Anion exchange membrane using single liquid-phase menshutkin polymerization and manufacturing method therefor

Abstract

The present invention relates to an anion exchange membrane and a method for manufacturing same, the anion exchange membrane comprising: a porous support; and a quaternary ammonium polymer having a three-dimensional crosslinked structure formed on the support or filled in the support, wherein the quaternary ammonium polymer is formed through Menshutkin polymerization between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

Description

Anion exchange membrane using single-liquid Menshkin polymerization reaction and method for manufacturing the same

[0001] The present invention relates to an anion exchange membrane using a single liquid Menshkin polymerization reaction and a method for manufacturing the same.

[0002] Anion-exchange membranes are membranes containing cationic functional groups (primarily quaternary ammonium) that selectively transport anions. Anion-exchange membranes are currently used as key materials in processes requiring the selective transport of anions, such as water electrolysis, electrolysis, fuel cells, electrodialysis, and redox flow batteries.

[0003] Here, anion exchange membrane water electrolysis is a process that produces hydrogen through the electrolysis of water using an anion exchange membrane. In this process, the anion exchange membrane is located between the reduction electrode (hydrogen generation electrode) and the oxidation electrode (oxygen generation electrode), and it plays a role in preventing the permeation / mixing of hydrogen and oxygen gases generated at each electrode, while selectively transferring the anion, hydroxide ion, to complete the reaction between the two electrodes. Therefore, the anion exchange membrane plays a crucial role in preventing explosion due to gas mixing, enabling a safe water electrolysis process, and in efficiently transferring hydroxide ions, thereby increasing hydrogen production efficiency.

[0004] Recently, active research has been conducted to increase the cationic functional group density of anion exchange membranes to improve hydrogen production efficiency. However, conventional anion exchange membranes have a structure in which cationic functional groups are attached to side chains (pendant groups) of the polymer backbone, limiting their ability to increase cationic functional group density. Furthermore, the cationic functional groups attached to the side chains form anisotropic arrangements within the anion exchange membrane, resulting in inefficient ion transport. Furthermore, many existing anion exchange membranes have linear polymer structures, resulting in low thermochemical (alkaline) stability, making long-term operation of water electrolysis difficult.

[0005] To solve these problems, a prior patent (Domestic Patent Registration No. 10-2778897) disclosed that a quaternary ammonium polymer structure with excellent anionic conductivity was produced by interfacial polymerization of the Menshutkin polymerization reaction between an alkyl halide monomer and a tertiary amine monomer. In the prior patent, since the solubility of the two monomers in the solvents is different, the interfacial polymerization technique was used. This is done by dissolving monomers with different functional groups in two immiscible solvents, and then inducing the Menshutkin polymerization reaction at the interface between the solutions to form a high-density quaternary ammonium polymer thin film. However, when interfacial polymerization is utilized, the quaternary ammonium polymer is formed only at the interface, so it is mainly obtained in the form of a thin film, and there are problems in that the thickness control is not easy and the quaternary ammonium polymer is formed non-uniformly in the thickness direction. Furthermore, the process for creating the interface is somewhat complex, making it difficult to manufacture quaternary ammonium polymers on a large scale. Therefore, to address this issue, the development of a technology capable of inducing the Menshkin polymerization reaction in a single liquid phase is required.

[0006] The present invention provides an anion exchange membrane comprising a porous support; and a quaternary ammonium polymer having a three-dimensional cross-linked structure formed on the support or filled inside the support, wherein the quaternary ammonium polymer is formed through a Menshutkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0007] However, the technical problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0008] The present invention provides an anion exchange membrane comprising a porous support; and a quaternary ammonium polymer having a three-dimensional cross-linked structure formed on the support or filled inside the support, wherein the quaternary ammonium polymer is formed through a Menshutkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0009] The porous support is polyethylene, polypropylene, polymethylpentene, polybutene-1, ethylene propylene rubber, polyacetylene, polyisobutylene, polyethylene terephthalate, polyvinyl chloride, polyvinylbenzyl chloride, polyvinyl fluoride, polyvinylene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polyethersulfone, polysulfone, polyacrylonitrile, polystyrene, polyamide, It may include at least one selected from the group consisting of polydimethylsiloxane, polyvinyl alcohol, ethylene vinyl alcohol, polycarbonate, polybenzimidazole, polyvinylpyrrolidone, polyetherimide, polyetheretherketone, cellulose, and cellulose acetate.

[0010] The above porous support can be hydrophilized.

[0011] The hydrophilic treatment of the above porous support can be performed by one or more methods selected from the group consisting of organic coating, inorganic coating, ozone treatment, ultraviolet treatment, plasma, atomic layer deposition, chemical vapor deposition, and chemical oxidation treatment.

[0012] The hydrophilic treatment of the above porous support is performed by an organic coating method, and the organic coating method comprises ethylene vinyl alcohol, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polydopamine, polyacrylic acid, polymethacrylic acid, polyetherimide, tannic acid, polyvinyl amine, poly(4-styrene sulfonic acid), poly(vinylsulfonic acid), polyethylenimine, polyaniline, polybenzimidazole, polyvinyl pyrrolidone, cellulose, cellulose acetate, Ploxamer, ploxamine, polyoxyethylene alkyl ether, polyoxyalkyl benzyl ether, polyoxyalkyl phenyl ether, polysorbate, sorbitan ester, alkyl ether surfate, alkyl benzene sulfonate, alkyl ammonium bromide, alkyl ammonium chloride,It may be a method for coating an organic material comprising at least one component selected from the group consisting of benzalkonium bromide and benzalkonium chloride.

