Composition for forming an anion exchange polymer, anion exchange membrane, and method for producing an anion exchange membrane

Abstract

The present invention provides a composition for forming an anion exchange polymer, an anion exchange membrane, and a method for producing an anion exchange membrane. [Solution] 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 producing the anion exchange membrane are disclosed: For explanations regarding chemical formulas A and B, please refer to this specification.

Description

[Technical Field]

[0001] This invention relates to a composition for forming an anion exchange polymer, an anion exchange membrane, and a method for producing an anion exchange membrane. [Background technology]

[0002] Ion exchange membranes are synthetic resin membranes that selectively allow the passage of either cations or anions. Cation exchange membranes have negatively charged functional groups, selectively allowing cations to pass through, while anion exchange membranes have positively charged functional groups, selectively allowing anions to pass through. Ion exchange membranes are widely used in many fields, including seawater concentration and desalination based on electrodialysis technology, purification of organic acids, and recovery of valuable metals. They are also being applied to hydrogen production technology via water electrolysis, which has recently attracted attention as a means of securing sustainable energy, along with addressing the issue of CO2 reduction due to global warming. Water electrolysis technology using ion exchange membranes includes cation exchange membrane or proton exchange membrane water electrolysis technology using proton transfer, and anion exchange membrane water electrolysis technology using anion exchange membranes in an alkaline solution environment. Anion exchange membrane water electrolysis technology uses water electrolysis through the conduction of hydroxide ions and has the advantage of being able to use less expensive water splitting catalysts compared to proton exchange membrane water electrolysis technology using hydrogen ion conduction, and much research has been conducted on it recently.

[0003] Such anion exchange membranes can be applied to water treatment systems such as electrodialysis, bipolar electrodialysis, energy storage desalination, and electrodeionization, or to systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries. Perfluoroanion exchange membranes, which have strong chemical resistance under acidic or basic conditions, can be used as anion exchange membranes, but they are expensive, so in practical systems, hydrocarbon anion exchange membranes can be used. However, the chemical resistance problems of hydrocarbon anion exchange membranes limit the processes and conditions under which they can be applied. [Overview of the project] [Problems that the invention aims to solve]

[0004] The problem to be solved by the present invention is to provide a hydrocarbon-based anion exchange membrane having excellent chemical resistance, low surface resistance, and high ion exchange capacity.

Means for Solving the Problem

[0005] According to one aspect, there is provided 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:

Chem.

[0006] In other aspects, an anion exchange membrane is provided, comprising a porous polymer support; and an anion exchange polymer; wherein the anion exchange polymer is a crosslinking product of the anion exchange polymer forming composition described above.

[0007] In other respects, a method for producing an anion exchange membrane is provided, comprising the steps of: producing an anion exchange polymer forming composition comprising a first monomer represented by the above-mentioned chemical formula A, a crosslinking agent represented by the above-mentioned chemical formula B, a photoinitiator, and a solvent; impregnating a porous polymer support with the anion exchange polymer forming composition to fill at least a portion of the surface and interior of the pores of the porous polymer support with the anion exchange polymer forming composition; pressing a film onto at least one surface of the porous polymer support filled with the anion exchange polymer forming composition to produce a laminate in which the film and the porous polymer support are laminated; irradiating the laminate with light to cause a crosslinking reaction of the anion exchange polymer forming composition to form an anion exchange polymer, which is a crosslinking product of the anion exchange polymer forming composition, on at least a portion of the surface and interior of the pores of the porous polymer support; and peeling the film from the porous polymer support on which the anion exchange polymer has been formed on at least a portion of the surface and interior of the pores to produce an anion exchange membrane. [Effects of the Invention]

[0008] An anion exchange membrane according to one embodiment can have excellent chemical resistance under acidic or basic conditions by being manufactured from an anion exchange polymer-forming composition comprising a first monomer represented by chemical formula A, a crosslinking agent represented by chemical formula B, and / or a second monomer selectively represented by chemical formula C. Specifically, the anion exchange membrane can have the characteristic of effectively minimizing changes in surface resistance and ion exchange capacity (IEC) over time under acidic or basic conditions. Furthermore, while having excellent chemical resistance, the anion exchange membrane can have low surface resistance and high ion exchange capacity under acidic or basic conditions. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic diagram of an anion exchange membrane according to one embodiment. [Modes for carrying out the invention]

[0010] The following describes in more detail a composition for forming an anion exchange polymer, an anion exchange membrane, and a method for producing an anion exchange membrane according to one embodiment. The following is presented as an example and does not limit the present invention, which is defined only by the claims described later.

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as they would normally be understood by a person skilled in the art to which this invention pertains. In case of any conflict, this specification, including its definitions, shall prevail.

[0012] Methods and materials similar to or equivalent to those described herein may be used in carrying out or testing the present invention, but suitable methods and materials are described herein.

[0013] In this specification, the term “includes” is used to indicate, unless otherwise stated, that other components may be added and / or interposed, rather than excluding them.

[0014] The figures stated in this specification may be understood to include the meaning of "approximately," even if not explicitly stated.

[0015] In this specification, "carbon number a to b" or "C a -C bIn this context, a and b refer to the number of carbon atoms in a specific functional group. That is, the functional group may contain carbon atoms from a to b. For example, "C1-C2 alkyl group" or "C1-C2 alkyl group" refers to an alkyl group having one or two carbon atoms, i.e., -CH3 and -CH2CH3.

[0016] In this specification, the term "alkyl" means a branched (branched-chain) or unbranched (straight-chain) aliphatic hydrocarbon. Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and each of them may be selectively substituted or unsubstituted.

