Composition for forming anion exchange polymer, anion exchange membrane and method for manufacturing anion exchange membrane

Abstract

A composition for forming an anion exchange polymer comprising a first monomer represented by chemical formula A; and a crosslinking agent represented by chemical formula B, an anion exchange membrane comprising the crosslinking product thereof, and a method for manufacturing the anion exchange membrane are disclosed: Refer to the present specification for the description of chemical formulas A and B.

Description

Technology Field

[0001] The present disclosure relates to a composition for forming an anion exchange polymer, an anion exchange membrane, and a method for manufacturing an anion exchange membrane. Background Technology

[0002] Ion exchange membranes are synthetic resin membranes that selectively allow only one type of ion to pass through, either cations or anions. Cation exchange membranes possess negatively charged functional groups, enabling the selective passage of cations, while anion exchange membranes possess positively charged functional groups, enabling the selective passage of anions. Based on electrodialysis technology, ion exchange membranes are widely used in various fields such as seawater concentration, desalination, purification of organic acids, and recovery of valuable metals. Furthermore, they are being applied to hydrogen production technology via water electrolysis, which has recently garnered attention for securing sustainable energy alongside the issue of CO2 reduction due to global warming. Water electrolysis technologies utilizing ion exchange membranes include cation exchange membrane or proton exchange membrane electrolysis technologies utilizing proton migration, and anion exchange membrane electrolysis technologies utilizing anion exchange membranes in an alkaline solution environment. Anion exchange membrane water electrolysis technology utilizes water electrolysis through the conduction of hydroxide ions. Compared to proton exchange membrane water electrolysis technology that utilizes hydrogen ion conduction, it has the advantage of allowing the use of low-cost water splitting catalysts, so much research is currently being conducted on it.

[0003] These 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. Perfluorinated anion exchange membranes, which have strong chemical resistance under acidic or basic conditions, can be used as anion exchange membranes, but due to their high cost, hydrocarbon anion exchange membranes are applied in actual systems. However, there are limitations to the application processes and conditions due to the chemical resistance issues of hydrocarbon anion exchange membranes. The problem to be solved

[0004] The invention provides a hydrocarbon-based anion exchange membrane having excellent chemical resistance, low sheet resistance, and high ion exchange capacity. means of solving the problem

[0005] According to one aspect, a composition for forming an anion exchange polymer is provided, comprising: a first monomer represented by the following formula A; and a crosslinking agent represented by the following formula B:

[0006] <Chemical Formula A>

[0007]

[0008] <Chemical Formula B>

[0009]

[0010] Among the above chemical formulas A and B,

[0011] Vi is a vinyl group, and

[0012] R 11 to R 16 , R 21 and R 22 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups, and substituted or unsubstituted C2-C 20 Selected from alkenyl groups,

[0013] R 11 and R 12 They optionally combine with each other,

[0014] R 13 and R 14 They optionally combine with each other,

[0015] R 21 and R 22 They optionally combine with each other,

[0016] a4 is selected from integers 0 to 4, and

[0017] L1 and L2 are independent of each other, single-bonded and substituted or unsubstituted C1-C 20 Selected from alkylene groups, and

[0018] X -and Y - are independent of each other, F - , Cl - , Br - and I - Selected from among,

[0019] n1, n2, m1 and m2 are each selected from integers from 0 to 10.

[0020] According to another aspect, an anion exchange membrane is provided comprising a porous polymer support; and an anion exchange polymer; wherein the anion exchange polymer is a crosslinked product of the composition for forming the anion exchange polymer described above.

[0021] According to another aspect, the method comprises the steps of: preparing a composition for forming an anion exchange polymer comprising a first monomer represented by the above-described chemical formula A, a crosslinking agent represented by the above-described chemical formula B, a photoinitiator, and a solvent; impregnating a porous polymer support with the composition for forming an anion exchange polymer to fill at least one portion of the surface and the interior of the pores of the porous polymer support with the composition for forming an anion exchange polymer; pressing a film onto at least one surface of the porous polymer support filled with the composition for forming an anion exchange polymer to produce a laminate in which the film and the porous polymer support are laminated; irradiating light onto the laminate and crosslinking the composition for forming an anion exchange polymer to form an anion exchange polymer, which is a crosslinking product of the composition for forming an anion exchange polymer, in at least one portion of the surface and the interior of the pores of the porous polymer support. A method for manufacturing an anion exchange membrane is provided, comprising the step of manufacturing an anion exchange membrane by peeling off a film from a porous polymer support in which the anion exchange polymer is formed in at least one part of the surface and the interior of the pores. Effects of the invention

[0022] According to one aspect, an anion exchange membrane can have excellent chemical resistance under acid or basic conditions by being prepared from a composition for forming an anion exchange polymer comprising a first monomer represented by Formula A, a crosslinking agent represented by Formula B, and / or optionally a second monomer represented by Formula C. Specifically, the anion exchange membrane can have the characteristic of having effectively small changes in sheet resistance and ion exchange capacity (IEC) over time under acid or basic conditions. In addition, the anion exchange membrane can have low sheet resistance and high ion exchange capacity under acid or basic conditions while having excellent chemical resistance. Brief explanation of the drawing

[0023] FIG. 1 is a schematic diagram of an anion exchange membrane according to one embodiment. Specific details for implementing the invention

[0024] Hereinafter, a composition for forming an anion exchange polymer, an anion exchange membrane, and a method for manufacturing an anion exchange membrane according to one embodiment will be described in more detail. The following is presented as an example and is not intended to limit the present invention, and the present invention is defined only by the claims set forth below.

[0025] 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.

[0026] Methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, but suitable methods and materials are described herein.

[0027] In this specification, the term “includes” is used to indicate that other components may be added and / or interposed, rather than being excluded, unless specifically stated otherwise.

[0028] The numerical values ​​described in this specification may be understood to include the meaning of "approximately" even if not explicitly stated.

[0029] In this specification, "carbon numbers a to b" or "C a -C b "a and b of [the expression] refer to the number of carbon atoms of a specific functional group. That is, the functional group may include carbon atoms from a to b. For example, "alkyl group having 1 to 2 carbon atoms" or "C1-C2 alkyl group" refers to an alkyl group having 1 to 2 carbons, namely -CH3 and -CH2CH3.

[0030] In this specification, the term “alkyl” means a branched (broken) or unbranched (straight-chain) aliphatic hydrocarbon. The alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc., and each of these may be optionally substituted or not substituted.

[0031] In this specification, the term "alkylene" means a divalent group having the same structure as "alkyl". The alkylene group includes, but is not necessarily limited to, methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, heptylene groups, etc., and each of these may be optionally substituted or not substituted.

[0032] In this specification, the term "alkenyl" means a monovalent hydrocarbon containing one or more carbon-carbon double bonds at the middle or terminal of an alkyl group. The alkenyl group includes, but is not necessarily limited to, an ethenyl group, a propenyl group, a butenyl group, etc., and each of these may be optionally substituted or not substituted. Meanwhile, the ethenyl group may also be referred to as a vinyl group.