[0013] The above organic coating method can be performed including a step of coating an organic material and then crosslinking the coated organic material.

[0014] The above multifunctional alkyl halide monomer has two or more alkyl halide groups and may have a weight average molecular weight of 50 g / mol to 1,000,000 g / mol.

[0015] The above multifunctional alkyl halide monomers are 1,3,5-tris(bromomethyl)benzene, 1,3,5-tris(chloromethyl)benzene, 1,3,5-tris(iodomethyl)benzene, 1,2-dibromoethane, 1,2-dichloroethane, 1,2-diiodoethane, 1,3-dibromopropane, 1,3-dichloropropane, 1,3-diiodopropane, 1,4-dibromobutane, 1,4-dichlorobutane, 1,4-diiodobutane, 1,6-dibromohexane, 1,6-dichlorohexane, 1,6-diiodohexane, 1,2-bis(bromomethyl)benzene, 1,2-bis(chloromethyl)benzene, 1,2-bis(iodomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,3-bis(iodomethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,4-bis(chloromethyl)benzene, 1,4-bis(iodomethyl)benzene, 1,4-bis(2-bromoethyl)benzene(1,4-bis(2-bromoethyl)benzene), 1,4-bis(2-chloroethyl)benzene, 1,4-bis(2-iodoethyl)benzene, 2,6-bis(bromomethyl)naphthalene, 2,6-bis(chloromethyl)naphthalene, 2,6-bis(iodomethyl)naphthalene, 1,4-bis(1,2-dibromoethyl)benzene, It may be at least one selected from the group consisting of 1,4-bis(1,2-dichloroethyl)benzene and 1,4-bis(1,2-diiodoethyl)benzene.

[0016] The above multifunctional tertiary amine monomer has two or more tertiary amine groups and may have a weight average molecular weight of 50 g / mol to 1,000,000 g / mol.

[0017] The above polyfunctional tertiary amine monomers are 4,4'-trimethylenebis(1-methylpiperidine), N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris[2-(dimethylamino)ethyl]amine, Tris(dimethylamino)methane, tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethylhexamethylenediamine, 1,4-dimethylpiperazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacylcotetradecane, N,N,N',N'-tetramethyl-1,4-phenylenediamine, N,N,N',N'-tetramethyl-1,3-phenylenediamine, 1,It may be at least one selected from the group consisting of 1,4-bis(diphenylamino)benzene, 4,4'-bipyridyl, 4,4'-trimethylenedipyridine, hexamine, altretamine, 2,4,6-tris(dimethylaminomethyl)phenol, and polyethyleneimine.

[0018] The partition coefficient (LogP) value of the above polar protic solvent may be -2.00 or more, and the dielectric constant value of the above polar aprotic solvent may be 2.0 or more.

[0019] The polar protic solvents are water, glycerol, ethylene glycol, diethylene glycol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, acetic acid, formic acid, formamide, 2,2,2-trifluoroethanol, lactic acid. acid), phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, salicylic acid, benzyl alcohol and 2-methoxyethanol, wherein the polar aprotic solvent comprises at least one selected from the group consisting of 1,4-dioxane, butyl acetate, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, acetone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Acetonitrile, sulfolane, sulfolene,It may include at least one selected from the group consisting of dimethyl sulfoxide, nitrometane, dimethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dimethyl sulfate, hexamethylphosphoramide, dichloromethane, chloroform, nitrobenzene, methyl formate, and ethyl formate.

[0020] In one embodiment of the present invention, a method for producing an anion exchange membrane is provided, characterized by comprising the steps of: (a) preparing a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent including a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer; and (b) forming a quaternary ammonium polymer having a three-dimensional cross-linked structure on or inside a porous support through a Menshkin polymerization reaction in the single liquid phase.

[0021] The concentration of the polyfunctional alkyl halide monomer in the single liquid phase of the above step (a) may be 2 (w / v)% to 40 (w / v)%, and the concentration of the polyfunctional tertiary amine monomer in the single liquid phase may be 2 (w / v)% to 40 (w / v)%.

[0022] The Menshkin polymerization reaction in the single liquid phase of the above step (b) can be carried out at 10°C to 120°C for 1 minute to 5 hours.

[0023] An anion exchange membrane according to the present invention comprises a porous support; and a quaternary ammonium polymer having a three-dimensional cross-linked structure formed on the support or filled inside the support, wherein the quaternary ammonium polymer is characterized in that it is formed through a Menshutkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0024] The anion exchange membrane according to the present invention has high ionic conductivity by forming an ion channel structure in which high-density cationic quaternary ammonium functional groups are uniformly arranged in an isotropic manner, and has high thermochemical stability due to its three-dimensional cross-linked structure. In particular, since the Menshkin polymerization reaction is simple and takes place in a single liquid phase, it is easy to manufacture in large quantities and over a large area.

[0025] Therefore, the anion exchange membrane according to the present invention can be widely used in fields requiring selective transport of anions and thermochemical stability, such as water electrolysis, electrolysis, fuel cells, electrodialysis, and redox flow batteries.

[0026] FIG. 1 schematically illustrates a method for producing a quaternary ammonium polymer and an anion exchange membrane having a three-dimensional cross-linked structure using a single-liquid Menshkin polymerization reaction according to one embodiment of the present invention.

[0027] Figure 2 shows the results of confirming the optimization of the solvent for a single liquid Menshkin polymerization reaction when each monomer concentration is 7.5 (w / v)%, as in Preliminary Example 1.

