Anion exchange membrane and manufacturing method therefor

Abstract

Disclosed are an anion exchange membrane and a manufacturing method therefor. The anion exchange membrane comprises: a porous polymer support; and an electrolyte containing an anion exchange polymer on the surface and inside pores of the porous polymer support, wherein the anion exchange polymer is a cross-linked product of a composition containing two or more types of monomers, and the two or more types of monomers comprise a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2, as described in the specification. The anion exchange membrane may have a high ion exchange capacity.

Description

Anion exchange membrane and method of manufacturing the same

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

[0002] An ion exchange membrane refers to a synthetic resin membrane that selectively allows only one type of ion to pass through, either cations or anions. Cation exchange membranes have negatively charged functional groups that allow for the selective passage of cations, while anion exchange membranes have positively charged functional groups that allow for the selective passage of anions. Generally, ion exchange membranes require high permeability selectivity, low electrical resistance, excellent mechanical strength, and high chemical stability.

[0003] Anion exchange membranes can be applied to water treatment systems such as electrodialysis, bipolar membrane electrodialysis, capacitive desalination, and electro-deionization, or to systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow cells. Systems to which anion exchange membranes are applied may use acidic or alkaline raw water in the process, and acid or alkali may be generated during the process operation of the raw water.

[0004] Perfluorinated anion exchange membranes can be used as anion exchange membranes, but due to their high cost, hydrocarbon anion exchange membranes are applied in actual systems.

[0005] However, hydrocarbon-based anion exchange membranes have limitations in application processes and conditions due to chemical resistance issues. Additionally, 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 exists within the membrane.

[0006] According to one aspect, by increasing the electrolyte content within the ion exchange membrane, an anion exchange membrane having a high ion exchange capacity is provided.

[0007] The present invention provides a method for manufacturing the anion exchange membrane described above according to other aspects.

[0008] Depending on one aspect,

[0009] porous polymer support; and

[0010] An electrolyte containing an anion exchange polymer on the surface and inside the pores of the porous polymer support; comprising

[0011] The above anion exchange polymer is a crosslinked product of a composition comprising two or more monomers, and

[0012] An anion exchange membrane is provided, wherein the above two or more monomers comprise a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:

[0013] [Chemical Formula 1]

[0014]

[0015] During the meal,

[0016] R1 may be a single bond, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, or a combination thereof;

[0017] R2 and R3 can each be vinyl groups;

[0018] R a , R b , R c , R d is independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a quaternary ammonium cation, or R a , R b , R c , R d C5-C5s that combine with each other to form substituted or unsubstituted C5s 50 aromatic heterocyclic groups or substituted or unsubstituted C5-C 50 It can form aliphatic heterocyclic rings;

[0019] Y1 - , Y2 - are independent of each other F - , Cl - , Br - , or I- It could be;

[0020] [Chemical Formula 2]

[0021]

[0022] During the meal,

[0023] A may be a single bond or a substituted or unsubstituted C1-C6 alkylene group;

[0024] R'1, R'2, and R'3 are independently substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C5-C 50 aryl groups, substituted or unsubstituted C6-C 50 arylalkylene groups of, substituted or unsubstituted C6-C 50 alkylarylene groups, substituted or unsubstituted C5-C 50 heteroaryl groups, substituted or unsubstituted C6-C 50 heteroarylalkylene groups of, substituted or unsubstituted C6-C 50 It may be an alkylheteroarylene group, or a combination thereof;

[0025] R'4 can be a vinyl group;

[0026] Y3 - is F - , Cl - , Br - , or I - It could be.

[0027] According to an exemplary embodiment, the first compound represented by Formula 1 may include one or more selected from the following compounds 1 to 6:

[0028] ,

[0029] , ,

[0030] , ,

[0031] .

[0032] According to an exemplary embodiment, the content of the first compound represented by Formula 1 may be 10% to 30% by weight based on 100% by weight of the total composition.

[0033] According to an exemplary embodiment, the second compound represented by the formula 2 is,

[0034] (2-acryloyloxyethyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium bromide, (2-acryloyloxyethyl)trimethylammonium iodide;

[0035] (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide;

[0036] 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;

[0037] 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;

[0038] 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;

[0039] 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;

[0040] 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;

[0041] 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;

[0042] 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;

[0043] 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;

[0044] 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; or

[0045] It may include 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, and 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide.

[0046] According to an exemplary embodiment, the weight ratio of the first compound represented by Formula 1 to the second compound represented by Formula 2 may be 1:1 to 1:3.

[0047] According to an exemplary embodiment, the total content of the first compound represented by Formula 1 and the second compound represented by Formula 2 may be 30% to 85% by weight based on 100% by weight of the entire composition.

[0048] According to an exemplary embodiment, the porous polymer support may be a membrane structure, a nonwoven structure, a fabric structure, or a mesh structure.

[0049] According to an exemplary embodiment, the porous polymer support may comprise one or more polymers selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyetheretherketone, polyethersulfone, polysulfone, polystyrene, polyaryleneethersulfone, and polyetherketone.

[0050] According to an exemplary embodiment, the porosity of the porous polymer support may be 30% to 80%, and the thickness of the porous polymer support may be 70 μm to 130 μm.

[0051] According to an exemplary embodiment, the ion exchange capacity (IEC) of the anion exchange membrane may be 1.8 meq / g or more.

[0052] According to an exemplary embodiment, the anion exchange membrane may be used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems.

[0053] Depending on other aspects of work,

[0054] Step of providing a porous polymer support;

[0055] A step of preparing a composition for forming an anion exchange polymer comprising a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2;

[0056] A step of impregnating the porous polymer support with the above-mentioned anion exchange polymer forming composition to fill the surface and the interior of the pores of the porous polymer support with the composition;

[0057] A step of manufacturing a laminate in which a polyester film and a porous polymer support are laminated by pressing a polyester film onto at least one surface of a porous polymer support filled with the above composition;

[0058] A step of irradiating light onto the laminate and crosslinking the composition to form an anion exchange polymer, which is a crosslinking product of the composition, on the surface of the porous polymer support and inside the pores; and

[0059] A method for manufacturing an anion exchange membrane is provided, comprising the step of manufacturing an anion exchange membrane by peeling off a polyester-based film from a porous polymer support in which the anion exchange polymer is formed on the surface and inside the pores.

