Anion exchange membrane and method for producing the same

Abstract

Disclosed is an anion exchange membrane comprising a first polymer having a repeating unit represented by Chemical Formula 1 and a second polymer which is a polymer or copolymer of a composition including a monomer represented by Chemical Formula 2, wherein the second polymer is entangled in a network formed by the first polymer to form a semi-interpenetrating polymer network (semi-IPN) structure. For explanations of Chemical Formulas 1 and 2, please refer to the present specification. JPEG2025539971000021.jpg79170

Description

[Technical Field]

[0001] The present invention relates to an anion exchange membrane and a method for producing the same. [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 and selectively allow cations to pass through, while anion exchange membranes have positively charged functional groups and selectively allow anions to pass through. Based on electrodialysis, ion exchange membranes are widely used in a variety of fields, such as seawater concentration and desalination, organic acid purification, and valuable metal recovery. They are also applied to hydrogen production via water electrolysis, which has recently attracted attention in the context of addressing the issue of CO2 reduction due to global warming and securing sustainable energy. Water electrolysis techniques using ion exchange membranes include cation exchange membrane or proton exchange membrane water electrolysis, which utilizes proton transfer, and anion exchange membrane water electrolysis, which utilizes anion exchange membranes in an alkaline solution environment. Anion exchange membrane water electrolysis technology utilizes water electrolysis via hydroxide ion conduction, which has the advantage of allowing the use of less expensive water splitting catalysts compared to proton exchange membrane water electrolysis technology, which utilizes hydrogen ion conduction. As such, much research has been conducted on this technology recently.

[0003] Such anion exchange membranes can be applied to water treatment systems such as electrodialysis, bipolar membrane electrodialysis, energy storage desalination, and electrodeionization, as well as to systems such as fuel cells, water electrolysis, reverse electrodialysis, and redox flow batteries. Perfluorinated anion exchange membranes can be used as the anion exchange membrane, but due to their high cost, hydrocarbon-based anion exchange membranes are used in actual systems. However, these hydrocarbon-based anion exchange membranes have limitations in terms of increasing membrane properties such as ion exchange capacity (IEC) because of the presence of a certain percentage or more of a porous support within the membrane. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides an anion exchange membrane that is formed as a free-standing membrane without a porous polymer support, that increases the mobility of hydroxide ions, that has a high current density, and that has a low hydrogen permeability, and a method for producing the same. [Means for solving the problem]

[0005] According to one aspect, a first polymer having a repeating unit represented by the following chemical formula 1; a second polymer that is a polymer or copolymer of a composition containing a monomer represented by the following chemical formula 2; Including, The second polymer is entangled in the network formed by the first polymer to form a semi-interpenetrating polymer network (semi-IPN) structure, thereby providing an anion exchange membrane: [ka]

[0006] In the above Chemical Formulas 1 and 2, R1 to R3, and R 11 Or R 14 are, independently of each other, substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, and -(CH2) n -N(Q1)(Q2), each of Q1 and Q2 is hydrogen or a substituted or unsubstituted C1-C3 alkyl group; R 11 and R 12 , R 11 and R 13 , R 11 and R 14 , R 12 and R 13 , R 12 and R 14 , and R13 and R 14 each may optionally be bonded to the other; L1 is a single bond and a substituted or unsubstituted C1-C 20 alkylene groups, a1 is 0 or 1, and when a1 is 0, (L1) a1 does not exist, and i)R 11 and R 12 , and ii) R 13 and R 14 at least one of them is bonded to each other, Vi is a vinyl group, X - , Y - and Z - are independent of each other, F - , Cl - , Br - and I - is selected from p is selected from the group consisting of 60 and 80; q is selected from the group consisting of 20 and 40; The sum of p and q is 100, Each of n, n1, and n2 is selected from integers of 1 or greater.

[0007] According to another aspect, mixing the first polymer and the monomer in a solvent; casting the mixture onto a substrate; exposing the cast mixture to ultraviolet light to form a film; peeling the substrate from the film; A method for producing an anion exchange membrane is provided, comprising: [Effects of the Invention]

[0008] An anion exchange membrane formed as a freestanding membrane without a porous polymer support and containing both the first polymer and the second polymer may have low surface resistance, high ionic conductivity, and high ion exchange capacity (IEC). Furthermore, as the second polymer is formed, it becomes entangled with the network formed by the first polymer, forming a semi-interpenetrating polymer network (semi-IPN) structure. An anion exchange membrane with such a dense structure may have low hydrogen permeability. DETAILED DESCRIPTION OF THE INVENTION

[0009] An ion exchange membrane and a method for manufacturing the same according to an embodiment will be described in more detail below. The following is provided as an example and is not intended to limit the scope of the present invention, which is defined only by the claims that follow.