[0028] Figure 3 shows the results of confirming the optimization of the solvent for a single-liquid Menshkin polymerization reaction when each monomer concentration is 10 (w / v)%, as in Preliminary Example 2.

[0029] Figure 4 shows the results of confirming the surface structure and cross-sectional structure of Example and Comparative Example A using a scanning electron microscope.

[0030] Figure 5 shows the results of confirming the surface structure and polymer phase of Example and Comparative Example A using an atomic force microscope.

[0031] Figure 6 shows the results of measuring the ionic conductivity of Examples A, B, and C using electrochemical impedance spectroscopy.

[0032] Figure 7 shows the results of evaluating the electrolysis performance of Examples A, B, and C by measuring the voltage according to the current density in a 1 M potassium hydroxide solution at 80°C.

[0033] Figures 8(a) and (b) show the results of evaluating thermochemical stability by observing changes in surface structure and ionic conductivity according to the immersion time by immersing Example and Comparative Example A in a 1 M potassium hydroxide solution at 80°C.

[0034] Figure 9 shows an example of a constant current density (1 A cm) in a 1 M potassium hydroxide solution at 60°C. -2 ) and measured the voltage change over time to evaluate the long-term operation stability.

[0035] In order to overcome the limitation due to the anisotropic arrangement of cationic functional groups within a conventional anion exchange membrane, the inventors of the present invention have effectively manufactured an anion exchange membrane having an ion channel structure in which high-density cationic quaternary ammonium functional groups are uniformly arranged isotropically by using the Menshutkin polymerization reaction between a high-concentration polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent, thereby completing the present invention.

[0036]

[0037] Hereinafter, the present invention will be described in detail.

[0038]

[0039] Anion exchange membrane using single-liquid Menshkin polymerization reaction

[0040]

[0041] The present invention provides an anion exchange membrane comprising a porous support; and a quaternary ammonium polymer having a three-dimensional cross-linked structure formed on the support or filled inside the support, wherein the quaternary ammonium polymer is formed through a Menshkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0042]

[0043] The term "Menshkin polymerization" in this specification refers to a polymerization reaction in which a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer react to form a quaternary ammonium polymer. In this case, the quaternary ammonium polymer has a three-dimensional cross-linked structure.

[0044] The term "anion exchange membrane" in this specification refers to a separation membrane containing a cationic functional group, and is characterized by enabling selective transfer of anions in water electrolysis, electrolysis, fuel cells, electrodialysis, redox flow batteries, etc.

[0045] First, the anion exchange membrane according to the present invention includes a porous support, and the porous support may be a polyolefin resin or a fluorine resin, and the weight average molecular weight may be 10,000 g / mol to 5,000,000 g / mol, and the water contact angle may be 160° or less.

[0046] The porous support is intended to reinforce the mechanical strength of the formed quaternary ammonium polymer, and its thickness may be 1 ㎛ to 1,000 ㎛, preferably 10 ㎛ to 120 ㎛, and more preferably 20 ㎛ to 70 ㎛, but is not limited thereto. In addition, the average pore size of the porous support may be 1 nm to 100 ㎛, and preferably 10 nm to 1 ㎛, and more preferably 10 nm to 500 nm, but is not limited thereto. In addition, the porosity (space ratio) of the porous support may be 5% to 95%, and preferably 40% to 90%, and more preferably 80% to 90%, but is not limited thereto.

[0047] Specifically, the porous support is polyethylene, polypropylene, polymethylpentene, polybutene-1, ethylene propylene rubber, polyacetylene, polyisobutylene, polyethylene terephthalate, polyvinylchloride, polyvinylbenzylchloride, polyvinylfluoride, polyvinylidenefluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polyethersulfone, polysulfone, polyacrylonitrile, polystyrene, polyamide, It may include at least one selected from the group consisting of polydimethylsiloxane, polyvinyl alcohol, ethylene vinyl alcohol, polycarbonate, polybenzimidazole, polyvinylpyrrolidone, polyetherimide, polyetheretherketone, cellulose, and cellulose acetate.

[0048]

[0049] Optionally, the porous support can be imparted with hydrophilicity through hydrophilization treatment, thereby facilitating the formation of a quaternary ammonium polymer described below.

[0050] The hydrophilic treatment may be applied to a single side, double side, or inner surface of the porous support, and may be performed through one or more processes selected from the group consisting of organic coating, inorganic coating, ozone treatment, ultraviolet treatment, plasma, atomic layer deposition, chemical vapor deposition, and chemical oxidation treatment.

[0051] Specifically, the hydrophilic treatment of the porous support is performed by an organic coating method, and the organic coating method is selected from the group consisting of ethylene vinyl alcohol, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polydopamine, polyacrylic acid, polymethacrylic acid, polyetherimide, tannic acid, polyvinyl amine, poly(4-styrene sulfonic acid), poly(vinylsulfonic acid), polyethylenimine, polyaniline, polybenzimidazole, polyvinyl pyrrolidone, cellulose, and cellulose acetate. acetate), floxamer, floxamine, polyoxyethylene alkyl ether, polyoxyalkyl benzyl ether, polyoxyalkyl phenyl ether, polysorbate, sorbitan ester, alkyl ether surfate, alkyl benzene sulfonate, alkyl ammonium bromide, alkyl ammonium chloride,It may be a method for coating an organic material comprising at least one component selected from the group consisting of benzalkonium bromide and benzalkonium chloride. More specifically, the organic material coating method may be performed including a step of coating an organic material and then crosslinking the coated organic material. Through the hydrophilization treatment of the porous support, a material including a hydrophilic functional group such as a hydroxyl group, a carboxyl group, an ether group, or an amine group can be coated on the porous support.