[0060] [Chemical Formula 1]

[0061]

[0062] During the meal,

[0063] R1 may be a single bond, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, or a combination thereof;

[0064] R2 and R3 can each be vinyl groups;

[0065] R a , R b , R c , R d is independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a quaternary ammonium cation, or R a , R b , R c , R d C5-C5s that combine with each other to form substituted or unsubstituted C5s 50 aromatic heterocyclic groups or substituted or unsubstituted C5-C 50 It can form aliphatic heterocyclic rings;

[0066] Y1 - , Y2 - are independent of each other F - , Cl - , Br - , or I - It could be;

[0067] [Chemical Formula 2]

[0068]

[0069] During the meal,

[0070] A may be a single bond or a substituted or unsubstituted C1-C6 alkylene group;

[0071] R'1, R'2, and R'3 are independently substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C5-C 50 aryl groups, substituted or unsubstituted C6-C 50 arylalkylene groups of, substituted or unsubstituted C6-C 50 alkylarylene groups, substituted or unsubstituted C5-C 50 heteroaryl groups, substituted or unsubstituted C6-C 50 heteroarylalkylene groups of, substituted or unsubstituted C6-C 50 It may be an alkylheteroarylene group, or a combination thereof;

[0072] R'4 can be a vinyl group;

[0073] Y3 - is F - , Cl - , Br - , or I - It could be.

[0074] An anion exchange membrane according to one aspect comprises a porous polymer support and an electrolyte containing an anion exchange polymer on the surface and inside the pores of the porous polymer support. The electrolyte surrounds the surface and inside the pores of the porous support, thereby increasing the electrolyte content within the anion exchange membrane. Therefore, the anion exchange membrane can have a high ion exchange capacity.

[0075] Figure 1 is a schematic diagram of an anion exchange membrane according to one embodiment.

[0076] Hereinafter, an anion exchange membrane according to one embodiment and a method for manufacturing the same will be described in more detail.

[0077] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. In the event of a conflict, the present specification, including definitions, shall prevail. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0078] In this specification, the term “comprising” means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. In this specification, the term “combination of these” means a mixture or combination with one or more of the described components.

[0079] In this specification, the term “and / or” means any combination of one or more items described in relation and all combinations thereof. In this specification, the term “or” means “and / or”.

[0080] In this specification, the expressions "at least one type" or "one or more" preceding the components are to supplement the list of all components and do not mean that they are to supplement the individual components described above. Where in this specification it is stated that one component is placed "on" or "above" another component, the component may be placed directly on the other component, or there may be components interposed between the components. On the other hand, where it is stated that one component is placed "directly" or "directly on" another component, there may be no interposed components.

[0081] In this specification, the terms “e.g.,” “e.g.,” “e.g.,” or “exemplary” are intended to introduce examples that clarify a more general subject. Unless otherwise stated, these examples are provided solely for the purpose of understanding the invention and are not intended to limit it in any manner.

[0082] In this specification, "~-type resin," "~-type polymer," "~-type polymer," or / and "~-type copolymer" are broad concepts that include all of "~-type resin," "~-type polymer," "~-type polymer," "~-type copolymer," or / and "derivatives of ~-type resin, polymer, polymer, or copolymer." In this specification, the term "polymer or copolymer cross-linked with these resins" means "polymer or copolymer cross-linked with the aforementioned resins."

[0083] In this specification, the term "crosslinked product" means that, in addition to the polymer formed by crosslinking two or more monomers, it includes the initial reaction product, intermediate reaction product, final reaction product, and unreacted material.

[0084] A typical anion exchange membrane has a structure in which an anion exchange polymer having cationic functional groups is disposed on top of a support. Anion exchange membranes require high selective permeability to anions, low electrical resistance, excellent mechanical strength, and chemical stability.

[0085] Anion exchange membranes are known to include perfluorinated anion exchange membranes or hydrocarbon anion exchange membranes. Among these, hydrocarbon anion exchange membranes are cheaper than perfluorinated anion exchange membranes, but their chemical resistance is insufficient. In addition, anion exchange membranes that utilize a support material have a certain proportion of the support material, which limits the increase in ion exchange capacity to enhance concentration and desalination performance.

[0086] The inventors provide an anion exchange membrane that increases the electrolyte content in the ion exchange membrane by solving the aforementioned problems.

[0087] An anion exchange membrane according to one embodiment comprises: a porous polymer support; and an electrolyte containing an anion exchange polymer on the surface of the porous polymer support and inside the pores; wherein the anion exchange polymer is a crosslinked product of a composition comprising two or more monomers, and the two or more monomers may include a first compound represented by the following Chemical Formula 1 and a second compound represented by the following Chemical Formula 2:

[0088] [Chemical Formula 1]

[0089]

[0090] During the meal,

[0091] R1 may be a single bond, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, or a combination thereof;

[0092] R2 and R3 can each be vinyl groups;

[0093] R a , R b , R c , R d is independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a quaternary ammonium cation, or R a , R b , R c , R d C5-C5s that combine with each other to form substituted or unsubstituted C5s 50 aromatic heterocyclic groups or substituted or unsubstituted C5-C 50 It can form aliphatic heterocyclic rings;

[0094] Y1 - , Y2 - are independent of each other F - , Cl - , Br - , or I - It could be;

[0095] [Chemical Formula 2]

[0096]

[0097] During the meal,

[0098] A may be a single bond or a substituted or unsubstituted C1-C6 alkylene group;

[0099] R'1, R'2, and R'3 are independently substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C5-C 50 aryl groups, substituted or unsubstituted C6-C 50 arylalkylene groups of, substituted or unsubstituted C6-C 50 alkylarylene groups, substituted or unsubstituted C5-C 50 heteroaryl groups, substituted or unsubstituted C6-C 50 heteroarylalkylene groups of, substituted or unsubstituted C6-C 50 It may be an alkylheteroarylene group, or a combination thereof;

[0100] R'4 can be a vinyl group;

[0101] Y3 - is F - , Cl - , Br - , or I - It could be.