[0017] In this specification, the term "alkylene" means a divalent group having the same structure as "alkyl." Alkylene groups include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, and heptylene groups, and each of them may be selectively substituted or unsubstituted.

[0018] In this specification, the term "alkenyl" means a monovalent hydrocarbon containing one or more carbon-carbon double bonds in the middle or terminal of an alkyl group. Alkenyl groups include, but are not limited to, ethenyl, propenyl, and butenyl groups, and each of them may be selectively substituted or unsubstituted. On the other hand, the ethenyl group is also called a vinyl group.

[0019] In this specification, "substitution" is induced by the exchange of one or more hydrogen atoms in an unsubstituted mother group for different atoms or functional groups. For example, when a functional group is considered to be "substituted", the functional group is deuterium, C1-C 40 Alkyl alkyl group, C1-C 40 Alkoxy group, C2-C40 Alkenyl group, C2-C 40 Alkynyl group, C3-C 40 Cycloalkyl groups, C3-C 40 Cycloalkenyl group, C6-C 40 This means that the functional group is substituted with one or more substituents selected from among the aryl groups. When it is stated that a functional group is "selectively substituted," it means that the functional group may be substituted with the substituents mentioned above.

[0020] Anion exchange membranes include perfluoroanion exchange membranes and hydrocarbon-based anion exchange membranes. Of these, hydrocarbon-based anion exchange membranes are less expensive than perfluoroanion exchange membranes, but their chemical resistance is insufficient. Furthermore, anion exchange membranes that use a support structure have a constant amount of support fraction present, which limits the reduction of surface resistance and / or the increase in ion exchange capacity that would otherwise enhance concentration and desalination capabilities.

[0021] The inventors of this invention have solved the above-mentioned problems and provide an anion exchange membrane that, while being a hydrocarbon-based anion exchange membrane, has sufficiently low surface resistance and sufficiently high ion exchange capacity, and has excellent chemical resistance.

[0022] In one aspect, a composition for forming an anion exchange polymer is provided, comprising a first monomer represented by the following chemical formula A; and a crosslinking agent represented by the following chemical formula B: [ka] In the above chemical formulas A and B, Vi is a vinyl group.

[0023] The vinyl group [ka] This is a group represented by (* indicates a bonding site with an adjacent atom), and is also called a C2 alkenyl group or ethenyl group.

[0024] First monomer In the above chemical formula A, R11 R 16 These are, independently of each other, hydrogen, deuterium, and substituted or unsubstituted C1-C 20 Alkyl groups, and substituted or unsubstituted C2-C 20 It can be selected from among the alkenyl groups.

[0025] According to one specific example, R 11 R 16 These are also, independently of each other, hydrogen, deuterium, methyl group, ethyl group, propyl group, ethenyl group, propylene group, etc.

[0026] According to one specific example, R 11 and R 12 These can be selectively coupled to one another. That is, R 11 and R 12 They either join together or do not join together. For example, N + -R 11 -R 12 -N + A ring consisting of -L1 can be formed.

[0027] According to one specific example, R 13 and R 14 These can be selectively coupled to one another. That is, R 13 and R 14 They either join together or do not join together. For example, N + -R 13 -R 14 -N + A ring consisting of -L1 can be formed.

[0028] In the above chemical formula A, R 15 and R 16 These are, independently of each other, hydrogen or deuterium.

[0029] In the aforementioned chemical formula A, a4 can be selected from integers between 0 and 4. In one example, a4 is also 0 or 4.

[0030] In the above chemical formula A, L1 is a single bond and a substituted or unsubstituted C1-C 20It can be selected from among alkylene groups.

[0031] According to one example, L1 can be a single bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group.

[0032] In the aforementioned chemical formula A, X - and Y - F - Cl - , Br - and I - It can be selected from among them.

[0033] According to one example, X - and Y - They are also identical to each other.

[0034] According to one example, X - and Y - At least one of them is Cl - That is the case.

[0035] In the aforementioned chemical formula A, n1 and n2 can each be selected from integers between 0 and 10.

[0036] In one concrete example, n1 and n2 can each be selected from integers between 0 and 2.

[0037] According to one example, n1 and n2 are also identical to each other.

[0038] According to one concrete example, at least one of n1 and n2 is also 1.

[0039] According to one example, the first monomer may be represented by any one of the following chemical formulas A-1 to A-6: [ka] [ka] In the above chemical formulas A-1 to A-6, Vi, R 11 R 14 L1, X - , Y - n1 and n2 are the same as those described in the chemical formula A above.

[0040] According to one example, in the above chemical formulas A and A-1 to A-6, [ka] The group represented by is represented by the following chemical formula A-11 or A-12: [ka] The * and *' above represent bonding sites with adjacent atoms.

[0041] Referring to the aforementioned chemical formula A-11, of the chemical formula A, R 11 and R 12 They do not bond to each other, R 13 and R 14 It can be confirmed that they do not combine with each other.

[0042] Referring to the aforementioned chemical formula A-12, in the aforementioned chemical formula A, L1 is ethylene, and R 11 and R 12 They bond to each other, R 13 and R 14 It can be confirmed that they combine with each other.

[0043] According to one example, the first monomer is one or more compounds selected from the following compounds A1 to A3: [ka]

[0044] For example, the first monomer is also compound A3.

[0045] Crosslinking agent Referring to the aforementioned chemical formula B, the crosslinking agent is a substance 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 surface resistance, a high level of ion exchange capacity, and excellent chemical resistance.

[0046] In the above chemical formula B, R 21 and R 22 These are, independently of each other, hydrogen, deuterium, and substituted or unsubstituted C1-C 20 Alkyl groups and substituted or unsubstituted C2-C groups 20 It can be selected from among the alkenyl groups.