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

[0011] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0012] In this specification, the phrases "at least one," "one or more," or "one or more" before an element may be used to refer to a complete list of elements, and not to a complete list of individual elements described above.

[0013] In this specification, the term "comprising" is used to indicate that other elements may be added or / and intervening elements, but not to exclude other elements, unless specifically stated to the contrary.

[0014] In this specification, unless otherwise specified, the unit "parts by weight" refers to the weight ratio between each component.

[0015] Numerical values ​​given herein can be understood to include the meaning of "about" even if not expressly stated.

[0016] As used herein, the term "semi-interpenetrating polymer network (semi-IPN) structure" refers to a structure in which one of two polymer components is selectively crosslinked while the other component is not affected.

[0017] In the present specification, "a to b carbon atoms" or "C a -C b " a and b refer to the number of carbon atoms in the specific functional group. That is, the functional group may contain carbon atoms from a to b. For example, "a C to C alkyl group" or "a C-C alkyl group" refers to an alkyl group having 1 to 2 carbons, i.e., -CH3 and -CH2CH3.

[0018] As used herein, the term "alkyl" refers to an aliphatic hydrocarbon that may be branched or unbranched. Alkyl groups include, but are not necessarily limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like, each of which may be optionally substituted or unsubstituted.

[0019] As used herein, the term "alkylene" refers to a divalent group having the same structure as "alkyl." Alkylene groups include, but are not necessarily limited to, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, and the like, each of which is optionally substituted or unsubstituted.

[0020] As used herein, the term "alkenyl" refers to a monovalent hydrocarbon containing one or more carbon-carbon double bonds, either central or terminal to the alkyl group. Alkenyl groups include, but are not necessarily limited to, ethenyl, propenyl, butenyl, and the like, each of which may be optionally substituted or unsubstituted.

[0021] As used herein, a substituent is derived from an unsubstituted mother group by replacing one or more hydrogen atoms with other atoms or functional groups. For example, when a functional group is "substituted," it means that the functional group is a C1-C 40 Alkyl groups, C1-C 40 Alkoxy groups, C2-C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, C3-C 40 Cycloalkenyl groups, C6-C 40 It means that the functional group is substituted with one or more substituents selected from the group consisting of aryl groups, etc. When a functional group is described as being "optionally substituted," it means that the functional group may be substituted with the aforementioned substituents.

[0022] A typical anion exchange membrane includes a porous polymer support that functions as a reinforcing material to improve ion conductivity and durability, and an electrolyte having anion exchange capacity is filled into the porous polymer support. Such anion exchange membrane has problems such as a relatively complicated manufacturing process, increased surface resistance, low hydroxide ion conductivity, and deterioration of durability and membrane properties due to separation between the bridging electrolyte and the reinforcing material during long-term operation.

[0023] The present inventors have solved the above-mentioned problems by providing an anion exchange membrane having a free-standing film form without a porous polymer support. Therefore, the anion exchange membrane according to one embodiment is clearly different from an anion exchange membrane having a form in which an electrolyte having an anion exchange capacity is filled on the surface or inside the pores of a porous polymer support.

[0024] According to one aspect, a first polymer having a repeating unit represented by the following chemical formula 1; a second polymer that is a polymer or copolymer of a composition containing a monomer represented by the following chemical formula 2; Including, The second polymer is entangled in the network formed by the first polymer to form a semi-interpenetrating polymer network structure, thereby providing an anion exchange membrane: [ka]

[0025] In the above Chemical Formulas 1 and 2, R1 to R3, and R 11 Or R 14 are, independently of each other, substituted or unsubstituted C1-C 20 Alkyl groups, substituted or unsubstituted C2-C 20 Alkenyl groups, and -(CH2) n -N(Q1)(Q2), each of Q1 and Q2 is hydrogen or a substituted or unsubstituted C1-C3 alkyl group; R11 and R 12 , R 11 and R 13 , R 11 and R 14 , R 12 and R 13 , R 12 and R 14 , and R 13 and R 14 each may optionally be bonded to the other; L1 is a single bond and a substituted or unsubstituted C1-C 20 alkylene groups, a1 is 0 or 1, and when a1 is 0, (L1) a1 does not exist, and i)R 11 and R 12 , and ii) R 13 and R 14 at least one of them is bonded to each other, Vi is a vinyl group, X - , Y - and Z - are independent of each other, F - , Cl - , Br - and I - is selected from p is selected from the group consisting of 60 and 80; q is selected from the group consisting of 20 and 40; The sum of p and q is 100, Each of n, n1, and n2 is selected from integers of 1 or greater.