[0102] In the second compound represented by Chemical Formula 2, the vinyl group is a functional group capable of crosslinking with the first compound represented by Chemical Formula 1.

[0103] For example, the first compound represented by the above chemical formula 1 may include one or more selected from the following compounds 1 to 6:,

[0104] ,

[0105] , ,

[0106] , ,

[0107]

[0108] An anion exchange membrane according to one embodiment can have low sheet resistance and high ion exchange capacity.

[0109] The content of the first compound represented by Chemical Formula 1 may be 10% to 30% by weight based on 100% by weight of the total composition. If the content of the first compound represented by Chemical Formula 1 is less than 10% by weight, the degree of crosslinking is low, so the anion exchange membrane may dissolve or the concentration rate of ionic substances in the solution may decrease. If the content of the first compound represented by Chemical Formula 1 is more than 30% by weight, the sheet resistance of the anion exchange membrane increases due to the high degree of crosslinking, and membrane breakage may occur.

[0110] The second compound represented by the above chemical formula 2 is,

[0111] (2-acryloyloxyethyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium bromide, (2-acryloyloxyethyl)trimethylammonium iodide;

[0112] (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide;

[0113] 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;

[0114] 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;

[0115] 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;

[0116] 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;

[0117] 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;

[0118] 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;

[0119] 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;

[0120] 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;

[0121] 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; or

[0122] It may include 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, and 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide.

[0123] For example, the second compound represented by Chemical Formula 2 is (2-acryloyloxyethyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium bromide, (2-acryloyloxyethyl)trimethylammonium iodide;

[0124] (2-methacryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium bromide, (2-methacryloyloxyethyl)trimethylammonium iodide; or

[0125] It may include N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium bromide, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium iodide.

[0126] The weight ratio of the first compound represented by Chemical Formula 1 to the second compound represented by Chemical Formula 2 may be 1:1 to 1:3. If the weight ratio of the first compound to the second compound is within the above range, the anion exchange performance of the anion exchange membrane can be improved without the solubility characteristics of the composition for forming an anion exchange polymer being reduced.

[0127] The total content of the first compound represented by Chemical Formula 1 and the second compound represented by Chemical Formula 2 may be 30% to 85% by weight based on 100% by weight of the entire composition. For example, the total content of the first compound and the second compound may be 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 the first compound and the second compound is less than 30% by weight, the anion exchange performance of the anion exchange membrane may be reduced, and if it exceeds 85% by weight, the solubility of the monomer constituting the anion exchange polymer may be reduced when preparing the electrolyte solution of the composition.

[0128] The above composition may further include a photoinitiator and a solvent.

[0129] The content of the photoinitiator may be 0.01% to 2% by weight based on 100% by weight of the total composition. For example, the content of the photoinitiator may be 0.1% to 1% by weight based on 100% by weight of the total composition. Any photoinitiator available in the relevant technical field may be used without limitation, but for example, it may be 2-hydroxy-2-methylpropiophenone.

[0130] The solvent may be any solvent available in the relevant technical field without limitation, but may be a water-soluble solvent such as water, methanol, or ethanol. For example, the solvent may be distilled water. In the composition, the solvent may be included in the remainder excluding the first compound represented by Formula 1, the second compound represented by Formula 2, and the photoinitiator.

[0131] Figure 1 is a schematic diagram of an anion exchange membrane according to one embodiment.

[0132] Referring to FIG. 1, in one embodiment, an anion exchange membrane (40) has an anion exchange polymer (31) having cationic functional groups located on the surface of a porous polymer support (20) and inside the pores (21). The anion exchange polymer (31) having cationic functional groups is uniformly distributed on the surface of the porous polymer support (20) and inside the pores (21), so a homogeneous anion exchange membrane (40) can be obtained. This anion exchange membrane (40) structure can have low sheet resistance and high ion conductivity. In addition, the porous polymer support (20) can improve mechanical durability and can have high dimensional stability.

[0133] The porous polymer support (20) may be in the shape of a sponge or a three-dimensional network. The porous polymer support (20) may be a membrane structure, a nonwoven structure, a fabric structure, or a mesh structure.

[0134] The porous polymer support (20) may include one or more polymers selected from polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyetheretherketone, polyethersulfone, polysulfone, polystyrene, polyaryleneethersulfone, and polyetherketone. For example, the porous polymer support (20) may include one or more polymers selected from polyethylene, polypropylene, and polyvinyl alcohol.

[0135] 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 the major axis length when the pores are non-spherical. The porosity and pore size of the porous polymer support (20) are measured from the BET method and / or surface SEM images, and the porosity can be obtained through the area ratio from cross-sectional SEM image analysis. The porosity can also be calculated using basis weight and thickness.

[0136] The thickness of the porous polymer support may be 70 μm to 130 μm. For example, the thickness of the porous polymer support may be 80 μm to 120 μm. Within the thickness range of the porous polymer support, the sheet resistance may be reduced and the ion exchange capacity may be increased.

[0137] The ion exchange capacity (IEC) of the anion exchange membrane (40) can be 1.8 meq / g or more.

[0138] The anion exchange membrane (40) can be used for electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis.

[0139] The anion exchange membrane (40) can also be used in energy systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries.

[0140] A method for manufacturing an anion exchange membrane according to another embodiment comprises: providing a porous polymer support; preparing a composition for forming an anion exchange polymer comprising a first compound represented by the following Chemical Formula 1 and a second compound represented by the following Chemical Formula 2; impregnating the porous polymer support with the composition for forming an anion exchange polymer to fill the composition on the surface and inside the pores of the porous polymer support; 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 light onto the laminate and crosslinking the composition 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; and peeling off the polyester film from the porous polymer support having the anion exchange polymer formed on the surface and inside the pores to produce an anion exchange membrane.