[0033] 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. For example, when a functional group is considered to be "substituted," said functional group is deuterium, C1-C 40 Alkyl group, C1-C 40 Alkoxy group, C2-C 40 alkenyl group, C2-C 40 alkynyl group, C3-C 40 Cycloalkyl group, C3-C 40 Cycloalkenyl group, C6-C 40 It means that it is substituted with one or more substituents selected from aryl groups, etc. If it is stated that the functional group is "optionally substituted," it means that the said functional group may be substituted with the substituents described above.

[0034] Perfluorinated anion exchange membranes or hydrocarbon anion exchange membranes are known. Among them, hydrocarbon anion exchange membranes are cheaper than perfluorinated anion exchange membranes, but their chemical resistance is insufficient. In addition, anion exchange membranes that use a support have a certain proportion of the support, which limits the reduction of sheet resistance and / or increase of ion exchange capacity to improve concentration and desalination performance.

[0035] The inventors provide an anion exchange membrane that solves the aforementioned problems and is a hydrocarbon-based anion exchange membrane, having sufficiently low sheet resistance and sufficiently high ion exchange capacity, and excellent chemical resistance.

[0036] According to one aspect, a composition for forming an anion exchange polymer is provided, comprising: a first monomer represented by the following formula A; and a crosslinking agent represented by the following formula B:

[0037] <Chemical Formula A>

[0038]

[0039] <Chemical Formula B>

[0040]

[0041] In the above chemical formulas A and B, Vi is a vinyl group.

[0042] The above vinyl device It is a group indicated by (* is a bonding site with an adjacent atom) and can be referred to as a C2 alkenyl group or an ethenyl group.

[0043] First monomer

[0044] In the above chemical formula A, R 11 to R 16 They are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups, and substituted or unsubstituted C2-C 20 It can be selected from alkenyl groups.

[0045] According to one embodiment, R 11 to R 16 They can be independently hydrogen, deuterium, methyl group, ethyl group, propyl group, ethenyl group, propylene group, etc.

[0046] According to one embodiment, R 11 and R 12 They can optionally combine with each other. That is, R 11 and R 12 They may or may not combine with each other. For example, N + -R 11 -R 12 -N + A ring composed of -L1 can be formed.

[0047] According to one embodiment, R 13 and R 14 They can optionally combine with each other. That is, R 13 and R 14 They may or may not combine with each other. For example, N + -R 13 -R 14 -N + A ring composed of -L1 can be formed.

[0048] In the above chemical formula A, R 15 and R 16 It can be hydrogen or deuterium independently of each other.

[0049] In the above chemical formula A, a4 may be selected from integers from 0 to 4. According to one embodiment, a4 may be 0 or 4.

[0050] In the above chemical formula A, L1 is a single bond and a substituted or unsubstituted C1-C 20 It can be selected from alkylene groups.

[0051] According to one embodiment, L1 may be a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group, etc.

[0052] Among the above chemical formula A, X - and Y - are independent of each other, F - , Cl - , Br - and I - It can be selected from among them.

[0053] According to one embodiment, X - and Y - They can be identical to each other.

[0054] According to one embodiment, X - and Y - At least one of them is Cl - It could be.

[0055] In the above chemical formula A, each of n1 and n2 can be selected from integers from 0 to 10.

[0056] According to one embodiment, n1 and n2 can each be selected from integers from 0 to 2.

[0057] According to one embodiment, n1 and n2 may be identical to each other.

[0058] According to one embodiment, at least one of n1 and n2 may be 1.

[0059] According to one embodiment, the first monomer may be represented by any one of the following chemical formulas A-1 to A-6:

[0060] <Chemical Formula A-1>

[0061]

[0062] <Chemical Formula A-2>

[0063]

[0064] <Chemical Formula A-3>

[0065]

[0066] <Chemical Formula A-4>

[0067]

[0068] <Chemical Formula A-5>

[0069]

[0070] <Chemical Formula A-6>

[0071]

[0072] Among the above chemical formulas A-1 to A-6, Vi, R 11 to R 14 , L1, X - , Y - , n1 and n2 are each the same as described in the above chemical formula A.

[0073] According to one embodiment, among the above formulas A and A-1 to A-6, The group represented by may be represented by the following chemical formula A-11 or A-12:

[0074] <Chemical Formula A-11>

[0075]

[0076] <Chemical Formula A-12>

[0077]

[0078] Each of the above * and *' is a bonding site with an adjacent atom.

[0079] Referring to the above chemical formula A-11, R in the above chemical formula A 11 and R 12 are not combined with each other, and R 13 and R 14 It can be confirmed that they do not combine with each other.

[0080] Referring to the above chemical formula A-12, L1 in the above chemical formula A is ethylene, and R 11 and R 12 are combined with each other, and R 13 and R 14 It can be confirmed that they combine with each other.

[0081] According to one embodiment, the first monomer may be one or more selected from the following compounds A1 to A3:

[0082]

[0083]

[0084] For example, the first monomer may be compound A3.

[0085] crosslinking agent

[0086] Referring to the above chemical formula B, the crosslinking agent is a material having two NC(=O) functional groups and two vinyl groups at both ends. As a result, an anion exchange membrane formed from a composition containing the crosslinking agent can have a low level of sheet resistance, a high level of ion exchange capacity, and excellent chemical resistance.

[0087] In the above chemical formula B, R 21 and R 22 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups and substituted or unsubstituted C2-C 20 It can be selected from alkenyl groups.

[0088] According to one embodiment, R 21 and R 22 It can be hydrogen, deuterium, methyl group, ethyl group, propyl group, ethenyl group, or propylene group independently of each other.

[0089] According to one embodiment, R 21 and R 22 They can optionally combine with each other. R 21 and R 22 For compounds bonded to each other, refer to the following compound B1:

[0090] . Referring to the above compound B1, L2 in the above chemical formula B is an ethylene group, and R 21 and R 22 It can be confirmed that they combine with each other.

[0091] In the above chemical formula B, L2 is a single bond and a substituted or unsubstituted C1-C 20 It can be selected from alkylene groups.

[0092] According to one embodiment, L2 may be a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group, etc.

[0093] In the above chemical formula B, m1 and m2 can each be selected from integers from 0 to 10.

[0094] According to one embodiment, m1 and m2 can each be selected from integers from 0 to 2.

[0095] According to one embodiment, m1 and m2 may be identical to each other.

[0096] According to one embodiment, at least one of m1 and m2 may be 0.

[0097] According to one embodiment, the crosslinking agent may be represented by the following chemical formula B-1:

[0098] <Chemical Formula B-1>

[0099]

[0100] In the above chemical formula B-1, Vi, R 21 , R 22 and L2 are each the same as described in the above chemical formula B.

[0101] According to one embodiment, the crosslinking agent may be one or more selected from the following compounds B1 to B3:

[0102]

[0103]

[0104] .

[0105] Second monomer

[0106] The above composition for forming an anion exchange polymer may further include a second monomer represented by the following chemical formula C:

[0107] <Chemical Formula C>

[0108]

[0109] In the above chemical formula C, Vi is a vinyl group.