[0026] First polymer The first polymer has a repeating unit represented by Chemical Formula 1 and also contains a quaternary ammonium salt. The first polymer can serve as the main chain of the anion exchange membrane. The first polymer can form a three-dimensional network. The first polymer is not chemically bonded to the second polymer. In the anion exchange membrane, the weight of the first polymer can be greater than the weight of the second polymer.

[0027] According to one embodiment, in Formula 1, at least one of R1 to R3 is a substituted or unsubstituted C1-C 20 For example, each of R1 to R3 can be a substituted or unsubstituted C1-C 20 It may also be an alkyl group. Specifically, each of R1 to R3 may be selected from the group consisting of a methyl group, an ethyl group, and a propyl group.

[0028] In Formula 1, q is selected from the range of 20 to 40, for example, q may be selected from the range of 25 to 35. If q is less than 20, the physical properties of the anion exchange membrane, such as sheet resistance, ionic conductivity, ion exchange capacity, current density, and hydrogen permeability, may be reduced. If q is more than 40, the mechanical strength may be reduced and there may be problems with reduced solubility when preparing the anion exchange membrane in a bath solution.

[0029] Second polymer The second polymer may also be a cross-linked product of a composition containing the monomer represented by Formula 2. During the preparation of the anion exchange membrane, the monomer may be distributed within the three-dimensional network formed by the first polymer. The monomer may also contain a vinyl group. Upon irradiation with ultraviolet light, bonds between the monomers may be formed via the vinyl groups. The second polymer formed by polymerization of the monomer may be entangled in the three-dimensional network formed by the first polymer. Therefore, the anion exchange membrane may have a semi-interpenetrating polymer network structure formed by the entanglement of the first polymer and the second polymer. That is, the first polymer and the second polymer are not chemically bonded but are physically entangled. In the anion exchange membrane, the weight of the second polymer may be greater than the weight of the first polymer.

[0030] According to one embodiment, the monomer may be represented by any one of the following formulas 2-1 to 2-6: [ka] [ka]

[0031] In the above chemical formulas 2-1 to 2-6, R 11 Or R 14 , L1, a1, Vi, Y - , Z - The explanations for n1 and n2 are the same as those for Formula 2. That is, the vinyl group, which is the part polymerized between the monomers, can be present at various positions of the benzene group in Formula 2.

[0032] R 11 and N + The bond with R can be a single or double bond. 12 and N + The bond with R can be a single or double bond. 13 and N + The bond with R can be a single or double bond. 14 and N + The bond with may be a single or double bond. For example, R 11 and R 12 are bonded to each other, and R 13 and R 14 are bonded together to form R 11 -R 12 -N + -R 14 -R 13 -N + The group is also a pyrazine group.

[0033] For example, R 11 Or R 14 If they do not combine with each other, a1 is 1, so (L1) a1 Another example is R 11 and R 12 are bonded to each other, and R 13 and R 14 are connected to each other and a1 is 0, so (L1) a1 is absent, a pyrazine group may be present. 11 and R 12 are bonded to each other, and R 13 and R14 are connected to each other and a1 is 1, so (L1) a1 When present, a bicyclo group may be present.

[0034] According to one embodiment, n, n1, and n2 may each be selected from integers from 1 to 10. For example, n, n1, and n2 may each be 1, 2, 3, 4, or 5.

[0035] According to an embodiment, in Formula 2 and Formulas 2-1 to 2-6, at least one of n1 and n2 can be 1. For example, each of n1 and n2 can be 1.

[0036] According to one embodiment, in the above-mentioned Formula 2, Formula 2-1 to Formula 2-6, [ka] The group represented by may be represented by any one of the following chemical formulas 3-1 to 3-4: [ka] Each of the * and *' above is a bonding site with the adjacent atom.