[0141] [Chemical Formula 1]

[0142]

[0143] During the meal,

[0144] R1 may be a single bond, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, or a combination thereof;

[0145] R2 and R3 can each be vinyl groups;

[0146] R a , R b , R c , R d is independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a quaternary ammonium cation, or R a , R b , R c , R dC5-C5s that combine with each other to form substituted or unsubstituted C5s 50 aromatic heterocyclic groups or substituted or unsubstituted C5-C 50 It can form aliphatic heterocyclic rings;

[0147] Y1 - , Y2 - are independent of each other F - , Cl - , Br - , or I - It could be;

[0148] [Chemical Formula 2]

[0149]

[0150] During the meal,

[0151] A may be a single bond or a substituted or unsubstituted C1-C6 alkylene group;

[0152] R'1, R'2, and R'3 are independently substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C5-C 50 aryl groups, substituted or unsubstituted C6-C 50 arylalkylene groups of, substituted or unsubstituted C6-C 50 alkylarylene groups, substituted or unsubstituted C5-C 50 heteroaryl groups, substituted or unsubstituted C6-C 50 heteroarylalkylene groups of, substituted or unsubstituted C6-C 50 It may be an alkylheteroarylene group, or a combination thereof;

[0153] R'4 can be a vinyl group;

[0154] Y3 - is F - , Cl - , Br - , or I - It could be.

[0155] First, a porous polymer support is provided.

[0156] The shape, structure, material, porosity, pore size, thickness, etc. of the porous polymer support are the same as described above, so the following explanation is omitted.

[0157] Before performing the step of preparing a porous polymer support by immersing it in an anionic 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 the step of immersing the porous polymer support in a surfactant solution and drying it to hydrophilize the surface of the porous polymer support.

[0158] 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 if the pores of the substrate are sufficiently large to be filled with an ion exchange resin solution.

[0159] 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, and if it is performed for more than 10 minutes, problems such as reduced production speed and increased production costs may occur.

[0160] Through the aforementioned immersion, the pores of the porous polymer support may be filled with an ion exchange resin solution, resulting in a pore-filled form. Additionally, the ion exchange resin may coat the outer surface of the porous polymer support.

[0161] In addition, in the hydrophilization step, drying can be performed immediately after immersion, or at a temperature of 40 to 90 ℃ for 1 to 20 minutes, or at a temperature of 40 to 80 ℃ for 1 to 10 minutes.

[0162] Meanwhile, the surfactant solution may contain 0.001 to 6 weight% of surfactant and the remainder of a solvent, or 0.01 to 4 weight% and the remainder of a solvent, or 0.05 to 3 weight% and the remainder of a solvent.

[0163] If the surfactant is included in the surfactant solution at a concentration of less than 0.001 weight%, the surface of the porous polymer support may not be hydrophilized, and thus the ion exchange resin solution may not be filled into the pores of the substrate. If the surfactant is included at a concentration exceeding 6 weight%, the surfactant may be eluted or the amount of ion exchange resin filled may decrease.

[0164] Surfactants may be used without restriction as long as they are known surfactants, but they may be substances having one or more alkyl groups having 12 to 20 carbon atoms within a single molecule. Examples include sulfonic acids such as dodecylbenzenesulfonic acid (DBSA), alkylbenzenesulfonic acid (ABS), linear alkylbenzenesulfonic acid (LAS), alphasulfonic acid (AS), alphaolefinsulfonic acid (AOS), and alcoholpolyoxyethyleneethersulfonic acid (AES); and alcoholpolyoxyethyleneether (AE). Quaternary ammonium salts such as dimethyldialkylammonium chloride quaternary ammonium salt, amidoamine quaternary ammonium salt, amidoesteramine quaternary ammonium salt; imidazoline ester systems, etc., may be included alone or in two or more types. The surfactant according to one embodiment may be a quaternary ammonium salt.

[0165] When a surfactant is bonded to the surface of a porous polymer support, where the hydrophobic part is hydrophobic, through hydrophobic-hydrophobic interaction, the hydrophilic part of the surfactant takes over the surface of the porous polymer support, thereby enabling hydrophilization. In this case, the entire surface of the internal pores, as well as the outer surface of the porous polymer support, can be hydrophilized by the surfactant. 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 a composition for forming an anion exchange polymer.

[0166] Next, an anion polymer forming composition is prepared, which is an ion exchange resin solution comprising a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2. The anion polymer forming composition may further include a photoinitiator and a solvent.

[0167] By irradiating an ion exchange resin solution with ultraviolet light, a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2 can be cross-linked to form a cross-linked product.

[0168] The total content of the first compound represented by Chemical Formula 1 and the second compound represented by Chemical Formula 2 is the same as described above, so the following explanation is omitted.

[0169] A polyester film is pressed onto at least one surface 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 laminated.

[0170] A polyester film can be pressed onto the upper and / or lower surfaces of a porous polymer support via roll calendering. The polyester film may be, for example, a polyethylene terephthalate film.

[0171] The thickness of the polyester film may be 50 μm to 150 μm, for example, 70 μm to 120 μm or 80 μm to 100 μm. If the thickness of the polyester film is less than 50 μm, lamination defects such as the film wrinkling may occur when laminating with a support filled with an anion exchange polymer. If the thickness of the polyester film is greater than 150 μm, the thickness of the polyester film is too thick during the crosslinking reaction described later, so light is not sufficiently irradiated onto the porous polymer support, and the crosslinking reaction may not occur sufficiently.

[0172] One side of the polyester film in contact with the porous polymer support may be untreated or have a release treatment. By using such a film, bonding with the porous polymer support having a hydrophilized surface can be hindered, thereby preventing the removal of the anion exchange polymer from the surface of the support. Compression can be performed at a temperature of 10°C to 35°C, for example, at a temperature of 15°C to 30°C, at a pressure of about 0 bar to 5 bar. The pressure can be appropriately adjusted considering the thickness of the porous polymer support and the thickness of the polyester film.