[0047] According to one specific example, R 21 and R 22 These are, independently of each other, hydrogen, deuterium, methyl group, ethyl group, propyl group, ethenyl group, or propylene group.

[0048] According to one specific example, R 21 and R 22 They can be selectively coupled to each other. 21 and R 22 The fact that they are bonded together can be seen in compound B1 below: [ka]

[0049] Referring to compound B1, L2 in chemical formula B is an ethylene group, and R 21 and R 22 It can be confirmed that they combine with each other.

[0050] In the above chemical formula B, L2 is a single bond and a substituted or unsubstituted C1-C 20 It can be selected from among alkylene groups.

[0051] According to one example, L2 can be a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group, etc.

[0052] In the chemical formula B, each of m1 and m2 can be selected from integers of 0 to 10.

[0053] According to one embodiment, each of m1 and m2 can be selected from integers of 0 to 2.

[0054] According to one embodiment, m1 and m2 are also the same as each other.

[0055] According to one embodiment, at least one of m1 and m2 is also 0.

[0056] According to one embodiment, the crosslinking agent can be represented by the following chemical formula B-1:

Chemical formula

[0057] According to one embodiment, the crosslinking agent is one or more selected from the following compounds B1 to B3:

Chemical formula

[0058] Second monomer The composition for forming the anion exchange polymer may further contain a second monomer represented by the following chemical formula C:

Chemical formula

[0059] According to one embodiment, R 31 or R 34 is, independently of one another, also hydrogen, deuterium, a methyl group, an ethyl group, a propyl group, an ethenyl group or a propylene group.

[0060] According to one embodiment, R 31 or R 33 are also identical to one another.

[0061] According to one embodiment, R 34 is also hydrogen or deuterium.

[0062] In the chemical formula C, a4 can be selected from integers of 0 to 4. According to one embodiment, a4 is also 0 or 4.

[0063] In the chemical formula C, Z - is F - , Cl - , Br - and I - and can be selected therefrom.

[0064] According to one embodiment, X - , Y - and Z - in the chemical formulas A and C are also identical to one another.

[0065] In the chemical formula C, p can be selected from integers of 0 to 10.

[0066] According to one embodiment, p is also 0, 1 or 2.

[0067] According to one embodiment, the second monomer can be represented by the following chemical formula C-1 or C-2:

Chemical formula

[0068] According to one example, the second monomer is also compound C1: [ka]

[0069] Composition for forming anion exchange polymers When the anion exchange polymer-forming composition is crosslinked, the first monomer, the crosslinking agent, and the second monomer described above can each be crosslinked to one another via vinyl groups.

[0070] According to one example, the ratio of moles of the first monomer to the number of moles of the crosslinking agent is also 0.9:1 to 4.5:1. For example, the molar ratio of the first monomer to the crosslinking agent is also 0.92:1 to 4.25:1.

[0071] In one example, the ratio of the number of moles of the first monomer to the number of moles of the second monomer is also 0.65:1 to 0.85:1. For example, the molar ratio of the first monomer to the second monomer is also 0.7:1 to 0.8:1.

[0072] In one example, the ratio of moles of the second monomer to the number of moles of the crosslinking agent is 1:0.2 to 1:0.7. For example, the molar ratio of the second monomer to the crosslinking agent is 1:0.3 to 1:0.5.

[0073] The anion exchange polymer-forming composition contains at least the first monomer and the crosslinking agent, and the content of the first monomer, crosslinking agent, and second monomer contained in the anion exchange polymer-forming composition satisfies the above-described range, thereby preventing a decrease in the solubility characteristics of the composition, and enabling the anion exchange polymer-forming composition to have excellent chemical resistance under acidic or basic conditions, and to have a low level of surface resistance and a high level of ion exchange capacity under acidic or basic conditions.

[0074] Anion exchange membrane In other aspects, an anion exchange membrane is provided, comprising a porous polymer support and an anion exchange polymer. The anion exchange polymer is a crosslinking product of the anion exchange polymer forming composition described above.

[0075] According to one example, the porous polymer support is also a membrane structure, a nonwoven fabric structure, a woven fabric structure, or a mesh structure. The porous polymer support is also in the shape of a sponge or a three-dimensional network.

[0076] According to one example, the membrane structure is either a structure in which pores are arranged regularly, or a three-dimensional mesh structure.

[0077] The anion exchange polymer may be located on the surface of the porous polymer support and in at least part of the interior of its pores. For example, the anion exchange polymer may be located on the surface of the porous polymer support. As another example, the anion exchange polymer may be located inside the pores of the porous polymer support. As yet another example, the anion exchange polymer may be located both on the surface of the porous polymer support and inside its pores.

[0078] According to one example, the anion exchange polymer can be uniformly distributed on the surface and inside the pores of the porous polymer support.

[0079] According to one example, the average thickness of the anion exchange membrane is 50 μm to 200 μm. For example, the average thickness of the anion exchange membrane is 50 μm to 150 μm.

[0080] Figure 1 is a schematic diagram of an anion exchange membrane according to one embodiment.

[0081] Referring to Figure 1, the anion exchange polymer 31 having cationic functional groups contained in the anion exchange membrane 40 can be uniformly located on the surface and inside the pores 21 of the porous polymer support 20.

[0082] The anion exchange polymer 31 is also a crosslinking product of the anion exchange polymer forming composition described above. That is, the first monomer and the crosslinking agent described above are crosslinked to form the anion exchange polymer, or the first monomer, the crosslinking agent, and the second monomer are all 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 the anion exchange polymer main chain 30. As another example, the bonding product of the first monomer and the crosslinking agent may form an anion exchange polymer main chain 30, and either the first monomer or the crosslinking agent may crosslink the anion exchange polymer main chain 30. As yet another example, the bonding product of the first monomer and the second monomer may form an anion exchange polymer main chain 30, and the crosslinking agent may crosslink the anion exchange polymer main chain 30.