[0037] According to one embodiment, the monomer is at least one selected from the following compounds 1 to 5: [ka] [ka]

[0038] That is, the monomers are N1,N1,N2,N2-tetramethyl-N1,N2-bis(4-vinylbenzyl)ethane-1,2-diaminium (compound 1 (which may be referred to as TMVE)), N1,N1,N6,N6-tetramethyl-N1,N6-bis(4-vinylbenzyl)hexane-1,6-diaminium (compound 2 (which may be referred to as TMVH)), 1,4-bis(4-vinylbenzyl)pyrazine-1, The compound may be one or more selected from the group consisting of 1,3-bis(4-vinylbenzyl)-1,3,5,7-tetraazaadamantane-1,3-diium (compound 3 (which may be referred to as VBP)), 1,3-bis(4-vinylbenzyl)-1,3,5,7-tetraazaadamantane-1,3-diium (compound 4 (which may be referred to as VTAA)), and 1,4-bis(4-vinylbenzyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium (compound 5 (which may be referred to as VBDAO)).

[0039] In the above-mentioned chemical formula 2 and chemical formulas 2-1 to 2-6, "R 11 Or R 14 are not bonded to each other" can refer to the above chemical formula 3-1 or the above compounds 1 and 2.

[0040] In the above-mentioned chemical formula 2 and chemical formulas 2-1 to 2-6, "R 11 and R 12 are bonded to each other, and R 13 and R 14 are bonded to each other" may refer to the above chemical formulas 3-2 to 3-4 or the above compounds 3 to 5.

[0041] In the above-mentioned chemical formula 2 and chemical formulas 2-1 to 2-6, "a1 is 0, so (L1) a1 "A compound in which a1 is not present" may refer to the above-mentioned Chemical Formula 3-2 or the above-mentioned Compound 3. Since a1 is 0, (L1) a1 If there is no R 11 and R 12 are bonded to each other, and ii) R 13 and R 14 can be bonded to each other.

[0042] According to one embodiment, R 11 Or R14 are each independently a substituted or unsubstituted C1-C5 alkyl group, a substituted or unsubstituted C2-C5 alkenyl group, and -(CH2) n -N(Q1)(Q2), where each of Q1 and Q2 is hydrogen or a substituted or unsubstituted C1-C3 alkyl group, and n is 0, 1, or 2. For example, R 11 Or R 14 may be selected independently from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl, ethenyl, propenyl, butenyl, -CH-NHCH and -CH-N(CH).

[0043] According to one embodiment, L1 is a substituted or unsubstituted C1-C 10 It can also be an alkylene group. For example, L can be -CH-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, and -(CH) 10 - can be selected from among.

[0044] Vi is [ka] where * is the bonding site to the adjacent atom.

[0045] Y - and Z - may be identical to or different from each other. For example, Y - and Z - Each is Cl - It is also.

[0046] According to one embodiment, the monomer may contain 2 to 4 nitrogen atoms. + In another example, the monomer may include two N + , and also those containing two Ns.

[0047] According to an embodiment, the composition including the monomer represented by Formula 2 further includes a photoinitiator, which may be at least one selected from the group consisting of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, and 1-hydroxy-cyclohexyl-phenyl-ketone.

[0048] Anion Exchange Membrane According to one embodiment, the weight of the first polymer contained in the anion exchange membrane may be greater than the weight of the second polymer contained in the anion exchange membrane. For example, the ratio of the weight of the first polymer to the weight of the second polymer may be 5:0.1 to 5:4. Specifically, the weight of the first polymer contained in the anion exchange membrane may be more than twice the weight of the second polymer contained in the anion exchange membrane. The ratio of the weight of the first polymer to the weight of the second polymer may be 5:0.5 to 5:2, or 5:1 to 5:2.

[0049] According to one embodiment, the anion exchange membrane may be a free-standing film. The anion exchange membrane may also be a monolayer membrane. That is, the anion exchange membrane does not include a separate substrate (support). For example, the first polymer or the second polymer may be present in any portion of the anion exchange membrane.

[0050] According to one embodiment, the anion exchange membrane does not include a porous polymer support, for example, the anion exchange membrane does not include polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polybenzimidazole, polyarylene sulfide, polyether ether ketone, polyether sulfone, polysulfone, polystyrene, polyarylene ether sulfone, and polyether ketone.