[0173] Next, light is irradiated onto the laminate and the composition is crosslinked to form an anion exchange polymer, which is a crosslinked product of the composition, on the surface of the porous polymer support and inside the pores.

[0174] In the step of forming the anion exchange polymer, the light may be ultraviolet. For example, UVA, UVB, UVC or / and UVV may be used.

[0175] The process may include performing irradiation using UVC as the light with a light intensity of 2,000 mJ / cm² to 10,000 mJ / cm². For example, it may be performed using UVC as the light with a light intensity of 2,000 mJ / cm² to 8,000 mJ / cm². When light irradiation is performed under these conditions, an ion exchange membrane with improved ion exchange capacity can be manufactured.

[0176] Finally, an anion exchange membrane is manufactured by peeling off the polyester film from a porous polymer support in which the anion exchange polymer is formed on the surface and inside the pores. Peeling can be performed by pulling the polyester film attached to the porous polymer support in the opposite direction using a detachment roller.

[0177] The anion exchange membrane manufactured according to the above manufacturing method may include a porous polymer support; and an anionic polymer, which is an ion exchange resin filled into the pores of the porous polymer support and covering the outer surface of the substrate.

[0178] 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 is reduced, raising concerns about membrane damage during operation and desalination and concentration performance may be reduced due to the permeation of unnecessary salts. If it exceeds 200 μm, the sheet resistance is high, resulting in high power consumption required for operation and desalination and concentration performance.

[0179] In addition, the ion exchange capacity (IEC) of the anion exchange membrane may be 1.8 meq / g or more, or 1.9 meq / g or more.

[0180]

[0181] In this specification, "substitution" is induced by the exchange of one or more hydrogens from an unsubstituted mother group with another atom or functional group. Unless otherwise noted, when a functional group is considered "substituted," it is because said functional group is C1-C 20 alkyl group of, C2-C 20 alkenyl group of, C2-C 20 alkynyl group of, C5-C 50 It means that the aryl group is substituted with one or more selected substituents. When a functional group is described as "optionally substituted," it means that the functional group can be substituted with the substituents described above.

[0182] In this specification, C1-C 20 The alkyl groups include, for example, straight-chain alkyl groups such as methyl, ethyl, hexyl, octyl, and decyl groups; branched alkyl groups such as isopropyl, tert-butyl, neopentyl, and hexyl groups; etc. Among these, they may be methyl or ethyl groups, considering the ease of procuring raw materials and the usefulness of the product. One or more hydrogen atoms of the alkyl groups may be substituted with substituents as defined in the "substitution" described above.

[0183] In this specification, a C1-C6 alkylene group refers to a divalent radical group obtained by removing one hydrogen atom from the alkyl group described above. For example, a C1-C6 alkylene group may be a straight-chain alkylene group such as a methylene group, an ethylene group, or a hexylene group; a branched alkylene group such as an isopropylene group, a tert-butylene group, a neopentylene group, or a hexylene group; etc. One or more hydrogen atoms of the alkylene group may be substituted with a substituent as defined in the "substitution" described above.

[0184] In this specification, C2-C 20 The alkenyl group of includes at least one double bond. For example, C2-C 20Examples of alkenyl groups include ethenyl groups, n-propenyl groups, isopropenyl groups, n-butenyl groups, isobutenyl groups, octenyl groups, decenyl groups, tetradecenyl groups, hexadecenyl groups, etc. One or more hydrogen atoms of the alkenyl groups can be substituted with substituents as defined in the "substitution" described above.

[0185] In this specification, C2-C 20 The alkynyl group of includes at least one triple bond. For example, C2-C 20 Examples of alkynyl groups include ethinyl, n-propynyl, etc. One or more hydrogen atoms of the alkynyl group can be substituted with substituents as defined in the "substitution" described above.

[0186] In this specification, C5-C 50 Unless otherwise specified, the aryl group refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly connected, or indirectly connected (so that different aromatic rings are bonded to a common group, e.g., methylene or ethylene moiety). For example, C5-C 40 Examples of aryl groups include phenyl groups, naphthyl groups, etc. One or more hydrogen atoms of the aryl group can be replaced with substituents as defined in the "substitution" described above.

[0187] In this specification, C6-C 50 The arylalkylene group refers to an aryl-substituted alkyl radical. For example, C6-C 50 The arylalkylene group of can be benzyl, etc. In this specification, C6-C 50 The alkylarylene group refers to an alkyl-substituted aryl radical. For example, C6-C 50 Examples of alkylarylene groups include methylphenylene, etc. The terms aryl and alkyl each have the meanings and contents described above.

[0188] In this specification, C5-C 50A heteroaryl group means that the aryl group contains one or more heteroatoms selected from N, O, S, and P, and the remainder are carbons. For example, C5-C 50 Examples of heteroaryl groups include pyrazines, etc. In the case where the heteroaryl group is a fused ring, at least one of the fused rings may contain one or more of the above heteroatoms. Each aryl term has the meaning and content described above.

[0189] In this specification, C6-C 50 The heteroarylalkylene group refers to an arylalkylene in which one or more heteroatoms selected from N, O, S, and P are contained within the aryl group, and the remainder is carbon. The term arylalkylene has the meaning and content described above.

[0190] In this specification, C6-C 50 The alkylheteroarylene group refers to an alkylheteroarylene in which the aryl group contains one or more heteroatoms selected from N, O, S, and P, and the remainder is carbon. The term alkylarylene has the meaning and content described above.

[0191]

[0192] The present invention will be explained below through the following examples. At this time, the following examples are presented merely to illustrate the invention, and the scope of the present invention is not limited by the following examples.