[0083] According to one example, the porous polymer support 20 may contain 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 contain polypropylene (PP).

[0084] According to one example, the anion exchange membrane 40 can be used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems. The anion exchange membrane can also be used in energy systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries.

[0085] Surface resistance, ion exchange capacity, and the degree of change of each. The anion exchange membrane described above may have a small change in surface resistance in acidic or basic solutions. The anion exchange membrane described above may have a small change in ion exchange capacity in acidic or basic solutions. In other words, the anion exchange membrane may have excellent chemical resistance. Examples of acidic solutions include H2SO4, HCl, and CH3COOH. Examples of basic solutions include NaOH, KOH, and Ca(OH)2.

[0086] According to one example, the anion exchange membrane may satisfy the following equation 1A:

number

[0087] The above equation 1A means that even after 20 days in an acidic solution, the surface resistance of the anion exchange membrane remains substantially unchanged.

[0088] According to one example, in the above formula 1A,

number

[0089] According to one example, in the above formula 1A, SR a 20 Both SR0 and SR0 have a resistance of 0.1 Ω·cm. 2 ~3.0Ω·cm 2 That is the case.

[0090] According to one example, the anion exchange membrane may satisfy the following equation 1B:

number

[0091] The above equation 1B means that even after 20 days in a basic solution, the surface resistance of the anion exchange membrane remains substantially unchanged.

[0092] According to one example, in the above formula 1B,

number

[0093] According to one example, in the above formula 1B, SR b 20 Both SR0 and SR0 have a resistance of 0.1 Ω·cm. 2 ~3.0Ω·cm 2 That is the case.

[0094] According to one example, the anion exchange membrane may satisfy the following equation 2A:

number

[0095] The above equation 2A means that even after 20 days in an acidic solution, the ion exchange capacity of the anion exchange membrane remains substantially unchanged.

[0096] According to one example, among the above number 2A,

number

[0097] According to one example, in the above number 2A, IEC0 and IEC a 20 Each of these is also equivalent to 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.

[0098] According to one example, the anion exchange membrane may satisfy the following equation 2B:

number

[0099] The aforementioned equation 2B means that even after 20 days in a basic solution, the ion exchange capacity of the anion exchange membrane remains substantially unchanged.

[0100] According to one example, in the above number 2B,

number

[0101] According to one example, in the above number 2B, IEC0 and IEC b 20 Each of these is also equivalent to 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.

[0102] Manufacturing method Furthermore, from another perspective, the process involves the steps of producing a composition for forming an anion exchange polymer, comprising a first monomer represented by the above-mentioned chemical formula A, a crosslinking agent represented by the above-mentioned chemical formula B, a photoinitiator, and a solvent, The steps include impregnating a porous polymer support with the anion exchange polymer forming composition to fill at least a portion of the surface and interior of the pores of the porous polymer support with the anion exchange polymer forming composition, 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 anion exchange polymer forming composition, The steps include: irradiating the laminate with light to cause the anion exchange polymer forming composition to undergo a crosslinking reaction, thereby forming an anion exchange polymer, which is a crosslinking product of the anion exchange polymer forming composition, on at least a portion of the surface and interior of the pores of the porous polymer support; A method for producing an anion exchange membrane is provided, which includes the step of peeling a film from a porous polymer support on which the anion exchange polymer is formed in at least a portion of the surface and the interior of the pores to produce an anion exchange membrane.

[0103] According to one example, the anion exchange polymer-forming composition may further contain the second monomer represented by the chemical formula C described above. That is, the anion exchange polymer-forming composition may contain any of the first monomer, the crosslinking agent, the second monomer, the photoinitiator, and the solvent.

[0104] The method for producing the anion exchange membrane may further include the step of immersing the porous polymer support in a surfactant solution and drying it to make the surface of the porous polymer support hydrophilic, before performing the step of impregnating the porous polymer support with the anion exchange polymer forming composition to fill at least a portion of the surface and interior of the pores of the porous polymer support with the anion exchange polymer forming composition.

[0105] The hydrophilization step is carried out 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 voids are sufficiently large and the anion exchange polymer forming composition can be sufficiently filled.

[0106] During the hydrophilization stage, immersion can be performed for 0.1 to 10 minutes, or 0.5 to 8 minutes. If immersion is performed for less than 0.1 minutes, the surface of the porous polymer support will not be sufficiently hydrophilized, resulting in problems such as the anion exchange polymer forming composition not filling the voids in the porous polymer support. If immersion is performed for more than 10 minutes, problems such as a decrease in production speed and an increase in production costs may occur.

[0107] The anion exchange membrane can also be in a form in which the anion exchange polymer-forming composition fills the pores of a porous polymer support, thereby filling the pores. Alternatively, the anion exchange polymer-forming composition can surround the outer surface of the porous polymer support.

[0108] Furthermore, during the hydrophilization stage, drying can be carried out immediately after immersion at a temperature of 40-90°C for 1-20 minutes, or at a temperature of 40-80°C for 1-10 minutes.

[0109] On the other hand, the surfactant solution may contain 0.001 to 6% by weight of the surfactant and the remainder of the solvent, or 0.01 to 4% by weight of the surfactant and the remainder of the solvent, or 0.05 to 3% by weight of the surfactant and the remainder of the solvent.