[0051] According to one embodiment, the anion exchange membrane has a surface resistance of 0.1 Ω cm when measured at 25°C in 1 M potassium hydroxide.2 or 1 Ω·cm 2 The surface resistance is also calculated by Evaluation Example 1 described later. For example, at 25°C in 1 M potassium hydroxide, the surface resistance of the anion exchange membrane calculated by Evaluation Example 1 is 0.15 Ω cm 2 or 0.5 Ω·cm 2 , or 0.2 Ω·cm 2 or 0.4Ω·cm 2 It is also.

[0052] According to one embodiment, the anion exchange membrane has an ionic conductivity of 5 mS / cm to 80 mS / cm measured at 25°C in 1 M potassium hydroxide. The ionic conductivity is calculated according to Evaluation Example 2, which will be described later. For example, the ionic conductivity of the anion exchange membrane measured at 25°C in 1 M potassium hydroxide according to Evaluation Example 2 is 5.5 mS / cm to 70 mS / cm, 6 mS / cm to 60 mS / cm, 6.5 mS / cm to 50 mS / cm, 7 mS / cm to 40 mS / cm, 7.5 mS / cm to 35 mS / cm, or 8 mS / cm to 30 mS / cm.

[0053] According to one embodiment, the anion exchange membrane has an ion exchange capacity of 1.0 meq / g to 3.0 meq / g. The ion exchange capacity is calculated according to Evaluation Example 3 described below. For example, the anion exchange membrane has an ion exchange capacity of 1.5 meq / g to 3.0 meq / g, 1.8 meq / g to 3.0 meq / g, 1.5 meq / g to 2.5 meq / g, or 1.8 meq / g to 2.5 meq / g.

[0054] According to one embodiment, the anion exchange membrane thickness is 30 μm to 100 μm. For example, the anion exchange membrane thickness is 40 μm to 80 μm, or 50 μm to 70 μm. If the anion exchange membrane thickness is outside the above range, physical properties such as durability, mechanical stability, surface resistance, ion conductivity, ion exchange capacity, and current density of the anion exchange membrane may be reduced.

[0055] Anion exchange membrane manufacturing method According to another aspect, mixing the first polymer and the monomer in a solvent; casting the mixture onto a substrate; exposing the cast mixture to ultraviolet light to form a film; peeling the substrate from the film; A method for producing an anion exchange membrane is provided, comprising:

[0056] The solvent may be a co-solvent including a first solvent that dissolves the first polymer and a second solvent that dissolves the monomer, for example, 1-methyl-2-pyrrolidone, and for example, methanol.

[0057] Examples of the substrate include a glass plate, a polyester film, and stainless steel (SUS).

[0058] Although the method for manufacturing the anion exchange membrane includes a step of peeling off the substrate, the manufactured anion exchange membrane does not include a substrate (support). For example, the substrate can be peeled off from the film by immersing the substrate and the film attached to the substrate in water or a potassium hydroxide (KOH) solution.

[0059] According to an embodiment, the ultraviolet light may be selected from ultraviolet A (UVA), ultraviolet B (UVB), ultraviolet C (UVC), and vacuum ultraviolet (VUV). The ultraviolet light intensity is 2,000 mJ / cm. 2 or 10,000mJ / cm 2 It is also.

[0060] According to one embodiment, the method for preparing an anion exchange membrane may further include drying the composition or the film at room temperature or higher for at least 1 minute to volatilize the solvent, for example, at 50°C to 100°C, or 60°C to 80°C, for 5 to 60 minutes, or 10 to 30 minutes.

[0061] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to such examples.

[0062] Example A1 The first polymer was dissolved in a mixed solvent of 1-methyl-2-pyrrolidone and methanol at 60°C in an amount of 25% by weight of the total bath volume, and then compound 1 was added and stirred at room temperature. At this time, the weight ratio of the first polymer to compound 1 was 5:1. After the first polymer and compound 1 were completely dissolved, 2-hydroxy-2-methylpropiophenone was added as a photoinitiator in an amount of 1% by weight of the total bath volume, and then the mixture was further stirred for about 10 minutes. After melting is complete, the mixture is cast onto a substrate with a blade or slot die setup. After casting, the mixture was charged with 3,000 mJ / cm 2 The film was then irradiated with UVC light at a dose of 1000 W to crosslink Compound 1. The film was then dried in a hot air oven at 70°C for 20 minutes to evaporate the solvent, forming a film. The film attached to the substrate was then immersed in water or potassium hydroxide (KOH), and the substrate was peeled off from the film to produce a 70 μm-thick anion-exchange membrane.