[0193]

[0194] [Example]

[0195]

[0196] Preparation Example 1: Preparation of Compound 1

[0197] A 4-vinylbenzyl chloride solution was added to a tetramethylenediamine (TMEDA) solution dissolved in acetonitrile such that the molar ratio of vinylbenzyl chloride to TMEDA was 2.08:1, and the mixture was stirred at room temperature under an inert atmosphere to prepare a mixture. The mixture was filtered and washed with acetonitrile, and then dried at 60°C under vacuum to obtain the first compound of Compound 1 below.

[0198]

[0199]

[0200] Preparation Example 2: Preparation of Compound 2

[0201] The first compound of the following compound 2 was obtained in the same manner as in Example 1, except that a 4-vinylbenzyl chloride solution was added to a tetramethylhexanediamine (TMDDA) solution dissolved in acetonitrile such that the molar ratio of vinylbenzyl chloride to TMHDA was 2.08:1.

[0202]

[0203]

[0204] Preparation Example 3: Preparation of Compound 3

[0205] The first compound of the following compound 3 was obtained in the same manner as in Example 1, except that a 4-vinylbenzyl chloride solution was added to a diazabicyclo[2.2.2] octane 1,2,3,4-tetramethyl (DABCO™) solution dissolved in acetonitrile such that the molar ratio of vinylbenzyl chloride to DABCO™ was 2.08:1.

[0206]

[0207]

[0208] Preparation Example 4: Preparation of Compound 4

[0209] The first compound of the following compound 4 was obtained in the same manner as in Example 1, except that a 4-vinylbenzyl chloride solution was added to a hexamethylenetetraamine (HMTA) solution dissolved in acetonitrile such that the molar ratio of vinylbenzyl chloride to HMTA was 2.08:1.

[0210]

[0211]

[0212] Preparation Example 5: Preparation of Compound 5

[0213] The first compound of the following compound 5 was obtained in the same manner as in Example 1, except that a 4-vinylbenzyl chloride solution was added to a pyrazine solution dissolved in acetonitrile such that the molar ratio of vinylbenzyl chloride to pyrazine was 2.08:1.

[0214]

[0215]

[0216] Example 1: Preparation of anion exchange membrane

[0217] A polypropylene (PP) porous polymer support with a thickness of 100 μm (porosity: 51%) was prepared. The porous polymer support was immersed in a 2 wt% quaternary ammonium-based aqueous solution for 10 minutes, and then dried in a 70°C hot air oven for 10 minutes to hydrophilize it. The hydrophilized porous support was 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.

[0218] At this time, the composition for forming an anion exchange polymer was prepared by mixing 20 wt% of the first compound of Compound 1 obtained according to Preparation Example 1, 40 wt% of the second compound of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, 0.5 wt% of a photoinitiator of 2-hydroxy-2-methylpropiophenone (manufactured by Ciba), and the remainder being distilled water.

[0219] The polypropylene porous polymer support was impregnated with the above composition for forming an anion exchange polymer, thereby filling the surface and the interior of the pores of the porous polymer support with the composition. The porous polymer support filled with the composition was fed into a compression roll, and a polyester film with a thickness of 50 μm was compressed 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. The laminate was irradiated with UVC ultraviolet light at a light intensity of 3000 mJ / cm² to form an anion exchange polymer, which is a crosslinking product of the composition, on the surface and the interior of 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 the interior of the pores to produce an anion exchange membrane.

[0220]

[0221] Example 2: Preparation of anion exchange membrane

[0222] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20% by weight of the first compound of Compound 2 obtained according to Preparation Example 2 was used in the composition for forming an anion exchange polymer.

[0223]

[0224] Example 3: Preparation of anion exchange membrane

[0225] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20% by weight of the first compound of Compound 3 obtained according to Preparation Example 3 was used in the composition for forming an anion exchange polymer.

[0226]

[0227] Example 4: Preparation of anion exchange membrane

[0228] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20 weight% of the first compound of Compound 4 obtained according to Preparation Example 4 was used in the composition for forming an anion exchange polymer.

[0229]

[0230] Example 5: Preparation of anion exchange membrane

[0231] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20% by weight of the first compound of Compound 5 obtained according to Preparation Example 5 was used in the composition for forming an anion exchange polymer.

[0232]

[0233] Example 6: Preparation of anion exchange membrane

[0234] An anion exchange membrane was prepared in the same manner as in Example 1, except that 10 wt% of the first compound of Compound 1 obtained according to Preparation Example 1 and 20 wt% of the second compound of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride were used in the composition for forming an anion exchange polymer.

[0235]

[0236] Example 7: Preparation of anion exchange membrane

[0237] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20 wt% of the first compound of Compound 1 obtained according to Preparation Example 1 and 22 wt% of the second compound of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride were used in the composition for forming an anion exchange polymer.

[0238]

[0239] Example 8: Preparation of anion exchange membrane

[0240] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20 wt% of the first compound of Compound 1 obtained according to Preparation Example 1 and 60 wt% of the second compound of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride were used in the composition for forming an anion exchange polymer.

[0241]

[0242] Example 9: Preparation of anion exchange membrane

[0243] An anion exchange membrane was prepared in the same manner as in Example 1, except that a polypropylene (PP) porous polymer support with a thickness of 100 μm (porosity: 30%) was used.

[0244]

[0245] Example 10: Preparation of anion exchange membrane

[0246] An anion exchange membrane was prepared in the same manner as in Example 1, except that a polypropylene (PP) porous polymer support with a thickness of 100 μm (porosity: 80%) was used.

[0247]

[0248] Example 11: Preparation of anion exchange membrane

[0249] An anion exchange membrane was prepared in the same manner as in Example 1, except that a polypropylene (PP) porous polymer support with a thickness of 70 μm (porosity: 51%) was used.

[0250]

[0251] Example 12: Preparation of anion exchange membrane

[0252] An anion exchange membrane was prepared in the same manner as in Example 1, except that a polypropylene (PP) porous polymer support with a thickness of 130 μm (porosity: 51%) was used.