[0110] If the surfactant is present in less than 0.001% by weight in the surfactant solution, the surface of the porous polymer support will not be hydrophilized, and the ion exchange resin solution will not fill the pores of the substrate. If the amount exceeds 6% by weight, the surfactant may be eluted or the amount of ion exchange resin filling may decrease.

[0111] Surfactants can be any known surfactant without restriction, but they can also be substances that have one or two alkyl chains with approximately 12 to 20 carbon atoms in their molecule. For example, surfactants 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 salts of amideamines, quaternary ammonium salts of amideesteramines, imidazoline, imidazoline esters, or any combination thereof. In one example, a surfactant is also a quaternary ammonium substance.

[0112] If a surfactant is bonded to the surface of a porous polymer support, where the hydrophobic portion is hydrophobic, via a hydrophobic-hydrophobic interaction, the hydrophilic portion of the surfactant can replace the surface of the porous polymer support, thus achieving hydrophilicity. Here, the surfactant can hydrophilize not only the surface of the porous polymer support but also the entire pore surface inside. However, this step can be omitted if the degree of hydrophilicity of the porous polymer support is sufficient, or if the pores of the porous polymer support are large enough to be filled with an anion exchange polymer-forming composition.

[0113] The content of the photoinitiator is 0.01% to 2% by weight, or 0.1% to 1% by weight, based on 100% by weight of the entire anion exchange polymer forming composition.

[0114] The photoinitiator can be any photoinitiator available in the art without limitation, but is, for example, one or more selected from 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone.

[0115] The solvent may be any solvent available in the art, without limitation, but may be a water-soluble solvent such as water, methanol, or ethanol, or distilled water. The solvent may be included in the anion exchange polymer-forming composition in the amount remaining after excluding the first monomer represented by chemical formula A, the crosslinking agent represented by chemical formula B, the second monomer represented by chemical formula C, and the photoinitiator (if the anion exchange polymer-forming composition does not contain the second monomer, the solvent is included in the amount remaining after excluding the first monomer, the crosslinking agent, and the photoinitiator).

[0116] The aforementioned film can be used without limitation as long as it is a film usable in the art, but it may also be, for example, a polyester film (specifically, polyethylene terephthalate film).

[0117] The film can be pressed onto the upper and / or lower surface of a porous polymer support by roll calendering. Pressing can be performed at a temperature of 10°C to 35°C, for example, 15°C to 30°C, and at a pressure of approximately 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.

[0118] The thickness of the film is 10 μm to 200 μm, for example, 10 μm to 150 μm, 20 μm to 120 μm, or 30 μm to 100 μm. If the thickness of the film is less than 10 μm, lamination defects such as wrinkles in the film may occur when laminating with a support filled with anion exchange polymer. If the thickness of the film exceeds 200 μm, the film is excessively thick during the crosslinking reaction, and light does not sufficiently irradiate the porous polymer support, resulting in an insufficient crosslinking reaction.

[0119] The light irradiated onto the laminate is also ultraviolet light. For example, UVA, UVB, UVC and / or UVV can be used.

[0120] Using UVC as the aforementioned light source, the flow rate is 2000 mJ / cm². 2 ~10000 mJ / cm 2 This may include a step of performing irradiation with a light intensity of 2000 mJ / cm². For example, using UVC as the light, the intensity could be 2000 mJ / cm². 2 ~8000 mJ / cm 2 This can be carried out with a light intensity of [specify]. When light irradiation is performed under such conditions, an ion exchange membrane with improved ion exchange capacity can be manufactured.

[0121] When peeling 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 opposite directions using a detachment roll.

[0122] As a result, the anion exchange membranes produced have an average thickness of 10 to 200 μm, or for example, 50 to 200 μm. If the average thickness is less than 10 μm, the durability of the anion exchange membrane decreases, there is a risk of membrane damage during operation, and the desalination and concentration performance decreases due to the permeation of unwanted salts. If it exceeds 200 μm, the surface resistance is high, the power consumption required for operation is large, and the desalination and concentration performance may decrease. [Examples]

[0123] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to such examples.

[0124] Example 1 A 100 μm thick porous polymer support made of polypropylene (PP) with a porosity of 51% was prepared. The porous polymer support was immersed in a 2% by weight quaternary ammonium aqueous solution for 10 minutes, and then dried in a 70°C hot air oven for 10 minutes to make it hydrophilic. The hydrophilic porous polymer support was then immersed in an anion exchange polymer-forming composition, which is an ion exchange resin solution, for 5 minutes to fill the porous polymer support with the ion exchange resin solution.

[0125] In this case, the composition for forming the anion exchange polymer was prepared by mixing 53% by weight of compound A3 as the first monomer belonging to chemical formula A, 6% by weight of compound B1 as a crosslinking agent belonging to chemical formula B, 0.5% by weight of 2-hydroxy-2-methylpropiophenone (manufactured by Ciba) as a photoinitiator, and the remainder of distilled water. Here, the ratio of moles of the first monomer to the moles of the crosslinking agent was 4:1.

[0126] The polypropylene porous polymer support was impregnated with the anion exchange polymer forming composition to fill the surface and pores of the porous polymer support with the composition. The porous polymer support filled with the composition was placed in a pressure roll, and a 50 μm thick polyester film was pressed onto the top and bottom 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 bonded together. 3000 mJ / cm³ was applied to the laminate. 2 An anion exchange polymer, which is a crosslinking product of the composition, was formed on the surface and inside the pores of the porous polymer support by irradiation with UVC ultraviolet light. An anion exchange membrane was manufactured by peeling the polyester film from the porous polymer support on which the anion exchange polymer had been formed on the surface and inside the pores.