[0110] Among the above chemical formula C, R 31 to R 34are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups and substituted or unsubstituted C2-C 20 It can be selected from alkenyl groups.

[0111] According to one embodiment, R 31 to R 34 It can be hydrogen, deuterium, methyl group, ethyl group, propyl group, ethenyl group, or propylene group independently of each other.

[0112] According to one embodiment, R 31 to R 33 They can be identical to each other.

[0113] According to one embodiment, R 34 It can be hydrogen or deuterium.

[0114] Among the above chemical formula C, a4 may be selected from integers from 0 to 4. According to one embodiment, a4 may be 0 or 4.

[0115] Among the above chemical formula C, Z - is F - , Cl - , Br - and I - It can be selected from among them.

[0116] According to one embodiment, X among the formulas A and C above - , Y - and Z - They can be identical to each other.

[0117] Among the above chemical formula C, p can be selected from integers from 0 to 10.

[0118] According to one embodiment, p can be 0, 1, or 2.

[0119] According to one embodiment, the second monomer may be represented by the following chemical formula C-1 or C-2:

[0120] <Chemical Formula C-1>

[0121]

[0122] <Chemical Formula C-2>

[0123]

[0124] Among the above chemical formulas C-1 and C-2, Vi, R 31 to R 33 , Z - and p are each the same as described in the above chemical formula C.

[0125] According to one embodiment, the second monomer may be the following compound C1:

[0126] .

[0127] Composition for forming anion exchange polymer

[0128] When the above-described composition for forming an anion exchange polymer is crosslinked, each of the first monomer, the crosslinking agent, and the second monomer described above can be crosslinked to each other through vinyl groups.

[0129] According to one embodiment, the ratio of the moles of the first monomer to the moles of the crosslinking agent may be 0.9:1 to 4.5:1. For example, the molar ratio of the first monomer to the crosslinking agent may be 0.92:1 to 4.25:1.

[0130] According to one embodiment, the ratio of the number of moles of the first monomer to the number of moles of the second monomer may be 0.65:1 to 0.85:1. For example, the molar ratio of the first monomer to the second monomer may be 0.7:1 to 0.8:1.

[0131] According to one embodiment, the ratio of the moles of the second monomer to the moles of the crosslinking agent may be 1:0.2 to 1:0.7. For example, the molar ratio of the second monomer to the crosslinking agent may be 1:0.3 to 1:0.5.

[0132] The above composition for forming an anion exchange polymer comprises at least the first monomer and the crosslinking agent, and the content of the first monomer, the crosslinking agent, and the second monomer included in the composition for forming an anion exchange polymer satisfies the range described above, thereby preventing a decrease in the solubility characteristics of the composition, and the composition for forming an anion exchange polymer has excellent chemical resistance under acidic or basic conditions, while simultaneously having a low level of sheet resistance and a high level of ion exchange capacity under acidic or basic conditions.

[0133] anion exchange membrane

[0134] According to another aspect, an anion exchange membrane is provided, comprising a porous polymer support; and an anion exchange polymer. The anion exchange polymer is a crosslinked product of the composition for forming the anion exchange polymer described above.

[0135] According to one embodiment, the porous polymer support may be a membrane structure, a nonwoven fabric structure, a fabric structure, or a mesh structure. The porous polymer support may be in the shape of a sponge or a three-dimensional network.

[0136] According to one embodiment, the membrane structure may be a structure in which pores are regularly arranged or a three-dimensional mesh structure.

[0137] The anion exchange polymer may be located on at least one part of the surface of the porous polymer support and the interior of the pores. For example, the anion exchange polymer may be located on the surface of the porous polymer support. For another example, the anion exchange polymer may be located inside the pores of the porous polymer support. For yet another example, the anion exchange polymer may be located on both the surface of the porous polymer support and the interior of the pores.

[0138] According to one embodiment, the anion exchange polymer can be uniformly distributed on the surface of the porous polymer support and inside the pores.

[0139] According to one embodiment, the average thickness of the anion exchange membrane may be 50 micrometers (μm) to 150 μm.

[0140] FIG. 1 is a schematic diagram of an anion exchange membrane according to one embodiment.

[0141] Referring to FIG. 1, the anion exchange polymer (31) having a cationic functional group included in the anion exchange membrane (40) can be uniformly positioned on the surface of the porous polymer support (20) and inside the pores (21).

[0142] The anion exchange polymer (31) may be a crosslinked product of the composition for forming an anion exchange polymer described above. That is, the first monomer and the crosslinking agent described above may be crosslinked to form the anion exchange polymer, or the first monomer, the crosslinking agent, and the second monomer may all be crosslinked to form the anion exchange polymer. For example, the bonding product between the first monomers may form an anion exchange polymer main chain (30), and the crosslinking agent may crosslink between the anion exchange polymer main chains (30). For another example, the bonding product between the first monomer and the crosslinking agent may form an anion exchange polymer main chain (30), and the first monomer or the crosslinking agent may crosslink between the anion exchange polymer main chains (30). As another example, the combined product of the first monomer and the second monomer may form an anion exchange polymer main chain (30), and the crosslinking agent may crosslink between the anion exchange polymer main chains (30).

[0143] According to one embodiment, the porous polymer support (20) may comprise 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 comprise polypropylene (PP).

[0144] According to one embodiment, the anion exchange membrane (40) may be used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems. Additionally, the anion exchange membrane may be used in energy systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries.

[0145] Sheet resistance, ion exchange capacity, and the degree of change in each

[0146] The anion exchange membrane described above may have a small rate of change in sheet resistance in acidic or basic solutions. The anion exchange membrane described above may have a small rate of change in ion exchange capacity in acidic or basic solutions. That is, the anion exchange membrane may have excellent chemical resistance. Examples of the acidic solutions include H2SO4, HCl, CH3COOH, etc. Examples of the basic solutions include NaOH, KOH, Ca(OH)2, etc.

[0147] According to one embodiment, the anion exchange membrane may satisfy the following Formula 1A:

[0148] <Equation 1A>

[0149]

[0150] Among the above formula 1A,

[0151] SR a 20 is the sheet resistance of an anion exchange membrane after 20 days in an acidic solution, and

[0152] SR0 is the initial sheet resistance of the anion exchange membrane.

[0153] Formula 1A above means that the sheet resistance of the anion exchange membrane did not substantially change even after 20 days in an acidic solution.