[0253]

[0254] Comparative Example 1: Preparation of anion exchange membrane

[0255] An anion exchange membrane was prepared in the same manner as in Example 1, except that only the first compound of Compound 1 obtained according to Preparation Example 1 was used in the composition for forming an anion exchange membrane without the second compound, at a weight of 60%.

[0256]

[0257] Comparative Example 2: Preparation of anion exchange membrane

[0258] An anion exchange membrane was prepared in the same manner as in Example 1, except that only the first compound of Compound 2 obtained according to Preparation Example 2 was used in the composition for forming an anion exchange membrane without the second compound, at a weight of 60%.

[0259]

[0260] Comparative Example 3: Preparation of anion exchange membrane

[0261] An anion exchange membrane was prepared in the same manner as in Example 1, except that only the first compound of Compound 3 obtained according to Preparation Example 3 was used in the composition for forming an anion exchange membrane without the second compound, at a weight of 60%.

[0262]

[0263] Comparative Example 4: Preparation of anion exchange membrane

[0264] An anion exchange membrane was prepared in the same manner as in Example 1, except that only the first compound of Compound 4 obtained according to Preparation Example 4 was used in the composition for forming an anion exchange membrane without the second compound, at a weight of 60%.

[0265]

[0266] Comparative Example 5: Preparation of anion exchange membrane

[0267] An anion exchange membrane was prepared in the same manner as in Example 1, except that only the first compound of Compound 5 obtained according to Preparation Example 5 was used in the composition for forming an anion exchange membrane without the second compound, at a weight of 60%.

[0268]

[0269] Comparative Example 6: Preparation of anion exchange membrane

[0270] An anion exchange membrane was prepared in the same manner as in Example 1, except that 9% by weight of the first compound of Compound 1 obtained according to Preparation Example 1 was used in the composition for forming an anion exchange polymer.

[0271]

[0272] Comparative Example 7: Preparation of anion exchange membrane

[0273] An anion exchange membrane was prepared in the same manner as in Example 1, except that 31% by weight of the first compound of Compound 1 obtained according to Preparation Example 1 was used in the composition for forming an anion exchange polymer.

[0274]

[0275] Comparative Example 8: Preparation of anion exchange membrane

[0276] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20 wt% of the first compound of Compound 1 obtained according to Preparation Example 1 and 20 wt% of the second compound of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride were used in the composition for forming an anion exchange polymer.

[0277]

[0278] Comparative Example 9: Preparation of anion exchange membrane

[0279] An anion exchange membrane was prepared in the same manner as in Example 1, except that 20 wt% of the first compound of Compound 1 obtained according to Preparation Example 1 and 62 wt% of the second compound of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride were used in the composition for forming an anion exchange polymer.

[0280]

[0281] Comparative Example 10: Preparation of anion exchange membrane

[0282] An anion exchange membrane was prepared in the same manner as in Example 1, except that a polypropylene (PP) porous polymer support with a thickness of 100 μm (porosity: 29%) was used.

[0283]

[0284] Evaluation Example 1: Evaluation of Physical Properties of Ion Exchange Membranes

[0285] The physical properties of the anion exchange membranes prepared in Examples 1 to 12 and Comparative Examples 1 to 10 were evaluated by experimenting as follows, and the evaluation results are shown in Table 1 below.

[0286] (1) Sheet resistance (Ω·cm²)

[0287] Each anion exchange membrane was cut into a 5 cm x 5 cm size 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 sheet resistance, and the linear resistance (R) of the anion exchange membrane was measured using an LCR meter (E4908A, Agilent). 11 ), resistance of 0.5 M NaCl aqueous solution (R 12 ) was measured. The measured resistance value (R 11 , R 12 Substitute ) into Equation 1 below to obtain the sheet resistance (R m ) was obtained.

[0288] [Equation 1]

[0289] R m (Ω·㎠) = (R 11 - R 12 ) x S

[0290] Among the foods,

[0291] R m is the sheet resistance of the anion exchange membrane, and

[0292] R 11 is the linear resistance of the anion exchange membrane, and

[0293] R 12 is the resistance of a 0.5 M NaCl aqueous solution, and

[0294] S is the area of ​​the electrode.

[0295] (2) Ion Exchange Capacity (IEC, meq / g)

[0296] Samples were prepared by cutting each anion exchange membrane into a size of 5 cm x 5 cm. The samples were washed with distilled water and dried with a tissue. 70 ml of 1 M NaCl solution was placed in a vial, and the dried samples were immersed in the 1 M NaCl solution for at least 12 hours for primary pretreatment. Afterward, the samples that had completed the primary pretreatment were washed several times with distilled water and dried with a tissue. 70 ml of 0.5 M Na2CO3 solution was placed in a vial, and the dried samples were immersed in the 0.5 M Na2CO3 solution for at least 12 hours for secondary pretreatment. Afterward, the samples that had completed the secondary pretreatment were removed from the vial, the remaining solution was titrated with 0.01 M AgNO3 solution, and the volume of AgNO3 solution added during 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 ion exchange capacity (IEC) was calculated by substituting the measured weight of the dried anion exchange membrane into Equation 2 below.

[0297] [Equation 2]

[0298] IEC(meq / g) = (Volume of titrant (ml) x 0.01) / Weight of dried anion exchange membrane (g)

[0299]

[0300] Referring to Table 1, the anion exchange membranes of Examples 1 to 12 were excellent, with a sheet resistance of 4.7 Ω·cm² or less and an ion exchange capacity of 1.8 meq / g or more.

[0301] In contrast, the anion exchange membranes of Comparative Examples 1 to 5, which did not use the second compound, had a high sheet resistance of 8.4 Ω·cm² or higher and a low ion exchange capacity of 1.5 meq / g or lower. The anion exchange membranes of Comparative Examples 6 and 7, which had low or high content of the first compound; the anion exchange membranes of Comparative Examples 8 and 9, in which the weight ratio of the first compound to the second compound fell outside the range of 1:1 to 1:3; and the anion exchange membrane of Comparative Example 10, in which the porosity of the porous polymer support was low, all had a low ion exchange capacity of 1.5 meq / g or lower. In addition, the anion exchange membrane of Comparative Example 10, in which the porosity of the porous polymer support was low, had a very high sheet resistance of 8.5 Ω·cm².