[0127] Example 2 An anion exchange membrane was manufactured using the same method as in Example 1, except that when producing the composition for forming an anion exchange polymer, compound C1 belonging to chemical formula C was further mixed in, and the ratio of moles of the first monomer:moles of the crosslinking agent:moles of the second monomer was adjusted to 0.85:0.2:1.

[0128] Examples 3 to 6 An anion exchange membrane was manufactured using the same method as in Example 2, except that the molar ratios of the first monomer, crosslinking agent, and second monomer were changed as shown in Table 1 below.

[0129] Comparative example 1 (chemical formula B absent) An anion exchange membrane was manufactured using the same method as in Example 3, 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 does not use any substance belonging to chemical formula B as described above.

[0130] Comparative Example 2 (Chemical Formula B Unsatisfactory) An anion exchange membrane was manufactured using the same method as in Example 3, except that a crosslinking agent belonging to chemical formula B was not used, and ethylene glycol dimethacrylate (hereinafter referred to as EGDMA) was used instead. Here, the ratio of moles of the first monomer, EGDMA, and second monomer was 0.8:0.3:1.

[0131] [ka]

[0132] Referring to the structure of EGDMA mentioned above, it can be confirmed that EGDMA does not belong to any of the chemical formulas A through C described above.

[0133] In Comparative Example 2, although EGDMA can play a role similar to that of a general cross-linking agent, it is a substance that does not belong to the above-described Chemical Formula B. Therefore, X was indicated in Table 1 below, and the type of the substance was described in parentheses.

[0134] Comparative example 3 (chemical formula B absent, chemical formula C insufficient) When producing the composition for forming an anion exchange polymer, an anion exchange membrane was produced in the same manner as in Comparative Example 1, except that a second monomer belonging to Chemical Formula C was not used, and (3-acrylamidopropyl)trimethylammonium chloride ((3-acrylamidopropyl)trimethylammonium chloride; hereinafter referred to as AMAC) was used, and the molar ratio of each substance was changed. The molar number of the first monomer: the molar number of AMAC was 0.8:1.

[0135]

Chemical formula

[0136] Referring to the structure of the above AMAC, it can be confirmed that AMAC does not belong to any of the above-described Chemical Formulas A to C.

[0137] In Comparative Example 3, since a substance belonging to the above-described Chemical Formula B was not applied, - was indicated in Table 1 below. Although AMAC can play a role similar to that of a general monomer, it is a substance that does not belong to the above-described Chemical Formula C. Therefore, X was indicated in Table 1 below, and the type of the substance was described in parentheses.

[0138] Example 7 When producing the composition for forming an anion exchange polymer, an anion exchange membrane was produced in the same manner as in Comparative Example 3, except that Compound B1 was further applied as a cross-linking agent belonging to Chemical Formula B, and the molar number of the first monomer: the molar number of the cross-linking agent: the molar number of AMAC = 0.8:0.3:1.

[0139] Comparative example 4 (chemical formula B absent, chemical formula C insufficient) An anion exchange membrane was manufactured using the same method as in Comparative Example 3, except that (N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride; hereinafter referred to as AEBA) was used instead of AMAC when producing the composition for forming an anion exchange polymer.

[0140] [ka]

[0141] By referring to the structure of AEBA mentioned above, it can be confirmed that AEBA does not belong to any of the chemical formulas A through C described above.

[0142] Comparative Example 4 is marked with a "-" in Table 1 below because it does not use a substance belonging to chemical formula B as described above. The AEBA is marked with an "X" in Table 1 below because, although it can perform a role similar to a general monomer, it is a substance that does not belong to chemical formula C as described above, and the type of substance is indicated in parentheses.

[0143] Comparative Examples 5 to 7 (Molar Ratio Change) An anion exchange membrane was manufactured using the same method as in Example 2, except that the molar ratio of each substance was changed as shown in Table 1 below.

[0144] Evaluation Example 1 (Surface Resistance) Each anion exchange membrane specimen was cut to a size of 5 cm x 5 cm to prepare the first and second samples. The first sample was for measuring the change in surface resistance in an acidic solution, and the second sample was for measuring the change in surface resistance in a basic solution. The first and second samples were positioned between electrodes specifically for surface resistance measurement under 0.5 M NaCl solution conditions, and the measured values ​​were stabilized.

[0145] The linear resistance R1 of the anion exchange membrane was measured using an LCR meter (Agilent, E4980A) with the first and second samples positioned between electrodes for surface resistance measurement. After removing the anion exchange membrane, the resistance R2 of the 0.5M NaCl solution was measured. The surface resistance SR of the anion exchange membrane was calculated using the following formula 1, and the results are shown in Table 1 below: <Number 1> SR = (R1 - R2) × S In the above formula 1, SR is the surface resistance (Ω·cm) of the anion exchange membrane. 2 ) and R1 is the linear resistance of the anion exchange membrane. R2 is the resistance of the 0.5M NaCl solution. S is the area of ​​the electrode.

[0146] After immersing the first sample, whose initial surface resistance had been measured, in a 9.8 wt% H2SO4 solution for 20 days, the above evaluation was repeated to calculate the surface resistance of the anion exchange membrane using formula 1, and the results are shown in Table 1 below.

[0147] After immersing the second sample, whose initial surface resistance had been measured, in an 8 wt% NaOH solution for 20 days, the above evaluation was repeated to calculate the surface resistance of the anion exchange membrane using formula 1, and the results are shown in Table 1 below.