[0154] According to one embodiment, among the above Formula 1A, 0 Ω·㎠ to 0.45 Ω·㎠, 0 Ω·㎠ to 4.4 Ω·㎠, 0 Ω·㎠ to 4.3 Ω·㎠, 0 Ω·㎠ to 4.2 Ω·㎠, 0 Ω·㎠ to 4.1 Ω·㎠, 0 Ω·㎠ to 4.0 Ω·㎠, 0 Ω·㎠ to 3.9 Ω·㎠, 0 Ω·㎠ to 3.8 Ω·㎠, 0 Ω·㎠ to 3.7 Ω·㎠, 0 Ω·㎠ to 3.6 Ω·㎠, 0 Ω·㎠ to 3.5 Ω·㎠, 0 Ω·㎠ to 3.4 Ω·㎠, 0 Ω·㎠ to 3.3 Ω·㎠, 0 Ω·㎠ to 3.2 Ω·㎠, 0 Ω·㎠ to 3.1 Ω·㎠, 0 Ω·㎠ to 3.0 Ω·㎠, 0 Ω·㎠ to 2.9 Ω·㎠, 0 Ω·㎠ to 2.8 Ω·㎠, 0 Ω·㎠ to 2.7 Ω·㎠, 0 Ω·㎠ to 2.6 Ω·㎠, 0 Ω·㎠ to 2.5 Ω·㎠, 0 Ω·㎠ to 2.4 Ω·㎠, 0 Ω·㎠ to 2.3 Ω·㎠, 0 Ω·㎠ to 2.2 Ω·㎠, 0 Ω·㎠ to 2.1 Ω·㎠, 0 Ω·㎠ to 2.0 Ω·㎠, 0 Ω·㎠ to 1.9 Ω·㎠, 0 Ω·㎠ to 1.8 Ω·㎠, 0 Ω·㎠ to 1.7 Ω·㎠, 0 Ω·㎠ to 1.6 Ω·㎠, 0 Ω·㎠ to 1.5 Ω·㎠, 0 Ω·㎠ to 1.4 Ω·㎠, 0 Ω·㎠ to 1.3 Ω·㎠, 0 Ω·㎠ to 1.2 Ω·㎠, 0 Ω·㎠ to 1.1 Ω·㎠, 0 Ω·㎠ to 1.0 Ω·㎠, 0 Ω·㎠ to 0.9 It may be Ω·㎠, 0 Ω·㎠ to 0.8 Ω·㎠, 0 Ω·㎠ to 0.7 Ω·㎠, 0 Ω·㎠ to 0.6 Ω·㎠, 0 Ω·㎠ to 0.5 Ω·㎠, 0 Ω·㎠ to 0.4 Ω·㎠, 0 Ω·㎠ to 0.3 Ω·㎠, 0 Ω·㎠ to 0.2 Ω·㎠, or 0 Ω·㎠ to 0.1 Ω·㎠.

[0155] According to one embodiment, among the above Formula 1A, SR a 20 and SR0 each may be 0.1 Ω·cm² to 3.0 Ω·cm².

[0156] According to one embodiment, the anion exchange membrane may satisfy the following Formula 1B:

[0157] <Formula 1B>

[0158]

[0159] Among the above formula 1B,

[0160] SR b 20 It is the sheet resistance of an anion exchange membrane after 20 days in a basic solution, and

[0161] SR0 is the initial sheet resistance of the anion exchange membrane.

[0162] Formula 1B above means that the sheet resistance of the anion exchange membrane did not substantially change even after 20 days in a basic solution.

[0163] According to one embodiment, among the above Formula 1B, 0 Ω·㎠ to 0.45 Ω·㎠, 0 Ω·㎠ to 4.4 Ω·㎠, 0 Ω·㎠ to 4.3 Ω·㎠, 0 Ω·㎠ to 4.2 Ω·㎠, 0 Ω·㎠ to 4.1 Ω·㎠, 0 Ω·㎠ to 4.0 Ω·㎠, 0 Ω·㎠ to 3.9 Ω·㎠, 0 Ω·㎠ to 3.8 Ω·㎠, 0 Ω·㎠ to 3.7 Ω·㎠, 0 Ω·㎠ to 3.6 Ω·㎠, 0 Ω·㎠ to 3.5 Ω·㎠, 0 Ω·㎠ to 3.4 Ω·㎠, 0 Ω·㎠ to 3.3 Ω·㎠, 0 Ω·㎠ to 3.2 Ω·㎠, 0 Ω·㎠ to 3.1 Ω·㎠, 0 Ω·㎠ to 3.0 Ω·㎠, 0 Ω·㎠ to 2.9 Ω·㎠, 0 Ω·㎠ to 2.8 Ω·㎠, 0 Ω·㎠ to 2.7 Ω·㎠, 0 Ω·㎠ to 2.6 Ω·㎠, 0 Ω·㎠ to 2.5 Ω·㎠, 0 Ω·㎠ to 2.4 Ω·㎠, 0 Ω·㎠ to 2.3 Ω·㎠, 0 Ω·㎠ to 2.2 Ω·㎠, 0 Ω·㎠ to 2.1 Ω·㎠, 0 Ω·㎠ to 2.0 Ω·㎠, 0 Ω·㎠ to 1.9 Ω·㎠, 0 Ω·㎠ to 1.8 Ω·㎠, 0 Ω·㎠ to 1.7 Ω·㎠, 0 Ω·㎠ to 1.6 Ω·㎠, 0 Ω·㎠ to 1.5 Ω·㎠, 0 Ω·㎠ to 1.4 Ω·㎠, 0 Ω·㎠ to 1.3 Ω·㎠, 0 Ω·㎠ to 1.2 Ω·㎠, 0 Ω·㎠ to 1.1 Ω·㎠, 0 Ω·㎠ to 1.0 Ω·㎠, 0 Ω·㎠ to 0.9 It may be Ω·㎠, 0 Ω·㎠ to 0.8 Ω·㎠, 0 Ω·㎠ to 0.7 Ω·㎠, 0 Ω·㎠ to 0.6 Ω·㎠, 0 Ω·㎠ to 0.5 Ω·㎠, 0 Ω·㎠ to 0.4 Ω·㎠, 0 Ω·㎠ to 0.3 Ω·㎠, 0 Ω·㎠ to 0.2 Ω·㎠, or 0 Ω·㎠ to 0.1 Ω·㎠.

[0164] According to one embodiment, among the above Formula 1B, SR b 20 and SR0 each may be 0.1 Ω·cm² to 3.0 Ω·cm².

[0165] According to one embodiment, the anion exchange membrane can satisfy the following Formula 2A:

[0166] <Equation 2A>

[0167]

[0168] Among the above formula 2A,

[0169] IEC a 20 is the ion exchange capacity of an anion exchange membrane after 20 days in an acidic solution, and

[0170] IEC0 is the ion exchange capacity of the initial anion exchange membrane.

[0171] Formula 2A above means that the ion exchange capacity of the anion exchange membrane has not substantially changed even after 20 days in an acidic solution.

[0172] According to one embodiment, among the above Formula 2A, is 0 meq / g to 0.19 meq / g, 0 meq / g to 0.18 meq / g, 0 meq / g to 0.17 meq / g, 0 meq / g to 0.16 meq / g, 0 meq / g to 0.15 meq / g, 0 meq / g to 0.14 meq / g, 0 meq / g to 0.13 meq / g, 0 meq / g to 0.12 meq / g, 0 meq / g to 0.11 meq / g, 0 meq / g to 0.10 meq / g, 0 meq / g to 0.09 meq / g, 0 meq / g to 0.08 meq / g, 0 meq / g to 0.07 meq / g, 0 meq / g to 0.06 meq / g, 0 meq / g It may be up to 0.05 meq / g, 0 meq / g to 0.04 meq / g, 0 meq / g to 0.03 meq / g, 0 meq / g to 0.02 meq / g, or 0 meq / g to 0.01 meq / g.