[0063] Examples A2 to A5 An anion exchange membrane was prepared in the same manner as in Example A1, except that the compounds listed in Table 1 below were used instead of Compound 1.

[0064] Comparative Example A1 (without second polymer) The first polymer is dissolved in a mixed solvent of 1-methyl-2-pyrrolidone and methanol at 60° C. in an amount of 25% by weight of the total amount of the solution, and then cooled to room temperature. The mixture was then cast onto a substrate using a blade or slot die. The mixture was dried in a hot air oven at 70°C for 20 minutes to evaporate the solvent, forming a film. The film attached to the substrate was immersed in water or potassium hydroxide (KOH), and the substrate was peeled off from the film to produce a 70 μm-thick anion-exchange membrane.

[0065] Comparative Examples A2 to A6 (without the first polymer) The compound shown in Table 1 below as the second polymer monomer is dissolved in a mixed solvent of 1-methyl-2-pyrrolidone and methanol at 25 wt % of the total bath volume. After the compound is completely dissolved, 2-hydroxy-2-methylpropiophenone as a photoinitiator is added at 1 wt % of the total bath volume, and the mixture is further stirred for about 10 minutes. After melting is complete, the mixture is cast onto a substrate with a blade or slot die equipment. After casting, the mixture was charged with 3,000 mJ / cm 2 The film is irradiated with UVC ultraviolet light at a light intensity to crosslink Compound 1. The film is then dried in a hot air oven at 70°C for 20 minutes.

[0066] Comparative Examples B1 to B5 (including a porous polymer support instead of the first polymer) A 60 μm thick polypropylene (PP) porous polymer support (porosity: 51%) was prepared. The compounds listed in Table 2 below as second polymer monomers were dissolved in a mixed solvent of 1-methyl-2-pyrrolidone and methanol at 25 wt % of the total bath volume. After the compounds were completely dissolved, 2-hydroxy-2-methylpropiophenone as a photoinitiator was added at 1 wt % of the total bath volume, and the mixture was further stirred for about 10 minutes to prepare a composition. The hydrophilized porous polymer support was immersed in the composition for 5 minutes, and the composition was filled on the surface of the porous polymer support and inside the pores. A polyester film having a thickness of 50 μm was pressed onto the upper and lower surfaces of the porous polymer support filled with the composition, to produce a laminate in which the polyester film and the porous polymer support were laminated. 3,000mJ / cm 2 The porous polymer support was irradiated with UVC rays at a dose of 1000 nm to form a second polymer, which was a polymer or copolymer of the compound, on the surface and inside the pores of the porous polymer support. The polyester film was peeled off from the porous polymer support with the second polymer formed on the surface and inside the pores to produce an anion exchange membrane.

[0067] Examples C1-1 to C5-2 and Comparative Examples C1-1 to C5-2 (anion exchange membrane thickness) An anion exchange membrane was prepared in the same manner as in Example A1, except that the compound shown in Table 3 below was used as the second polymer monomer and the anion exchange membrane thickness was the value shown in Table 3 below.

[0068] Evaluation example 1 (surface resistance) Each anion exchange membrane specimen was cut into a 5 cm x 5 cm size to prepare a sample. The sample was immersed in a 1 M KOH solution for 12 hours or more. In the 1 M KOH solution, the sample was placed between electrodes for measuring sheet resistance, and the measured value was stabilized. The sample was placed between electrodes for measuring sheet resistance, and the linear resistance (R1) of the anion exchange membrane was measured using an LCR meter (E4980A (Agilent)). After removing the anion exchange membrane, the resistance (R2) of the 1M KOH solution was measured. The sheet resistance of the anion exchange membrane was calculated using the following equation 1.

[0069] [Formula 1] Rm = (R1 - R2) × S In the above formula 1, Rm is the surface resistance of the anion exchange membrane (Ω cm 2 ) and R1 is the linear resistance of the anion exchange membrane, R2 is the resistance of the 1M KOH solution, S is the area of ​​the electrode.