[0052]

[0053] Next, the anion exchange membrane according to the present invention comprises a quaternary ammonium polymer having a three-dimensional cross-linked structure, and is characterized in that the quaternary ammonium polymer is formed on the support or filled inside the support.

[0054] The above quaternary ammonium polymer may be formed in the form of a uniform film on one side or both sides of the support, and may also be formed and filled inside the pores of the support.

[0055] The thickness of the above quaternary ammonium polymer may be 1 ㎛ to 1,000 ㎛, preferably 10 ㎛ to 120 ㎛, and more preferably 20 ㎛ to 70 ㎛, but is not limited thereto. The thickness and shape of the above quaternary ammonium polymer can be variously controlled by using a single-liquid Menshkin polymerization reaction.

[0056]

[0057] Meanwhile, the anion exchange membrane according to the present invention comprises a quaternary ammonium polymer having a three-dimensional cross-linked structure, and the quaternary ammonium polymer is characterized in that it is formed through a Menshkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0058] The above polyfunctional alkyl halide monomer has two or more alkyl halide groups. In addition, the polyfunctional alkyl halide monomer may have a weight average molecular weight of 50 g / mol to 1,000,000 g / mol. Specifically, the polyfunctional alkyl halide monomer is 1,3,5-tris(bromomethyl)benzene, 1,3,5-tris(chloromethyl)benzene, 1,3,5-tris(iodomethyl)benzene, 1,2-dibromoethane, 1,2-dichloroethane, 1,2-diiodoethane, 1,3-dibromopropane, 1,3-dichloropropane, 1,3-diiodopropane, 1,4-dibromobutane, 1,4-dichlorobutane, 1,4-diiodobutane, 1,6-dibromohexane, 1,6-dichlorohexane, 1,6-diiodohexane, 1,2-bis(bromomethyl)benzene, 1,2-bis(chloromethyl)benzene, 1,2-bis(iodomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,3-bis(iodomethyl)benzene, 1,4-bis(bromomethyl)benzene,1,4-bis(chloromethyl)benzene, 1,4-bis(iodomethyl)benzene, 1,4-bis(2-bromoethyl)benzene, 1,4-bis(2-chloroethyl)benzene, 1,4-bis(2-iodoethyl)benzene, 2,6-bis(bromomethyl)naphthalene, 2,6-bis(chloromethyl)naphthalene, It is preferable that at least one is selected from the group consisting of 2,6-bis(iodomethyl)naphthalene, 1,4-bis(1,2-dibromoethyl)benzene, 1,4-bis(1,2-dichloroethyl)benzene and 1,4-bis(1,2-diiodoethyl)benzene, but is not limited thereto.

[0059] The above polyfunctional tertiary amine monomer has two or more tertiary amine groups. In addition, the polyfunctional tertiary amine monomer may have a weight average molecular weight of 50 g / mol to 1,000,000 g / mol. At this time, in the polyfunctional tertiary amine monomer, when the tertiary amine group is included in a ring structure, high energy is required for the ring structure to be deformed and decomposed, so it is preferable in terms of alkaline stability, but is not limited thereto. Specifically, the polyfunctional tertiary amine monomer is 4,4'-trimethylenebis(1-methylpiperidine), N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris[2-(dimethylamino)ethyl]amine, Tris(dimethylamino)methane, tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethylhexamethylenediamine, 1,4-dimethylpiperazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacylcotetradecane, N,N,N',N'-tetramethyl-1,4-phenylenediamine, N,N,N',N'-tetramethyl-1,3-phenylenediamine, 1,4-bis(diphenylamino)benzene, 4,4'-bipyridyl, 4,4'-trimethylenedipyridine, hexamine, Preferably, at least one selected from the group consisting of altretamine, 2,4,6-tris(dimethylaminomethyl)phenol and polyethyleneimine, but is not limited thereto.

[0060] In particular, when one of the polyfunctional alkyl halide monomer and the polyfunctional tertiary amine monomer has two functional groups, it is preferable that the other one has three or more functional groups. For example, when the polyfunctional alkyl halide monomer has two alkyl halide groups, the polyfunctional tertiary amine monomer must have three or more tertiary amine groups to properly form a three-dimensional crosslinked structure. Conversely, when the polyfunctional tertiary amine monomer has two tertiary amine groups, the polyfunctional alkyl halide monomer must have three or more alkyl halide groups to properly form a three-dimensional crosslinked structure.

[0061] In the above single-liquid Menshkin polymerization reaction, the single-liquid phase is characterized in that it is based on a mixed solvent of a polar protic solvent and a polar aprotic solvent including a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer.

[0062] The mixed solvent for the above single-liquid Menshkin polymerization reaction is characterized by being optimized, and is characterized by being a mixed solvent of a polar protic solvent and a polar aprotic solvent containing a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer. As a result, the two monomers are dissolved at a high concentration, and an appropriate reaction rate between the high-concentration monomers is induced, while at the same time, the mixed solvent has a high affinity for the produced quaternary ammonium polymer, thereby enabling uniform film formation.

[0063] Specifically, the partition coefficient (LogP) value of the polar protic solvent included in the mixed solvent is preferably -2.00 or more, but is not limited thereto. At this time, the polar protic solvent may be composed of one or more solvents. The term "partition coefficient (LogP) value of the polar protic solvent" in the present specification means, when the polar protic solvent is composed of one solvent, the partition coefficient value of that solvent as it is, and, when the polar protic solvent is composed of two or more solvents, means an average value of the partition coefficient values ​​of each solvent in consideration of the volume ratio between each solvent. For example, the polar protic solvent may be water, glycerol, ethylene glycol, diethylene glycol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, acetic acid, formic acid, formamide, 2,2,2-trifluoroethanol, It is preferably at least one selected from the group consisting of lactic acid, phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, salicylic acid, benzyl alcohol, and 2-methoxyethanol, but is not limited thereto.