[0173] According to one embodiment, among the above Formula 2A, IEC0 and IEC a 20Each may be 1 meq / g to 5 meq / g, 1.1 meq / g to 5 meq / g, 1.2 meq / g to 5 meq / g, 1.3 meq / g to 5 meq / g, 1.4 meq / g to 5 meq / g, 1.5 meq / g to 5 meq / g, 1.6 meq / g to 5 meq / g, 1.7 meq / g to 5 meq / g, 1.75 meq / g to 5 meq / g, 1.8 meq / g to 5 meq / g, or 1.85 meq / g to 5 meq / g.

[0174] According to one embodiment, the anion exchange membrane may satisfy the following Formula 2B:

[0175] <Formula 2B>

[0176]

[0177] Among the above formula 2B,

[0178] IEC b 20 is the ion exchange capacity of an anion exchange membrane after 20 days in a basic solution, and

[0179] IEC0 is the ion exchange capacity of the initial anion exchange membrane.

[0180] Formula 2B above means that the ion exchange capacity of the anion exchange membrane did not substantially change even after 20 days in a basic solution.

[0181] According to one embodiment, among the above Formula 2B, is 0 meq / g to 0.19 meq / g, 0 meq / g to 0.18 meq / g, 0 meq / g to 0.17 meq / g, 0 meq / g to 0.16 meq / g, 0 meq / g to 0.15 meq / g, 0 meq / g to 0.14 meq / g, 0 meq / g to 0.13 meq / g, 0 meq / g to 0.12 meq / g, 0 meq / g to 0.11 meq / g, 0 meq / g to 0.10 meq / g, 0 meq / g to 0.09 meq / g, 0 meq / g to 0.08 meq / g, 0 meq / g to 0.07 meq / g, 0 meq / g to 0.06 meq / g, 0 meq / g It may be up to 0.05 meq / g, 0 meq / g to 0.04 meq / g, 0 meq / g to 0.03 meq / g, 0 meq / g to 0.02 meq / g, or 0 meq / g to 0.01 meq / g.

[0182] According to one embodiment, among the above Formula 2B, IEC0 and IEC b 20 Each may be 1 meq / g to 5 meq / g, 1.1 meq / g to 5 meq / g, 1.2 meq / g to 5 meq / g, 1.3 meq / g to 5 meq / g, 1.4 meq / g to 5 meq / g, 1.5 meq / g to 5 meq / g, 1.6 meq / g to 5 meq / g, 1.7 meq / g to 5 meq / g, 1.75 meq / g to 5 meq / g, 1.8 meq / g to 5 meq / g, or 1.85 meq / g to 5 meq / g.

[0183] Manufacturing method

[0184] According to another aspect, a step of preparing a composition for forming an anion exchange polymer comprising a first monomer represented by the above-described chemical formula A, a crosslinking agent represented by the above-described chemical formula B, a photoinitiator, and a solvent;

[0185] A step of impregnating a porous polymer support with the above-mentioned anion exchange polymer forming composition to fill at least one portion of the surface and the interior of the pores of the porous polymer support with the above-mentioned anion exchange polymer forming composition;

[0186] A step of manufacturing a laminate in which the film and the porous polymer support are laminated by pressing a film onto at least one surface of a porous polymer support filled with the above-mentioned anion exchange polymer forming composition;

[0187] A step of irradiating light onto the laminate and crosslinking the anion exchange polymer forming composition to form an anion exchange polymer, which is a crosslinking product of the anion exchange polymer forming composition, in at least one portion of the surface of the porous polymer support and the interior of the pores; and

[0188] A method for manufacturing an anion exchange membrane is provided, comprising the step of manufacturing an anion exchange membrane by peeling off a film from a porous polymer support in which the anion exchange polymer is formed in at least one part of the surface and the interior of the pores.

[0189] According to one embodiment, the composition for forming an anion exchange polymer may further include a second monomer represented by the formula C described above. That is, the composition for forming an anion exchange polymer may include all of the first monomer, the crosslinking agent, the second monomer, the photoinitiator, and the solvent.

[0190] The method for manufacturing the above anion exchange membrane 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 before performing the step of impregnating the porous polymer support with the anion exchange polymer forming composition and filling at least one part of the surface and the interior of the pores of the porous polymer support with the anion exchange polymer forming composition.

[0191] 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 may be omitted if the degree of hydrophilization is sufficient or if the pores are sufficiently large so that the composition for forming anion exchange polymer can be sufficiently filled.

[0192] In the hydrophilization step, immersion can be performed for 0.1 to 10 minutes, or for 0.5 to 8 minutes. If immersion is performed for less than 0.1 minutes, the surface of the porous polymer support is not sufficiently hydrophilized, which may result in a problem where the composition for forming an anion exchange polymer is not filled into the pores of the porous polymer support, and if it is performed for more than 10 minutes, problems such as a decrease in production speed and an increase in production costs may occur.

[0193] The anion exchange membrane may be in a pore-filled form in which the composition for forming the anion exchange polymer is filled into the pores of a porous polymer support. Additionally, the composition for forming the anion exchange polymer may be in a form in which it covers the outer surface of the porous polymer support.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] Surfactants may be used without restriction as long as they are known surfactants, but they may be substances having one or two alkyl chains with 12 to 20 carbon atoms in the molecule. For example, the surfactant may include dodecylbenzenesulfonic acid (DBSA), alkylbenzenesulfonic acid (ABS), linear alkylbenzenesulfonic acid (LAS), alphasulfonic acid (AS), alphaolefinsulfonic acid (AOS), alcohol polyoxyethylene ether (AE), alcohol polyoxyethylene ethersulfonic acid (AES), dimethyldialkylammonium chloride, quaternary ammonium salt of amidoamine, quaternary ammonium salt of amidoesteramine, imidazoline, imidazoline esters, or any combination thereof. According to one embodiment, the surfactant may be a quaternary ammonium-based material.

[0198] 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.

[0199] The content of the above photoinitiator may be 0.01% to 2% by weight or 0.1% to 1% by weight based on 100% by weight of the total composition for forming the anion exchange polymer.

[0200] The above photoinitiator may be used without limitation as long as it is a photoinitiator available in the relevant technical field, but may be, for example, one or more selected from 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone and 1-hydroxy-cyclohexyl-phenyl-ketone.

[0201] The above solvent may be used without limitation as long as it is a solvent available in the relevant technical field, but, for example, it may be a water-soluble solvent such as water, methanol, or ethanol, or distilled water. The above solvent may be included in the composition for forming an anion exchange polymer as the remainder excluding the first monomer represented by Formula A, the crosslinking agent represented by Formula B, the second monomer represented by Formula C, and the photoinitiator (if the composition for forming an anion exchange polymer does not include the second monomer, the solvent is included as the remainder excluding the first monomer, the crosslinking agent, and the photoinitiator).

[0202] The above film may be used without limitation as long as it is a film available in the relevant technical field, but for example, it may be a polyester-based film (specifically, a polyethylene terephthalate film).