[0302] From this, it can be confirmed that the anion exchange membranes of Examples 1 to 12 can provide anion exchange membranes with high ion exchange capacity.

[0303]

[0304] Although an exemplary embodiment has been described in detail above with reference to the attached drawings, the present creative idea is not limited to such examples. It is obvious that a person skilled in the art to which the present creative idea belongs can derive various variations or modifications within the scope of the technical idea described in the patent claims, and these also naturally fall within the technical scope of the present creative idea.

[0305]

[0306] [Explanation of the symbol]

[0307] 20: Porous polymer support, 21: Pores,

[0308] 30: Anion exchange polymer main chain having cationic functional groups,

[0309] 31: Anion exchange polymer

Claims

1. Porous polymer support; and An electrolyte containing an anion exchange polymer on the surface and inside the pores of the porous polymer support; comprising The above anion exchange polymer is a crosslinked product of a composition comprising two or more monomers, and Anion exchange membrane comprising two or more monomers, wherein the above two or more monomers comprise a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2: [Chemical Formula 1] During the meal, R1 is a single bond, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, or a combination thereof; R2 and R3 are vinyl groups, respectively; R a , R b , R c , R d is an independently substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a quaternary ammonium cation, or R a , R b , R c , R d C5-C5s that combine with each other to form substituted or unsubstituted C5s 50 aromatic heterocyclic groups or substituted or unsubstituted C5-C 50 Forming an aliphatic heterocyclic ring; Y1 - , Y2 - are independent of each other F - , Cl - , Br - , or I - is; [Chemical Formula 2] During the meal, A is a single-bonded, substituted, or unsubstituted C1-C6 alkylene group; R'1, R'2, and R'3 are independently substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C5-C 50 aryl groups, substituted or unsubstituted C6-C 50 arylalkylene groups of, substituted or unsubstituted C6-C 50 alkylarylene groups, substituted or unsubstituted C5-C 50 heteroaryl groups, substituted or unsubstituted C6-C 50 heteroarylalkylene groups of, substituted or unsubstituted C6-C 50 alkylheteroarylene groups of, or a combination thereof; R'4 is a vinyl group; Y3 - is F - , Cl - , Br - , or I - am.

2. In Paragraph 1, Anion exchange membrane comprising a first compound represented by the above chemical formula 1, comprising one or more selected from the following compounds 1 to 6: , , , , .

3. In Paragraph 1, An anion exchange membrane having a content of the first compound represented by the above chemical formula 1 of 10% to 30% by weight based on 100% by weight of the total composition.

4. In Paragraph 1, The second compound represented by the above chemical formula 2 is, (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; 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; or Anion exchange membrane comprising 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, and 2-(acryloyloxy)-N((9,10-dihydropyrene-4-yl)methyl)-N,N-dimethylethane-1-ammonium iodide.

5. In Paragraph 1, An anion exchange membrane having a weight ratio of a first compound represented by Chemical Formula 1 to a second compound represented by Chemical Formula 2 of 1:1 to 1:

3.

6. In Paragraph 1, An anion exchange membrane having a total content of a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2 of 30% to 85% by weight based on 100% by weight of the entire composition.

7. In Paragraph 1, Anion exchange membrane in which the above porous polymer support is a membrane structure, a nonwoven structure, a fabric structure, or a mesh structure.

8. In Paragraph 1, The above 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, forming an anion exchange membrane.

9. In Paragraph 1, An anion exchange membrane having a porosity of 30% to 80% and a thickness of 70 μm to 130 μm of the porous polymer support.

10. In Paragraph 1, An anion exchange membrane having an ion exchange capacity (IEC) of 1.8 meq / g or more.

11. In Paragraph 1, The above anion exchange membrane is an anion exchange membrane used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems.

12. A step of providing a porous polymer support; A step of preparing a composition for forming an anion exchange polymer comprising a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2; A step of impregnating the porous polymer support with the above-mentioned anion exchange polymer forming composition to fill the surface and the interior of the pores of the porous polymer support with the composition; A step of manufacturing a laminate in which a polyester film and a porous polymer support are laminated by pressing a polyester film onto at least one surface of a porous polymer support filled with the above composition; A step of irradiating light onto the laminate and crosslinking the composition to form an anion exchange polymer, which is a crosslinking product of the composition, on the surface of the porous polymer support and inside the pores; and A method for manufacturing an anion exchange membrane, comprising the step of peeling off a polyester-based film from a porous polymer support in which the anion exchange polymer is formed on the surface and inside the pores to manufacture an anion exchange membrane; [Chemical Formula 1] During the meal, R1 is a single bond, a substituted or unsubstituted C1-C6 alkylene group, a substituted or unsubstituted C2-C6 alkenylene group, or a combination thereof; R2 and R3 are vinyl groups, respectively; R a , R b , R c , R d is an independently substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a quaternary ammonium cation, or R a , R b , R c , R d C5-C5s that combine with each other to form substituted or unsubstituted C5s 50 aromatic heterocyclic groups or substituted or unsubstituted C5-C 50 Forming an aliphatic heterocyclic ring; Y1 - , Y2 - are independent of each other F - , Cl - , Br - , or I - is; [Chemical Formula 2] During the meal, A is a single-bonded, substituted, or unsubstituted C1-C6 alkylene group; R'1, R'2, and R'3 are independently substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C5-C 50 aryl groups, substituted or unsubstituted C6-C 50 arylalkylene groups of, substituted or unsubstituted C6-C 50 alkylarylene groups, substituted or unsubstituted C5-C 50 heteroaryl groups, substituted or unsubstituted C6-C 50 heteroarylalkylene groups of, substituted or unsubstituted C6-C 50 alkylheteroarylene groups of, or a combination thereof; R'4 is a vinyl group; Y3 - is F - , Cl - , Br - , or I - am.

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