[0070] Evaluation example 2 (ionic conductivity) The sheet resistance (Rm) of the anion exchange membrane calculated in Evaluation Example 1 was substituted into the following formula 2 to calculate the ionic conductivity. [Formula 2] Ionic conductivity (mS / cm) = [anion exchange membrane thickness (μm) / Rm (Ω cm 2 )] / 10

[0071] Evaluation Example 3 (Ion Exchange Capacity) Each anion exchange membrane was cut into 5cm x 5cm pieces to prepare samples. The samples were washed with distilled water and then removed with tissue paper. 70 mL of 1M NaCl solution was filled into a vial, and the dehydrated samples were placed in the 1M NaCl solution and immersed for at least 12 hours for primary pretreatment. After primary pretreatment, the samples were washed several times with distilled water and then removed with tissue paper. 70 mL of 0.5M Na2CO3 solution was filled into a vial, and the dehydrated samples were placed in the 0.5M Na2CO3 solution and immersed for at least 12 hours for secondary pretreatment. After secondary pretreatment, the samples were removed from the vials, and the remaining solution was titrated with 0.01M AgNO3 solution. The volume of AgNO3 solution added during titration was recorded. The 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 completed, the weight of the dried anion exchange membrane was measured, and the measured weight of the dried anion exchange membrane was substituted into the following equation 3 to calculate the ion exchange capacity (IEC). [Formula 3] IEC (meq / g) = [volume of titration reagent (mL) x 0.01] / weight of dried anion exchange membrane (g)

[0072] Evaluation example 4 (current density) Each anion exchange membrane specimen was cut into a 5cm x 5cm size to prepare samples. The samples were pretreated by immersing them in a 1M KOH solution at room temperature for 12 hours, and then a water electrolysis system was used to measure the current density by applying a constant voltage of 1.5V to 2V and recording the current value.

[0073] Evaluation example 5 (appearance evaluation) The appearance of each anion exchange membrane was visually observed and evaluated according to the following criteria. Good: The surface is smooth and free of cracks and peeling. Poor: The surface is not smooth, cracked, or peeling

[0074] Evaluation example 6 (leak evaluation) Each anion exchange membrane specimen was cut into a size of 5 cm x 5 cm to prepare a sample. After assembling the sample into a unit cell, hydrogen at a pressure of 20 kPa was introduced into the cathode (at this time, the anode side port was open and in a state equivalent to atmospheric pressure). The unit cell was left to stand for 5 minutes or more to allow the internal pressure to stabilize. The hydrogen pressure was measured with a manometer one minute later on the side opposite the anion exchange membrane from the hydrogen introduction point.

[0075] [Table 1]

[0076] From Table 1, it can be seen that membrane formation was impossible in Comparative Examples A2 to A6, which did not use the first polymer having the repeating unit represented by Chemical Formula 1. This indicates that when the second polymer using the monomer represented by Chemical Formula 2 is used without the first polymer, a separate configuration is required for application as an anion exchange membrane. Therefore, Comparative Examples B1 to B5, which use a separate configuration, will be described below with reference to Table 2.

[0077] The anion exchange membranes prepared in Examples A1 to A5 had a resistance of 0.05 Ω·cm 2It has a low surface resistance of 1000 kJ / cm or less and a high ionic conductivity of 15 mS / cm or more, and has a higher ion exchange capacity than the anion exchange membrane of Comparative Example A1 which uses the first polymer without the second polymer.It is also clear that it has low hydrogen permeability as evidenced by the low hydrogen pressure in the leak evaluation.

[0078] [Table 2]

[0079] When the second polymer using the monomer represented by Formula 2 is used without the first polymer, a free-standing anion exchange membrane cannot be prepared. Therefore, anion exchange membranes in which the second polymer is present on the surface and inside the pores of a porous polymer support can be prepared and their physical properties can be compared.

[0080] Referring to Tables 1 and 2 above, it can be seen that the anion exchange membranes prepared according to Examples A1 to A5, which include the first polymer and the second polymer without a porous polymer support, have lower surface resistance, higher ionic conductivity, higher ion exchange capacity, and higher current density than the anion exchange membranes prepared according to Comparative Examples B1 to B5, which use a porous polymer support instead of the first polymer.

[0081] [Table 3]

[0082] Referring to Tables 1 and 3 together, it can be seen that the anion exchange membranes prepared by Examples A1 to A5 and C1-1 to C5-2 and having a thickness of 30 μm to 100 μm have stronger durability, or lower surface resistance, higher current density, higher ion exchange capacity, and / or lower hydrogen permeability than the anion exchange membranes prepared by Comparative Examples C1-1 to C5-2 and having a thickness outside the range of 30 μm to 100 μm.