[0203] The above film can be compressed onto the upper and / or lower surface of a porous polymer support through roll calendering. Compression 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 considering the thickness of the porous polymer support and the thickness of the film.

[0204] The thickness of the above film may be 10 μm to 150 μm, for example, 20 μm to 120 μm or 30 μm to 100 μm. If the thickness of the above film is less than 10 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 above film is greater than 150 μm, the film thickness is too thick during the crosslinking reaction, so light is not sufficiently irradiated onto the porous polymer support, and the crosslinking reaction may not occur sufficiently.

[0205] The light irradiated onto the laminate may be ultraviolet light. For example, UVA, UVB, UVC, and / or UVV may be used.

[0206] The process may include irradiating with a light intensity of 2,000 mJ / cm² to 10,000 mJ / cm² using UVC as the light. For example, it may be performed with a light intensity of 2,000 mJ / cm² to 8,000 mJ / cm² using UVC as the light. When light irradiation is performed under these conditions, an ion exchange membrane with improved ion exchange capacity can be manufactured.

[0207] When peeling off the film from the porous polymer support on which the anion exchange polymer is formed, this can be done by pulling the film attached to the porous polymer support in the opposite direction using a detachment roll.

[0208] Accordingly, the manufactured anion exchange membrane may have an average thickness of 10 to 200 μm, for example, 50 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, and if it exceeds 200 μm, the sheet resistance is high, resulting in high power consumption required for operation and desalination and concentration performance may be reduced.

[0209] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0210] Example 1

[0211] 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 polymer 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.

[0212] At this time, the composition for forming an anion exchange polymer was prepared by mixing 53% by weight of compound A3 as a first monomer belonging to formula A, 6% by weight of compound B1 as a crosslinking agent belonging to formula B, 0.5% by weight of 2-hydroxy-2-methylpropiophenone (manufactured by Ciba) photoinitiator, and the remainder being distilled water. Here, the ratio of the moles of the first monomer to the moles of the crosslinking agent was 4:1.

[0213] The above-mentioned composition for forming an anion exchange polymer was impregnated with the above-mentioned polypropylene porous polymer support to fill 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 ℃) to produce a laminate in which the polyester film and the porous polymer support were laminated. UVC ultraviolet rays with a light intensity of 3000 mJ / ㎠ were irradiated onto the laminate 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.

[0214] Example 2

[0215] An anion exchange membrane was prepared using the same method as in Example 1, except that when preparing the composition for forming an anion exchange polymer, compound C1 was further mixed as a second monomer belonging to chemical formula C, and the ratio of the first monomer:molar of crosslinking agent:molar of second monomer was adjusted to 0.85:0.2:1.

[0216] Examples 3 to 6

[0217] An anion exchange membrane was prepared using the same method as in Example 2 above, except that the molar ratios of the first monomer, crosslinking agent, and second monomer were changed as shown in Table 1 below.

[0218] Comparative Example 1 (Chemical Formula B absent)

[0219] An anion exchange membrane was prepared using the same method as in Example 3 above, except that compound B1, which belongs to chemical formula B, was not used as a crosslinking agent. Comparative Example 1 is marked with a '-' in Table 1 below because it did not use a substance belonging to chemical formula B as described above.

[0220] Comparative Example 2 (Chemical Formula B unsatisfactory)

[0221] An anion exchange membrane was prepared using the same method as in Example 3 above, except that when preparing the composition for forming an anion exchange polymer, a crosslinking agent belonging to Formula B was not used, and ethylene glycol dimethacrylate (hereinafter referred to as EGDMA) was used. Here, the moles of the first monomer:moles of EGDMA:moles of the second monomer were 0.8:0.3:1.

[0222]

[0223] Referring to the structure of the above-described EGDMA, it can be confirmed that EGDMA does not belong to any of the chemical formulas A to C described above.

[0224] In Comparative Example 2, since the EGDMA can play a role similar to a general crosslinking agent but is a substance that does not belong to the chemical formula B described above, X is indicated in Table 1 below and the type of substance is listed in parentheses.

[0225] Comparative Example 3 (Chemical Formula B absent, Chemical Formula C unsatisfactory)

[0226] An anion exchange membrane was prepared using the same method as in Comparative Example 1 above, except that when preparing a composition for forming an anion exchange polymer, (3-acrylamidopropyl)trimethylammonium chloride (hereinafter referred to as AMAC) was used instead of the second monomer belonging to Formula C, and the molar ratio of each substance was changed. The molar ratio of the first monomer to AMAC was 0.8:1.

[0227]

[0228] Referring to the structure of the above-described AMAC, it can be confirmed that AMAC does not belong to any of the chemical formulas A to C described above.

[0229] Comparative Example 3 is marked with a '-' in Table 1 below because it does not use a substance belonging to the chemical formula B described above, and is marked with an 'X' in Table 1 below and the type of substance is indicated in parentheses because the AMAC can play a role similar to a general monomer but is a substance that does not belong to the chemical formula C described above.

[0230] Example 7

[0231] When preparing a composition for forming an anion exchange polymer, compound B1 was further applied as a crosslinking agent belonging to chemical formula B, and an anion exchange membrane was prepared in the same manner as Comparative Example 3 above, except that the moles of the first monomer:moles of the crosslinking agent:moles of AMAC = 0.8:0.3:1.

[0232] Comparative Example 4 (Chemical Formula B absent, Chemical Formula C unsatisfactory)

[0233] An anion exchange membrane was prepared using the same method as Comparative Example 3 above, except that when preparing the composition for forming an anion exchange polymer, (N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride; hereinafter referred to as AEBA) was used instead of AMAC.

[0234]

[0235] Referring to the structure of the above-mentioned AEBA, it can be confirmed that AEBA does not belong to any of the chemical formulas A to C described above.

[0236] Comparative Example 4 is marked with a '-' in Table 1 below because it does not use a substance belonging to the chemical formula B described above, and is marked with an 'X' in Table 1 below and the type of substance is indicated in parentheses because the AEBA can play a role similar to a general monomer but is a substance that does not belong to the chemical formula C described above.

[0237] Comparative Examples 5 to 7 (Molar Ratio Change)

[0238] An anion exchange membrane was prepared using the same method as in Example 2 above, except that the molar ratio of each substance was changed as shown in Table 1 below.

[0239] Evaluation Example 1 (Sheet Resistance)

[0240] Each anion exchange membrane specimen was cut into a 5cm × 5cm size to prepare a first sample and a second sample. The first sample was for measuring the change in sheet resistance in an acidic solution, and the second sample was for measuring the change in sheet resistance in a basic solution. Each of the first sample and the second sample was placed between electrodes dedicated to measuring sheet resistance under 0.5M NaCl solution conditions to stabilize the measured values.