[0064] In addition, it is preferable that the dielectric constant value of the polar aprotic solvent included in the mixed solvent is 2.0 or more, but is not limited thereto. At this time, the polar aprotic solvent may be composed of one or more solvents, and the "dielectric constant value of the polar aprotic solvent" in the present specification means, when the polar aprotic solvent is composed of one solvent, the dielectric constant value of the solvent as it is, and when the polar aprotic solvent is composed of two or more solvents, it means an average value of the dielectric constant values ​​of each solvent in consideration of the volume ratio between each solvent.For example, the polar aprotic solvent may be 1,4-dioxane, butyl acetate, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, acetone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, acetonitrile, sulfolane, sulfolene, dimethyl sulfoxide, nitrometane, dimethyl carbonate, ethylene carbonate, propylene carbonate, It is preferably at least one selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dimethyl sulfate, hexamethylphosphoramide, dichloromethane, chloroform, nitrobenzene, methyl formate, and ethyl formate, but is not limited thereto.

[0065]

[0066] More specifically, i) when the mixed solvent is a combination of a polar protic main solvent (≥ 50 (v / v)%) and a polar aprotic secondary solvent (≤ 50 (v / v)%), the polar protic main solvent plays a main role and must have a high distribution coefficient in order to uniformly dissolve the polyfunctional alkyl halide monomer. Therefore, it is more preferable that the distribution coefficient value of the polar protic main solvent is -1.75 or more (preferably, -1.35 or more), and the dielectric constant value of the polar aprotic secondary solvent is 6.1 or more, but is not limited thereto. For example, the polar protic main solvent may include at least one selected from the group consisting of water, ethylene glycol, diethylene glycol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, acetic acid, formic acid, and formamide, and the polar aprotic secondary solvent may include at least one selected from the group consisting of tetrahydrofuran, acetone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide, nitromethane, ethylene carbonate, and propylene carbonate, but is not limited thereto.

[0067] ⅱ) When the above mixed solvent is a combination of a polar aprotic main solvent (> 50 (v / v)%) and a polar protic secondary solvent (< 50 (v / v)%), the polar aprotic main solvent plays a major role, and the dielectric constant value of the polar aprotic solvent must be maintained high in order to stabilize the charge of the quaternary ammonium polymer and prevent aggregation. Therefore, it is more preferable that the dielectric constant value of the polar aprotic main solvent be 5.1 or higher (preferably, 6.1 or higher), but is not limited thereto. For example, the polar aprotic main solvent may include at least one selected from the group consisting of ethyl acetate, tetrahydrofuran, acetone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, acetonitrile, sulfolane, dimethylsulfoxide, nitromethane, ethylene carbonate, and propylene carbonate, and the polar protic secondary solvent may include at least one selected from the group consisting of glycerol, water, ethylene glycol, diethylene glycol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, acetic acid, formic acid, and formamide, but is not limited thereto.

[0068] On the other hand, when both the main solvent and the secondary solvent are polar protic solvents, it has been confirmed that there is a problem in which the polyfunctional alkyl halide monomer cannot be dissolved at high concentrations. Furthermore, when both the main solvent and the secondary solvent are polar aprotic solvents, it has been confirmed that there is a limitation in which the excessively fast reaction rate leads to excessive nucleation, preventing the proper formation of a uniform film.

[0069]

[0070] Method for manufacturing an anion exchange membrane using a single-liquid Menshkin polymerization reaction

[0071]

[0072] The present invention provides a method for producing an anion exchange membrane, characterized by comprising the steps of: (a) preparing a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent including a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer; and (b) forming a quaternary ammonium polymer having a three-dimensional cross-linked structure on or inside a porous support through a Menshkin polymerization reaction in the single liquid phase.

[0073] Figure 1 schematically illustrates a method for producing a quaternary ammonium polymer and an anion exchange membrane with a three-dimensional cross-linked structure using a single-liquid Menshkin polymerization reaction according to one embodiment of the present invention.

[0074]

[0075] First, the method for manufacturing an anion exchange membrane according to the present invention includes a step [step (a)] of manufacturing a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent including a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer.

[0076] The single liquid phase based on the mixed solvent of the above-mentioned multifunctional alkyl halide monomer, the above-mentioned multifunctional tertiary amine monomer, and the above-mentioned polar protic solvent and polar aprotic solvent has been described above, so a redundant description will be omitted.

[0077] The above single liquid phase can be prepared by simultaneously or sequentially dissolving a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0078] Alternatively, the single liquid phase may be prepared by preparing a solution containing a polyfunctional alkyl halide monomer and a solution containing a polyfunctional tertiary amine monomer, respectively, and then mixing them. In this case, the single liquid phase obtained by mixing the respective solutions may be based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0079] The concentration of the polyfunctional alkyl halide monomer in the single liquid phase may be 2 (w / v)% to 40 (w / v)% (preferably, 7.5 (w / v)% to 15 (w / v)%). In addition, the concentration of the polyfunctional tertiary amine monomer in the single liquid phase may be 2 (w / v)% to 40 (w / v)% (preferably, 7.5 (w / v)% to 15 (w / v)%). In this way, by maintaining the concentrations of the polyfunctional alkyl halide monomer and the polyfunctional tertiary amine monomer in the single liquid phase at high concentrations, the quaternary ammonium functional group density of the produced quaternary ammonium polymer can be increased. By having a high quaternary ammonium functional group density, there is an advantage of being able to improve ionic conductivity.