[0083] From the above Evaluation Examples 1 to 6, it can be seen that the anion exchange membranes prepared in Examples A1 to A5 and Examples C1-1 to C5-2 are suitable for use in electrodialysis, bipolar membrane electrodialysis, electrodeionization, capacitive deionization, or water electrolysis systems.

[0084] The above description is for illustrative purposes only, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. Therefore, the above-described embodiments should be understood to be illustrative in all respects and not limiting.

Claims

1. a first polymer having a repeating unit represented by the following chemical formula 1; a second polymer that is a polymer or copolymer of a composition containing a monomer represented by the following chemical formula 2; Including, The second polymer is entangled in the network formed by the first polymer to form a semi-interpenetrating polymer network (semi-IPN) structure. 【Chemistry 1】 In the above Chemical Formulas 1 and 2, R １ Or R ３ , and R １１ Or R １４ are each independently a substituted or unsubstituted C １ -C ２０ alkyl group, substituted or unsubstituted C ２ -C ２０ Alkenyl groups, and —(CH ２ ) ｎ -N(Q １ ) (Q ２ ) and Q １ and Q ２ Each of is hydrogen or substituted or unsubstituted C １ -C ３ is an alkyl group, R １１ and R １２ , R １１ and R １３ , R １１ and R １４ , R １２ and R １３ , R １２ and R １４ , and R １３ and R １４ may be optionally linked to each other; L １ represents a single bond and a substituted or unsubstituted C １ -C ２０ alkylene groups, a1 is 0 or 1, and when a1 is 0, (L １ ) ａ１ does not exist, and i) R １１ and R １２ , and ii) R １３ and R １４ at least one of them is bonded to each other, Vi is a vinyl group; X － , Y － and Z － are, independently of each other, F － , Cl － ,Br － and I － is selected from p is selected from the group consisting of 60 and 80; q is selected from the group consisting of 20 and 40; The sum of p and q is 100, Each of n, n1, and n2 is selected from integers of 1 or greater.

2. R １ Or R ３ Each of １ -C ２０ The anion exchange membrane according to claim 1 , wherein the anion exchange membrane is an alkyl group.

3. The anion exchange membrane of claim 1, wherein the monomer is represented by any one of the following chemical formulas 2-1 to 2-6: 【Chemistry 2A】 【Chemistry 2B】 。

4. The anion exchange membrane according to claim 1 , wherein at least one of n1 and n2 is 1.

5. In the above Chemical Formula 2, 【Transformation 3】 The anion exchange membrane according to claim 1, wherein the group represented by the formula: 【Chemistry 4】 Each of the aforementioned * and *' is a bonding site with an adjacent atom.

6. The anion exchange membrane according to claim 1, wherein the monomer is at least one selected from the following compounds 1 to 5: [Chemical 5A] 【Chem.5B】 。

7. 2. The anion exchange membrane according to claim 1, wherein the weight ratio of the first polymer to the second polymer is 5:0.1 to 5:

4.

8. The composition containing the monomer represented by Formula 2 further contains a photoinitiator, The anion exchange membrane according to claim 1, wherein the photoinitiator is one or more selected from the group consisting of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, and 1-hydroxy-cyclohexyl-phenyl-ketone.

9. 2. The anion exchange membrane according to claim 1, wherein the anion exchange membrane is a free-standing film.

10. The anion exchange membrane of claim 1 , wherein the anion exchange membrane does not include a porous polymer support.

11. At 25°C and in 1M potassium hydroxide, the surface resistance is 0.1 Ω cm ２ or 1 Ω cm ２ The anion exchange membrane according to claim 1, wherein

12. 2. The anion exchange membrane according to claim 1, which has an ionic conductivity of 5 mS / cm to 80 mS / cm at 25°C and in 1 M potassium hydroxide.

13. 2. The anion exchange membrane according to claim 1, wherein the ion exchange capacity is from 1.0 meq / g to 3.0 meq / g.

14. 2. The anion exchange membrane according to claim 1, having a thickness of 30 μm to 100 μm.

15. mixing the first polymer defined in claim 1 and the monomer defined in claim 1 in a solvent; casting the mixture onto a substrate; irradiating the cast mixture with ultraviolet light to form a film; peeling the substrate from the film; A method for producing an anion exchange membrane, comprising:

16. The method for producing an anion exchange membrane according to claim 15, wherein the ultraviolet light is selected from ultraviolet A (UVA), ultraviolet B (UVB), ultraviolet C (UVC), and vacuum ultraviolet (VUV).

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