[0241] Each of the above first and second samples was placed between the electrodes for measuring sheet resistance, and the linear resistance (R1) of the anion exchange membrane was measured using an LCR meter (Agilent, E4980A). After removing the anion exchange membrane, the resistance (R2) of the 0.5M NaCl solution was measured. The sheet resistance (SR) of the anion exchange membrane was calculated using Equation 1 below, and the results are shown in Table 1 below:

[0242] <Formula 1>

[0243] SR = (R1- R2) × S

[0244] Among the above Formula 1,

[0245] SR is the sheet resistance (Ω·cm) of the anion exchange membrane 2 ) and,

[0246] R1 is the linear resistance of the anion exchange membrane, and

[0247] R2 is the resistance of a 0.5M NaCl solution, and

[0248] S is the area of ​​the electrode.

[0249] After immersing the first sample, in which the initial sheet resistance was measured, in a 9.8 wt% H2SO4 solution for 20 days, the evaluation described above was repeated to calculate the sheet resistance of the anion exchange membrane according to Equation 1, and the results are shown in Table 1 below.

[0250] After immersing the second sample, in which the initial sheet resistance was measured, in an 8 wt% NaOH solution for 20 days, the evaluation described above was repeated to calculate the sheet resistance of the anion exchange membrane according to Formula 1, and the results are shown in Table 1 below.

[0251] Evaluation Example 2 (Ion Exchange Capacity)

[0252] Each anion exchange membrane was cut to a size of 5 cm x 5 cm to prepare the third and fourth samples. The third sample was intended to measure the change in ion exchange capacity in an acidic solution, and the fourth sample was intended to measure the change in ion exchange capacity in a basic solution. Each of the third and fourth samples was washed with distilled water, and excess moisture was removed with a tissue. After filling a vial with 70 ml of 1 M NaCl solution, the dried third and fourth samples were placed in the 1 M NaCl solution and immersed for at least 12 hours to perform the first pretreatment. After completing the first pretreatment, each of the third and fourth samples was washed several times with distilled water, and excess moisture was removed with a tissue. After filling a vial with 70 ml of 0.5 M Na2CO3 solution, the third and fourth samples, each with water removed, were placed in the 0.5 M Na2CO3 solution and immersed for at least 12 hours for secondary pretreatment. After completing the secondary pretreatment, the third and fourth samples were removed from the vial, and the remaining solution was titrated with 0.01 M AgNO3 solution, and the volume of AgNO3 solution added during titration was recorded. The third and fourth samples were washed several times with distilled water and then dried in a hot air oven at 70°C for at least 1 hour. 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.

[0253] Formula 2: IEC(meq / g) = (Volume of titrant (ml) x 0.01) / Weight of dried anion exchange membrane (g)

[0254] After immersing the third sample, in which the initial ion exchange capacity was measured, in a 9.8 wt% H2SO4 solution for 20 days, the evaluation described above was repeated to calculate the ion exchange capacity of the anion exchange membrane according to Equation 2, and the results are shown in Table 1 below.

[0255] After immersing the fourth sample, in which the initial ion exchange capacity was measured, in an 8 wt% NaOH solution for 20 days, the evaluation described above was repeated to calculate the ion exchange capacity of the anion exchange membrane according to Equation 2, and the results are shown in Table 1 below.

[0256] No. Molar ratio of each substance Sheet resistance (Ω·cm²) IEC (meq / g) Acid (Sample 1) Base (2nd sample) Acid (3rd sample) Base (4th sample) First monomer crosslinking agent Second monomer beginning 20th beginning 20th beginning 20th beginning 20th Example 1 4 1 - 3.08 3.09 3.07 3.51 2.31 2.32 2.32 2.19 Example 2 0.85 0.2 1 2.21 2.25 2.20 2.24 1.87 1.85 1.86 1.87 Example 3 0.8 0.3 1 2.41 2.40 2.41 2.43 1.86 1.84 1.86 1.87 Example 4 0.75 0.4 1 2.45 2.48 2.44 2.49 1.84 1.83 1.84 1.85 Example 5 0.7 0.5 1 2.69 2.71 2.70 2.72 1.83 1.82 1.83 1.84 Example 6 0.65 0.7 1 2.96 2.97 2.95 2.96 1.78 1.77 1.78 1.78 Comparative Example 1 0.8 - 1 1.64 1.65 1.65 2.21 2.09 2.08 2.08 1.79 Comparative Example 2 0.8 X(EGDMA) 1 1.95 1.96 1.94 3.84 1.98 1.97 1.97 1.58 Comparative Example 3 0.8 - X(AMAC) 1.59 1.60 1.59 4.51 2.10 2.09 2.11 1.1 Example 7 0.8 0.3 X(AMAC) 2.98 3.0 2.97 3.51 2.11 2.10 2.10 1.90 Comparative Example 4 0.8 - X(AEBA) 1.79 1.80 1.81 5.10 2.08 2.07 2.09 0 Comparative Example 5 0.5 0.1 1 1.91 1.92 1.91 2.77 1.90 1.91 1.91 1.61 Comparative Example 6 1 0.3 1 2.11 2.11 2.10 2.75 1.79 1.78 1.79 1.57 Comparative Example 7 0.8 1 1 Unable to unveil due to non-use

[0257] From Table 1 above, it can be seen that the anion exchange membranes according to Examples 1 to 7 exhibit effectively low changes in sheet resistance and ion exchange capacity over time in acidic and basic solutions, respectively. However, it can be seen that the anion exchange membranes according to Comparative Examples 1 to 6 exhibit relatively large changes in sheet resistance and ion exchange capacity over time in acidic or basic solutions, respectively. As a result, it can be seen that the anion exchange membrane according to one embodiment possesses excellent chemical resistance.

[0258] Referring to Examples 3 and 7, it can be seen that the sheet resistance is effectively lowered by applying a secondary monomer satisfying chemical formula C.

[0259] It can be seen that Example 7 possesses excellent chemical resistance by using a second monomer satisfying Formula C, but using a first monomer satisfying Formula A and a crosslinking agent satisfying Formula B. Referring to Example 7 together with Comparative Examples 3 and 4, it can be seen that when a crosslinking agent belonging to Formula B is not applied, the sheet resistance and ion exchange capacity change significantly over time under basic conditions. Specifically, when the crosslinking agent is not applied, the sheet resistance increased excessively and the ion exchange capacity decreased excessively over time.

[0260] By referring to Examples 2 to 6 and Comparative Examples 5 and 6 together, it can be seen that by controlling the content of each of the first monomer belonging to Formula A, the crosslinking agent belonging to Formula B, and the second monomer belonging to Formula C, the change in sheet resistance and / or ion exchange capacity over time can be suppressed.

[0261] In addition, referring to Comparative Example 7, at a specific content ratio of the first monomer belonging to Formula A, the crosslinking agent belonging to Formula B, and the second monomer belonging to Formula C, the composition was not formed because they did not dissolve in the solvent, so an anion exchange membrane could not be manufactured.

[0262] In addition, it can be confirmed that the anion exchange membranes according to Examples 1 to 7 have excellent chemical resistance, while simultaneously having low levels of good sheet resistance and high levels of ion exchange capacity characteristics in acidic solutions and basic solutions, respectively.