[0080]

[0081] Next, the method for manufacturing an anion exchange membrane according to the present invention includes a step [step (b)] of forming a quaternary ammonium polymer having a three-dimensional cross-linked structure on or inside a porous support through a Menshkin polymerization reaction in the single liquid phase.

[0082]

[0083] The above single liquid phase can be impregnated into the porous support to perform a Menshkin polymerization reaction, and specifically, the Menshkin polymerization reaction in the above single liquid phase can be performed through a reaction at 10°C to 120°C for 1 minute to 5 hours (preferably, at 20°C to 60°C for 3 minutes to 2 hours).

[0084] If necessary, halogen ions (e.g., chlorine ions (Cl)) included in the manufactured anion exchange membrane - ), bromo ion (Br - ) and / or iodine ions (I - )) to hydroxide ion (OH -) can be exchanged. Specifically, by immersing the anion exchange membrane in a basic solution (e.g., sodium hydroxide, potassium hydroxide, etc.) containing hydroxide ions at a temperature of 10°C to 40°C for 10 minutes to 48 hours (preferably, 12 to 24 hours at 25°C), halogen ions (e.g., chlorine ions, bromo ions, and / or iodine ions) can be exchanged with hydroxide ions. Thus, it can be applied to a water electrolysis process. It can be omitted or changed in other processes that do not use hydroxide ions as counter ions.

[0085]

[0086] As reviewed above, the anion exchange membrane according to the present invention comprises a porous support; and a quaternary ammonium polymer having a three-dimensional cross-linked structure formed on the support or filled inside the support, wherein the quaternary ammonium polymer is characterized in that it is formed through a Menshkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0087] The anion exchange membrane according to the present invention has high ionic conductivity by forming an ion channel structure in which high-density cationic quaternary ammonium functional groups are uniformly arranged in an isotropic manner, and has high thermochemical stability due to its three-dimensional cross-linked structure. In particular, since the Menshkin polymerization reaction is carried out in a simple single liquid phase, it is easy to manufacture in large quantities and over a large area.

[0088] Therefore, the anion exchange membrane according to the present invention can be widely used in fields requiring selective transport of anions and thermochemical stability, such as water electrolysis, electrolysis, fuel cells, electrodialysis, and redox flow batteries.

[0089]

[0090] Hereinafter, preferred examples are presented to aid in understanding the present invention. However, the following examples are provided solely to facilitate a better understanding of the present invention, and the scope of the present invention is not limited by the following examples.

[0091]

[0092] [Example]

[0093] Preliminary Example 1: Solvent optimization for single-liquid Menshkin polymerization when each monomer concentration is 7.5 (w / v)%.

[0094] A single liquid phase was prepared by dissolving an alkyl halide monomer (1,3,5-tris(bromomethyl)benzene) at a concentration of 7.5 (w / v)% and a tertiary amine monomer (4,4'-trimethylenebis(1-methylpiperidine)) at a concentration of 7.5 (w / v)% in a mixed solvent having a volume ratio of 70:30 for the main solvent and the secondary solvent. Then, a Menshkin polymerization reaction was performed at 25 °C for 1 hour. Afterwards, the bromo ion generated by the Menshkin polymerization reaction was exchanged with hydroxide ion by immersing in a 1 M potassium hydroxide solution at 25 °C for more than 1 hour. At this time, the specific combination of the main solvent and the secondary solvent and the form of the product according to the single liquid Menshkin polymerization reaction are shown in Fig. 2.

[0095] As shown in Fig. 2, when both the main solvent and the secondary solvent are polar protic solvents, it is confirmed that there is a problem in which the 1,3,5-tris(bromomethyl)benzene monomer cannot be dissolved. In addition, when both the main solvent and the secondary solvent are polar aprotic solvents, it is confirmed that there is a limitation in which a uniform film is not properly formed due to excessive nucleation caused by an excessively fast reaction rate.

[0096] However, when a mixed solvent of a polar protic solvent and a polar aprotic solvent is used, uniform film formation is possible due to the high affinity with the quaternary ammonium polymer produced with an appropriate reaction rate.

[0097] At this time, the affinity of the mixed solvent with the quaternary ammonium polymer is determined by the partition coefficient (LogP) value of the polar protic solvent or the dielectric constant value of the polar aprotic solvent. The partition coefficient values ​​for each specific type of polar protic solvent are shown in Table 1, and the dielectric constant values ​​for each specific type of polar aprotic solvent are shown in Table 2.

[0098] Polar protic solvent partition coefficient (LogP) Glycerol (GC) - 1.76 Water (water) - 1.38 Ethylene glycol (EG) - 1.36 Diethylene glycol (DEG) - 1.00 Methanol (MeOH) - 0.82 Ethanol (EtOH) - 0.30 1-Propanol (1-PrOH) 0.25 1-Butanol (1-BuOH) 0.88

[0099] Polar aprotic solvent dielectric constant 1,4-dioxane 2.2 Butyl acetate 5.0 Ethyl acetate 6.0 Tetrahydrofuran 7.6 Acetone 20.7 Acetonitrile 35.9 Sulfolane 43.3 Dimethyl sulfoxide 46.7 Propylene carbonate 64.4