[0148] Evaluation Example 2 (Ion Exchange Capacity) Each anion exchange membrane was cut into a size of 5 cm x 5 cm to prepare the third sample and the fourth sample. The third sample is a sample for measuring the change in ion exchange capacity with an acidic solution, and the fourth sample is a sample for measuring the change in ion exchange capacity with a basic solution. After washing each of the third sample and the fourth sample with distilled water, excess moisture was removed with tissue paper. After filling a vial with 70 ml of 1M NaCl solution, each of the third sample and the fourth sample with the removed moisture was placed in the 1M NaCl solution and immersed for 12 hours or more for the primary pretreatment. Each of the third sample and the fourth sample after the primary pretreatment was washed several times with distilled water and excess moisture was removed with tissue paper. After filling a vial with 70 ml of 0.5M Na2CO3 solution, each of the third sample and the fourth sample with the removed moisture was placed in the 0.5 M Na2CO3 solution and immersed for 12 hours or more for the secondary pretreatment. Each of the third sample and the fourth sample after the secondary pretreatment was taken out from the vial, the residual solution was titrated with 0.01M AgNO3 solution, and the volume of the AgNO3 solution introduced during titration was recorded. Each of the third sample and the fourth sample was washed several times with distilled water and then dried in a hot air oven at 70°C for 1 hour or more. After drying was completed, the weight of the dried anion exchange membrane was measured. The measured weight of the dried anion exchange membrane was substituted into the following formula 2 to determine the ion exchange capacity (IEC). Formula 2: IEC (meq / g) = (Volume of titrant (ml) x 0.01) / Weight of dried anion exchange membrane (g)

[0149] The third sample with the measured initial ion exchange capacity was immersed in a 9.8 wt% H2SO4 solution for 20 days, and then the above-described evaluation was repeated to calculate the ion exchange capacity of the anion exchange membrane according to the above formula 2, and the results are shown in Table 1 below.

[0150] After immersing the fourth sample, whose initial ion exchange capacity had been measured, in an 8 wt% NaOH solution for 20 days, the above evaluation was repeated to calculate the ion exchange capacity of the anion exchange membrane using Equation 2, and the results are shown in Table 1 below.

[0151] [Table 1]

[0152] From Table 1 above, it can be confirmed that the anion exchange membranes according to Examples 1 to 7 exhibit effectively low changes in surface resistance and ion exchange capacity over time in both acidic and basic solutions, respectively. However, it can be confirmed that the anion exchange membranes according to Comparative Examples 1 to 6 exhibit relatively large changes in at least one of the following over time in either acidic or basic solutions: changes in surface resistance and changes in ion exchange capacity. This demonstrates that the anion exchange membrane according to one embodiment has excellent chemical resistance.

[0153] By referring to Examples 3 and 7, it can be confirmed that applying a second monomer satisfying chemical formula C effectively lowers the surface resistance.

[0154] Example 7 does not use a second monomer satisfying chemical formula C, but it can be seen that by using a first monomer satisfying chemical formula A and a crosslinking agent satisfying chemical formula B, it exhibits excellent chemical resistance. Referring to both Example 7 and Comparative Examples 3 and 4, it can be seen that when a crosslinking agent belonging to chemical formula B is not applied, the surface resistance and ion exchange capacity change significantly over time under basic conditions. Specifically, when no crosslinking agent is applied, the surface resistance increases excessively over time, and the ion exchange capacity decreases excessively.

[0155] By referring to Examples 2 to 6 and Comparative Examples 5 and 6, it can be seen that the change in surface resistance and / or ion exchange capacity over time can be suppressed by adjusting the content of the first monomer belonging to chemical formula A, the crosslinking agent belonging to chemical formula B, and the second monomer belonging to chemical formula C.

[0156] Furthermore, referring to Comparative Example 7, at specific content ratios of the first monomer belonging to chemical formula A, the crosslinking agent belonging to chemical formula B, and the second monomer belonging to chemical formula C, the materials were insoluble in the solvent and no composition was formed, making it impossible to manufacture an anion exchange membrane.

[0157] Furthermore, it can be confirmed that the anion exchange membranes according to Examples 1 to 7 possess excellent chemical resistance while simultaneously exhibiting low levels of good surface resistance and high levels of ion exchange capacity characteristics in both acidic and basic solutions, respectively.

[0158] The above description is merely illustrative, and a person with ordinary skill in the art to which this invention belongs will understand that it can be easily modified into other specific forms without changing the technical idea or essential features of the invention. Therefore, the embodiments described above should be understood in all respects as illustrative and not limiting. [Explanation of Symbols]

[0159] 20 Porous polymer support 21 Stomata 30 Anion exchange polymer main chain 31 Anion exchange polymer 40 Anion exchange membrane

Claims

1. The first monomer represented by the following chemical formula A, A composition for forming an anion exchange polymer, comprising a crosslinking agent represented by the following chemical formula B: 【Chemistry 1】 In the aforementioned chemical formulas A and B, Vi is a vinyl group, R １１ R １６ , R ２１ and R ２２ These are, independently of each other, hydrogen, deuterium, and substituted or unsubstituted C １ -C ２０ Alkyl alkyl groups, and substituted or unsubstituted C ２ -C ２０ Selected from among alkenyl groups, R １１ and R １２ are selectively bonded to each other, R １３ and R １４ They selectively bind to each other, R ２１ and R ２２ They selectively bind to each other, a4 is selected from integers between 0 and 4. L １ and L ２ These are C elements that are independent of each other, consisting of single bonds and substituted or unsubstituted elements. １ -C ２０ Selected from among alkylene groups, X － and Y － F － , Cl － , Br － and I － Selected from among, n1, n2, m1, and m2 are each selected from integers between 0 and 10.

2. The anion exchange polymer forming composition according to claim 1, wherein the crosslinking agent is one or more selected from the following compounds B1 to B3: 【Chemistry 2】

3. The composition for forming an anion exchange polymer according to claim 1, wherein the ratio of the number of moles of the first monomer to the number of moles of the crosslinking agent is 0.9:1 to 4.5:

1.