[0263] The foregoing description is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. Explanation of the symbols

[0264] 20: Porous polymer support 21: Pores 30: Anion exchange polymer main chain 31: Anion exchange polymer 40: Anion exchange membrane

Claims

Claim 1 A composition for forming an anion exchange polymer comprising: a first monomer represented by the following chemical formula A; and a crosslinking agent represented by the following chemical formula B, wherein the ratio of the moles of the first monomer to the moles of the crosslinking agent is 0.9:1 to 4.5:1: <Chemical Formula A> <Chemical Formula B> In the above chemical formulas A and B, Vi is a vinyl group, and R 11 to R 16 , R 21 and R 22 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups, and substituted or unsubstituted C2-C 20 Selected from alkenyl groups, R 11 and R 12 are optionally combined with each other, and R 13 and R 14 are optionally combined with each other, and R 21 and R 22 are optionally combined with each other, a4 is selected from integers 0 to 4, and L1 and L2 are independently single-bonded and substituted or unsubstituted C1-C 20 Selected from alkylene groups, and X - and Y - are independent of each other, F - , Cl - , Br - and I - Among them, n1, n2, m1 and m2 are each selected from integers from 0 to 10. Claim 2 A composition for forming an anion exchange polymer according to claim 1, wherein the crosslinking agent is one or more selected from the following compounds B1 to B3: . Claim 3 delete Claim 4 The composition for forming an anion exchange polymer according to claim 1, further comprising a second monomer represented by the following chemical formula C: <Chemical Formula C> In the above chemical formula C, Vi is a vinyl group, and R 31 to R 34 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups and substituted or unsubstituted C2-C 20 Selected from alkenyl groups, a4 is selected from integers from 0 to 4, and Z - is F - , Cl - , Br - and I - It is selected from among, and p is selected from integers from 0 to 10. Claim 5 A composition for forming an anion exchange polymer according to claim 4, wherein the ratio of the moles of the first monomer to the moles of the second monomer is 0.65:1 to 0.85:

1. Claim 6 A composition for forming an anion exchange polymer according to claim 4, wherein the ratio of the moles of the second monomer to the moles of the crosslinking agent is 1:0.2 to 1:0.

7. Claim 7 An anion exchange membrane comprising: a porous polymer support; and an anion exchange polymer; wherein the anion exchange polymer is a crosslinked product of a composition for forming an anion exchange polymer according to any one of claims 1, 2 and 4 to 6. Claim 8 In claim 7, the porous polymer support is an anion exchange membrane that is a membrane structure, a nonwoven fabric structure, a fabric structure, or a mesh structure. Claim 9 In claim 8, the membrane structure is an anion exchange membrane having a structure in which pores are regularly arranged or a three-dimensional mesh structure. Claim 10 In claim 7, the anion exchange polymer is an anion exchange membrane uniformly distributed on the surface of the porous polymer support and inside the pores. Claim 11 In claim 7, the anion exchange membrane, wherein the average thickness of the anion exchange membrane is 50 micrometers (μm) to 150 μm. Claim 12 In claim 7, the anion exchange membrane satisfies the following formula 1A, anion exchange membrane: <Formula 1A> Among the above formula 1A, SR a 20 ≠ is the sheet resistance of the anion exchange membrane after 20 days in an acidic solution, and SR0 is the initial sheet resistance of the anion exchange membrane. Claim 13 In Clause 12, among the above Formula 1A, SR a 20 Anion exchange membrane, wherein SR0 and SR0 are each 0.1 Ω·cm² to 3.0 Ω·cm². Claim 14 In claim 7, the anion exchange membrane satisfies the following formula 1B, anion exchange membrane: <Formula 1B> Among the above formula 1B, SR b 20 is the sheet resistance of the anion exchange membrane after 20 days in a basic solution, and SR0 is the initial sheet resistance of the anion exchange membrane. Claim 15 In Clause 14, among the above Formula 1B, SR b 20 Anion exchange membrane, wherein SR0 and SR0 are each 0.1 Ω·cm² to 3.0 Ω·cm². Claim 16 In claim 7, the anion exchange membrane satisfies the following formula 2A, anion exchange membrane: <Formula 2A> Among the above Formula 2A, IEC a 20 IE is the ion exchange capacity of the anion exchange membrane after 20 days in an acidic solution, and IEC0 is the initial ion exchange capacity of the anion exchange membrane. Claim 17 In claim 7, the anion exchange membrane satisfies the following formula 2B, anion exchange membrane: <Formula 2B> In the above Formula 2B, IEC b 20 IE is the ion exchange capacity of the anion exchange membrane after 20 days in a basic solution, and IEC0 is the initial ion exchange capacity of the anion exchange membrane. Claim 18 In claim 7, the anion exchange membrane is an anion exchange membrane used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems. Claim 19 A step of preparing a composition for forming an anion exchange polymer comprising a first monomer represented by the following chemical formula A, a crosslinking agent represented by the following chemical formula B, a photoinitiator, and a solvent; a step of impregnating a porous polymer support with the composition for forming an anion exchange polymer to fill at least one portion of the surface and the interior of the pores of the porous polymer support with the composition for forming an anion exchange polymer; a step of pressing a film onto at least one surface of the porous polymer support filled with the composition for forming an anion exchange polymer to produce a laminate in which the film and the porous polymer support are laminated; a step of irradiating light onto the laminate and crosslinking the composition for forming an anion exchange polymer to form an anion exchange polymer, which is a crosslinking product of the composition for forming an anion exchange polymer, in at least one portion of the surface and the interior of the pores of the porous polymer support. A method for manufacturing an anion exchange membrane comprising: a step of manufacturing an anion exchange membrane by peeling off a film from a porous polymer support in which the anion exchange polymer is formed in at least one portion of the surface and the interior of the pores; wherein the ratio of the molar amount of the first monomer to the molar amount of the crosslinking agent in the composition for forming the anion exchange polymer is 0.9:1 to 4.5:1: <Chemical Formula A> <Chemical Formula B> In the above chemical formulas A and B, Vi is a vinyl group, and R 11 to R 16 , R 21 and R 22 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups, and substituted or unsubstituted C2-C 20 Selected from alkenyl groups, R 11 and R 12 are optionally combined with each other, and R 13 and R 14 are optionally combined with each other, and R 21 and R 22 are optionally combined with each other, a4 is selected from integers 0 to 4, and L1 and L2 are independently single-bonded and substituted or unsubstituted C1-C 20 Selected from alkylene groups, and X - and Y - are independent of each other, F - , Cl - , Br - and I - Among them, n1, n2, m1 and m2 are each selected from integers from 0 to 10. Claim 20 In claim 19, a method for manufacturing an anion exchange membrane, wherein the composition for forming an anion exchange polymer further comprises a second monomer represented by the following chemical formula C: <Chemical Formula C> In the above chemical formula C, Vi is a vinyl group, and R 31 to R 34 are independently hydrogen, deuterium, substituted or unsubstituted C1-C 20 Alkyl groups and substituted or unsubstituted C2-C 20 Selected from alkenyl groups, a4 is selected from integers from 0 to 4, and Z - is F - , Cl - , Br - and I - It is selected from among, and p is selected from integers from 0 to 10.

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