[0100] Meanwhile, when considering a case where each monomer concentration is a high concentration of 7.5 (w / v)%, and comprehensively considering Tables 1 and 2 along with FIG. 2, i) in the case of a mixed solvent of a polar protic main solvent and a polar aprotic secondary solvent, it can be seen that the distribution coefficient value of the polar protic main solvent is -1.75 or more (e.g., water, ethylene glycol, diethylene glycol, methanol, ethanol, 1-propanol, or 1-butanol), and the dielectric constant value of the polar aprotic secondary solvent is 6.1 or more (e.g., tetrahydrofuran, acetone, acetonitrile, sulfolane, dimethyl sulfoxide, or propylene carbonate), which is particularly preferable for uniform film formation. ⅱ) When the above mixed solvent is a mixed solvent of a polar aprotic main solvent and a polar protic secondary solvent, if the dielectric constant value of the polar aprotic main solvent is 5.1 or higher (e.g., ethyl acetate, tetrahydrofuran, acetone, acetonitrile, sulfolane, dimethyl sulfoxide or propylene carbonate), it can be considered particularly preferable for uniform film formation.

[0101]

[0102] Preliminary Example 2: Solvent optimization for single-liquid Menshkin polymerization when each monomer concentration is 10 (w / v)%.

[0103] A single-liquid Menshkin polymerization reaction was performed in the same manner as in Preliminary Example 1, except that the concentration of each monomer was changed to 10 (w / v)%. The specific combination of the main solvent and auxiliary solvent and the form of the product according to the single-liquid Menshkin polymerization reaction are shown in Fig. 3.

[0104] As shown in Fig. 3, when both the main solvent and the secondary solvent are polar protic solvents, it is confirmed that there is a problem in which the 1,3,5-tris(bromomethyl)benzene monomer cannot be dissolved. In addition, when both the main solvent and the secondary solvent are polar aprotic solvents, it is confirmed that there is a limitation in which a uniform film is not properly formed due to excessive nucleation caused by an excessively fast reaction rate.

[0105] As in Preliminary Example 1, when a mixed solvent of a polar protic solvent and a polar aprotic solvent is used, a uniform film can be formed due to the high affinity with the quaternary ammonium polymer produced with an appropriate reaction rate.

[0106] Meanwhile, when considering a case where each monomer concentration is an ultra-high concentration of 10 (w / v)%, comprehensively considering Tables 1 and 2 along with FIG. 3, i) in the case of a mixed solvent of a polar protic main solvent and a polar aprotic secondary solvent, it can be seen that the distribution coefficient value of the polar protic main solvent is -1.35 or more (e.g., diethylene glycol, methanol, ethanol, 1-propanol, or 1-butanol), and the dielectric constant value of the polar aprotic secondary solvent is 6.1 or more (e.g., tetrahydrofuran, acetone, acetonitrile, sulfolane, dimethyl sulfoxide, or propylene carbonate) is particularly preferable for uniform film formation. ⅱ) When the above mixed solvent is a mixed solvent of a polar aprotic main solvent and a polar protic secondary solvent, it can be considered particularly preferable for uniform film formation if the dielectric constant value of the polar aprotic main solvent is 6.1 or higher (e.g., tetrahydrofuran, acetone, acetonitrile, sulfolane, dimethyl sulfoxide or propylene carbonate).

[0107]

[0108] Example: Menshkin polymerization in a single liquid phase based on an optimal mixed solvent of a polar protic solvent and a polar aprotic solvent.

[0109] (1) Materials

[0110] -Porous support: A commercial porous Teflon membrane (Synopex) with a thickness of 40 μm was used as the porous support.

[0111] -Hydrophilic treatment material for porous support: Ethylene vinyl alcohol was used as a material for hydrophilic treatment of the porous support, and ethanol and water were used as solvents for dissolving this hydrophilic treatment material.

[0112] -Each monomer and optimal mixed solvent: 1,3,5-tris(bromomethyl)benzene was used as a polyfunctional alkyl halide monomer, 4,4'-trimethylenebis(1-methylpiperidine) was used as a polyfunctional tertiary amine monomer, 1-propanol (partition coefficient value = 0.25) was used as a polar protic main solvent, and dimethyl sulfoxide (dielectric constant value = 46.7) was used as an optimal mixed solvent.

[0113] (2) Manufacturing of anion exchange membrane

[0114] -Hydrophilic treatment of porous support: Ethylene vinyl alcohol was sufficiently dissolved at a concentration of 0.05 g / L in a solvent containing ethanol and water (70:30 by volume) at 50°C. A porous Teflon membrane was immersed in this solution for 4 hours. After immersion, the solution was washed with water to remove any remaining solution.

[0115] - Preparation of a single liquid phase: A mixed solvent with a volume ratio of 70:30, consisting of 1-propanol as a polar protic main solvent and dimethyl sulfoxide as a polar aprotic secondary solvent, was prepared. Here, 1,3,5-tris(bromomethyl)benzene monomer was dissolved at a concentration of 10 (w / v)%, and 4,4'-trimethylenebis(1-methylpiperidine) monomer was dissolved at a concentration of 10 (w / v)% to prepare a single liquid phase.

[0116] - Preparation of anion exchange membrane: A hydrophilic porous Teflon membrane was deposited on the prepared single solution. After removing excess solution from the surface of the porous support using a roller, Menshkin polymerization was performed for 1 hour at 25°C. Subsequently, the membrane was immersed in a 1 M potassium hydroxide solution at 25°C for more than 1 hour, thereby exchanging the bromo ions generated by the Menshkin polymerization reaction with hydroxide ions.

[0117]

[0118] Comparative example: Preparation of a commercial anion exchange membrane

[0119] - Comparative Example A: Fumatech's FAA-3-50 membrane was used.

