005.82.6Good embodiment 12PP511004.82.8Good embodiment 13PP511003.81.8Good embodiment 14PP511003.51.9Good embodiment 15PP511003.51.9Good embodiment 16PP511004.01.7Good embodiment 17PP511003.41.9Good comparative example 1PP511006.32.9Defective (crack) comparative example 2PP511003.71.4Defective (peeling) comparative example 3PP511006.12.7Defective (crack)

[0269] Referring to Table 1 above, it can be confirmed that the anion exchange membranes of Examples 1 to 17 have excellent sheet resistances of 6 Ω·cm2 or less and ion exchange capacities of 1.5 meq / g or more, and good appearances. In contrast, the ion exchange membrane of Comparative Example 1, which did not use an ionic monomer, had a high sheet resistance of 6.3 Ω·cm2, and cracks occurred on the surface, resulting in poor appearance. The ion exchange membrane of Comparative Example 2, which used a composition for forming an anion exchange polymer prepared in a weight ratio of 1:9 of the crosslinkable monomer of Chemical Formula 1-1 and the ionic monomer obtained according to Preparation Example 1, had a low ion exchange capacity of 1.4 meq / g, and it can be confirmed that electrolyte peeling occurred on the surface, resulting in poor appearance. The ion exchange membrane of Comparative Example 3 using the composition for forming an anion exchange polymer prepared in a weight ratio of 1:0.1 of the crosslinkable monomer and ionic monomer of Chemical Formula 1-1 obtained according to Manufacturing Example 1 had a high surface resistance of 6.1 Ω·㎠, and it was confirmed that cracks occurred on the surface, resulting in a poor appearance.

[0270] From this, the anion exchange membranes of Examples 1 to 17 can provide anion exchange membranes having high ion exchange capacity and good appearance.

[0271]

[0272] While exemplary embodiments have been described in detail with reference to the attached drawings, the present invention is not limited to these examples. It is self-evident that those skilled in the art to which the present invention pertains can devise various modifications or variations within the scope of the technical concepts described in the patent claims, and these also naturally fall within the technical scope of the present invention.

[0273]

[0274] [Explanation of symbols]

[0275] 20: porous polymer support, 21: pores,

[0276] 30: Anion exchange polymer backbone having a cationic functional group,

[0277] 31: Anion exchange polymer

Claims

1. Porous polymer support; and An electrolyte containing an anion exchange polymer; The electrolyte is located on 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 comprising a crosslinkable monomer represented by the following chemical formula 1 and an ionic monomer represented by the following chemical formula 2, an anion exchange membrane: [Chemical Formula 1] [Chemical Formula 2] In chemical formula 1, X - is a halogen anion; In chemical formula 2, A is -O-, , or 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, R3 are independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group; p is 0 or 1; q is an integer from 0 to 6; r is an integer from 0 to 6; and Y - is a halogen anion.

2. In paragraph 1, In the above chemical formula 2, An anion exchange membrane, wherein R4 is a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

3. In paragraph 1, In the above chemical formula 2, The above A is -O-; An anion exchange membrane, wherein R4 is a substituted or unsubstituted C1 to C5 alkyl group, or a substituted or unsubstituted C6 to C15 aryl group.

4. In paragraph 1, The above ionic monomer (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-oxoallyl)oxyethyl]ammonium chloride, benzyldimethyl[2-(2-methyl-1-oxoallyl)oxyethyl]ammonium bromide, benzyldimethyl[2-(2-methyl-1-oxoallyl)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-(naphthalen-1-ylmethyl)ethane-1-ammonium chloride, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium bromide, 2-(acryloyloxy)-N,N-dimethyl-N-(naphthalen-1-ylmethyl)ethane-1-ammonium iodide; 2-(Acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium chloride, 2-(acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium bromide, 2-(acryloyloxy)-N((9,10-dihydropyren-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide; (Vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium bromide, (vinylbenzyl)trimethylammonium iodide; and An anion exchange membrane comprising (2-methylvinylbenzyl)trimethylammonium chloride, (2-methylvinylbenzyl)trimethylammonium bromide, and (2-methylvinylbenzyl)trimethylammonium iodide.

5. In paragraph 1, An anion exchange membrane, wherein the weight ratio of the crosslinking monomer and the ionic monomer is 1:0.2 to 1:

8.

6. In paragraph 1, An anion exchange membrane, wherein the total content of the crosslinking monomer and the ionic monomer is 30% to 85% by weight based on 100% by weight of the entire composition.

7. In paragraph 1, The above composition further comprises a photoinitiator, An anion exchange membrane, wherein the content of the photoinitiator is 0.01 wt% to 2 wt% based on 100 wt% of the total composition.

8. In paragraph 1, The above porous polymer support is an anion exchange membrane which is a membrane structure, a non-woven structure, a fabric structure or a mesh structure.

9. In paragraph 1, The above porous polymer support is an anion exchange membrane comprising at least one polymer selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyetheretherketone, polyethersulfone, polysulfone, polystyrene, polyaryleneethersulfone, and polyetherketone.

10. In paragraph 1, An anion exchange membrane, wherein the porosity of the porous polymer support is 30% to 80% and the thickness of the porous polymer support is 10 ㎛ to 150 ㎛.

11. In paragraph 1, The surface resistance (R) of the above anion exchange membrane according to the following equation 1 m ) Anion exchange membrane having a thickness of 6 Ω·㎠ or less: [Formula 1] R m (Ω·㎠) = (R 11 - R 12 ) x S Among the foods, R m is the surface resistance of the anion exchange membrane, R 11 is the line resistance of the anion exchange membrane, R 12 is the resistance of 0.5 M NaCl aqueous solution, S is the area of ​​the electrode.

12. In paragraph 1, An anion exchange membrane having an ion exchange capacity (IEC) of 1.5 meq / g or more.

13. In paragraph 1, An anion exchange membrane, wherein the anion exchange membrane is used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis.

14. A step of providing a porous polymer support; A step of preparing a composition for forming an anion exchange polymer, comprising a crosslinking monomer represented by the following chemical formula 1, an ionic monomer represented by the following chemical formula 2, a photoinitiator, and a solvent; A step of impregnating the porous polymer support with the composition for forming the anion exchange polymer and filling at least a portion of the surface and the interior of the pores of the porous polymer support with the composition; A step of pressing a polyester film onto at least one side of a porous polymer support filled with the above composition to produce a laminate in which the polyester film and the porous polymer support are combined; A step of irradiating light on the laminate and crosslinking 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 the interior of the pores of the porous polymer support; and A method for manufacturing an anion exchange membrane, comprising: a step of manufacturing an anion exchange membrane by peeling off the polyester film from a porous polymer support in which the anion exchange polymer is formed on at least a portion of the surface and the interior of the pores; a method for manufacturing an anion exchange membrane according to any one of claims 1 to 13; [Chemical Formula 1] [Chemical Formula 2] In chemical formula 1, X - is a halogen anion; In chemical formula 2, A is -O-, , or 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, R3 are independently a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C5 to C40 aryl group; R4 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C5 to C30 aryl group; p is 0 or 1; q is an integer from 0 to 6; r is an integer from 0 to 6; and Y - is a halogen anion.

15. In paragraph 14, In the step of forming the above anion exchange polymer, the light is ultraviolet light, A method for manufacturing an anion exchange membrane, comprising a process of irradiating the above light with a light amount of 2000 mJ / cm2 to 10000 mJ / cm2.

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