4. The anion exchange polymer-forming composition according to claim 1, further comprising a second monomer represented by the following chemical formula C: 【Transformation 3】 In the aforementioned chemical formula C, Vi is a vinyl group, R ３１ R ３４ These are, independently of each other, hydrogen, deuterium, and substituted or unsubstituted C １ -C ２０ Alkyl and substituted or unsubstituted C ２ -C ２０ Selected from among alkenyl groups, a4 is selected from integers between 0 and 4. Z － is F － , Cl － , Br － and I － Selected from among, p is selected from integers between 0 and 10.

5. The anion exchange polymer forming composition according to claim 4, wherein the ratio of the number of moles of the first monomer to the number of moles of the second monomer is 0.65:1 to 0.85:

1.

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

7.

7. A porous polymer support, It contains an anion exchange polymer, The anion exchange membrane is an anion exchange polymer which is a crosslinked product of the anion exchange polymer forming composition according to any one of claims 1 to 6.

8. The anion exchange membrane according to claim 7, wherein the porous polymer support is a membrane structure, a nonwoven fabric structure, a woven fabric structure, or a mesh structure.

9. The anion exchange membrane according to claim 8, wherein the membrane structure has a structure in which pores are regularly arranged or a three-dimensional mesh structure.

10. The anion exchange membrane according to claim 7, wherein the anion exchange polymer is uniformly distributed on the surface and inside the pores of the porous polymer support.

11. The anion exchange membrane according to claim 7, wherein the average thickness of the anion exchange membrane is 50 μm to 200 μm.

12. The anion exchange membrane described above is the anion exchange membrane according to claim 7, satisfying the following formula 1A: [Math 1] In the above formula 1A, SR ａ ２０ This is the surface resistance of an anion exchange membrane after 20 days in an acidic solution. SR ０ This is the surface resistance of the initial anion exchange membrane.

13. In the above formula 1A, SR ａ ２０ and SR ０ Each has a resistance of 0.1 Ω·cm. ２ ~3.0Ω·cm ２ The anion exchange membrane according to claim 12.

14. The anion exchange membrane described above is the anion exchange membrane according to claim 7, satisfying the following formula 1B: [Math 2] In the above formula 1B, SR ｂ ２０ This is the surface resistance of an anion exchange membrane after 20 days in a basic solution. SR ０ This is the surface resistance of the initial anion exchange membrane.

15. In the above formula 1B, SR ｂ ２０ and SR ０ Each has a resistance of 0.1 Ω·cm. ２ ~3.0Ω·cm ２ The anion exchange membrane according to claim 14.

16. The anion exchange membrane described above is the anion exchange membrane according to claim 7, satisfying the following formula 2A: [Math 3] In the above equation 2A, IEC ａ ２０ This represents the ion exchange capacity of an anion exchange membrane after 20 days in an acidic solution. IEC ０ This represents the ion exchange capacity of the initial anion exchange membrane.

17. The anion exchange membrane described above is the anion exchange membrane according to claim 7, satisfying the following formula 2B: [Math 4] In the above number 2B, IEC ｂ ２０ This represents the ion exchange capacity of an anion exchange membrane after 20 days in a basic solution. IEC ０ This represents the ion exchange capacity of the initial anion exchange membrane.

18. The anion exchange membrane according to claim 7, wherein the anion exchange membrane is used in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis.

19. A step of producing 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; The steps include impregnating a porous polymer support with the anion exchange polymer forming composition to fill at least a portion of the surface and interior of the pores of the porous polymer support with the anion exchange polymer forming composition, 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 anion exchange polymer forming composition, The steps include: irradiating the laminate with light to cause the anion exchange polymer forming composition to undergo a crosslinking reaction, thereby forming an anion exchange polymer, which is a crosslinking product of the anion exchange polymer forming composition, on at least a portion of the surface and interior of the pores of the porous polymer support; A method for producing an anion exchange membrane, comprising the step of peeling the film from a porous polymer support on which the anion exchange polymer is formed in at least a portion of the surface and interior of the pores, in order to produce an anion exchange membrane: 【Chemistry 4】 In the aforementioned chemical formulas A and B, Vi is a vinyl group, R １１ R １６ , R ２１ and R ２２ These are, independently of each other, hydrogen, deuterium, and substituted or unsubstituted C １ -C ２０ Alkyl alkyl groups, and substituted or unsubstituted C ２ -C ２０ Selected from among alkenyl groups, R １１ and R １２ They selectively bind to each other, R １３ and R １４ They selectively bind to each other, R ２１ and R ２２ They selectively bind to each other, a4 is selected from integers between 0 and 4. L １ and L ２ These are C elements that are independent of each other, consisting of single bonds and substituted or unsubstituted elements. １ -C ２０ Selected from among alkylene groups, X － and Y － F － , Cl － , Br － and I － Selected from among, n1, n2, m1, and m2 are each selected from integers between 0 and 10.

20. The method for producing an anion exchange membrane according to claim 19, wherein the anion exchange polymer forming composition further comprises a second monomer represented by the following chemical formula C: 【Transformation 5】 In the aforementioned chemical formula C, Vi is a vinyl group, R ３１ R ３４ These are, independently of each other, hydrogen, deuterium, and substituted or unsubstituted C １ -C ２０ Alkyl and substituted or unsubstituted C ２ -C ２０ Selected from among alkenyl groups, a4 is selected from integers between 0 and 4. Z － is selected from － F － Cl － Br － and I p is selected from integers between 0 and 10.

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