[0120] - Comparative Example B: Dioxide Materials' X37-50 membrane was used.

[0121] - Comparative Example C: Versogen's PiperION membrane was used.

[0122]

[0123] [Experimental Example]

[0124] Experimental Example 1: Observation of the surface structure and cross-sectional structure of an anion exchange membrane.

[0125] The surface structure and cross-sectional structure of Example and Comparative Example A were confirmed using a scanning electron microscope, and are shown in Fig. 4.

[0126] As shown in Fig. 4, the anion exchange membrane manufactured in the example is confirmed to have a high-density surface structure and cross-sectional structure.

[0127]

[0128] Experimental Example 2: Observation of the polymer phase of an anion exchange membrane

[0129] The surface structure and polymer phase of Example and Comparative Example A were confirmed using an atomic force microscope, and are shown in Fig. 5.

[0130] As shown in Fig. 5, both Example A and Comparative Example A have a uniform surface structure, but it is confirmed that Example A forms a more uniform polymer phase than Comparative Example A. This is because, unlike Comparative Example A, which has an anisotropic structure, Example A has an isotropic structure.

[0131]

[0132] Experimental Example 3: Measurement of ion conductivity of an anion exchange membrane

[0133] The ionic conductivity of Examples A, B, and C was measured by electrochemical impedance spectroscopy in water at 25°C to 80°C using a potentiostat, and the results are shown in Fig. 6.

[0134] As shown in Fig. 6, the ionic conductivity of Examples A and C and Comparative Examples increased linearly as the temperature increased, but the ionic conductivity of Comparative Example B increased as the temperature increased and then decreased again. This is because Comparative Example B has poor stability at high temperatures. In addition, the Examples were confirmed to have higher ionic conductivity than Comparative Examples A, B, and C under all temperature conditions.

[0135]

[0136] Experimental Example 4: Evaluation of the Water Electrolysis Performance of an Anion Exchange Membrane

[0137] The electrolysis performance of Examples A, B, and C was evaluated by measuring the voltage according to the current density in a 1 M potassium hydroxide solution at 80°C, and the results are shown in Fig. 7.

[0138] Specifically, the reaction area is 4 cm 2A load cell capable of evaluating performance while maintaining a constant clamping pressure (100 kgf) was used, and a 1 M potassium hydroxide solution at 80°C was used as the electrolyte. As the electrode catalyst, a non-precious metal electrode catalyst for water electrolysis from Dioxide Materials (hydrogen generation electrode: nickel-iron-cobalt alloy (NiFeCo) at 2.0 mg cm -2 Electrode coated with , oxygen evolution electrode: nickel ferrite (NiFe2O4) 2.0 mg cm -2 (electrode coated with ) was used.

[0139] As shown in Fig. 7, it is confirmed that the embodiment shows a lower voltage value at the same current density compared to comparative examples A, B, and C. This means that the embodiment has a lower resistance (i.e., higher electrolysis efficiency) compared to comparative examples A, B, and C.

[0140]

[0141] Experimental Example 5: Thermochemical Stability of Anion Exchange Membranes

[0142] Example and Comparative Example A were immersed in a 1 M potassium hydroxide solution at 80°C for 1,000 hours, and the changes in surface structure and ionic conductivity according to the immersion time were observed to evaluate the thermochemical stability, which is shown in Figs. 8(a) and (b).

[0143] As shown in Figs. 8(a) and (b), the surface structure and ionic conductivity of the Example showed little change depending on the immersion time in a 1 M potassium hydroxide solution at 80°C, but the surface structure of Comparative Example A changed and the ionic conductivity gradually decreased as the immersion time increased. This means that the Example has superior thermochemical stability compared to Comparative Example A.

[0144]

[0145] Experimental Example 6: Long-term operating stability of an anion exchange membrane

[0146] The long-term operation stability was evaluated by measuring the voltage change over time while operating the example for 1,000 hours, and the results are shown in Fig. 9.

[0147] Specifically, a 1 M potassium hydroxide solution at 60°C was used as the electrolyte during electrolysis, and a constant current density (1.0 A cm -2 ) was applied, and the voltage change over time was measured.

[0148] As shown in Fig. 9, it was confirmed that there was no significant voltage change while the embodiment was operated for 1,000 hours, which means that the embodiment has high long-term operation stability.

[0149]

[0150] The foregoing description of the present invention is for illustrative purposes only. Those skilled in the art will readily appreciate that modifications to other specific embodiments can be made without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. Porous support; and A quaternary ammonium polymer having a three-dimensional cross-linked structure formed on the support or filled inside the support, An anion exchange membrane characterized in that the above quaternary ammonium polymer is formed through a Menshutkin polymerization reaction between a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer in a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent.

2. In paragraph 1, The porous support is polyethylene, polypropylene, polymethylpentene, polybutene-1, ethylene propylene rubber, polyacetylene, polyisobutylene, polyethylene terephthalate, polyvinylchloride, polyvinylbenzylchloride, polyvinylfluoride, polyvinylidenefluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polyethersulfone, polysulfone, polyacrylonitrile, polystyrene, polyamide, An anion exchange membrane characterized by comprising at least one selected from the group consisting of polydimethylsiloxane, polyvinyl alcohol, ethylene vinyl alcohol, polycarbonate, polybenzimidazole, polyvinylpyrrolidone, polyetherimide, polyetheretherketone, cellulose, and cellulose acetate.

3. In paragraph 1, An anion exchange membrane, characterized in that the porous support is hydrophilic treated.

4. In paragraph 3, An anion exchange membrane, characterized in that the hydrophilic treatment of the porous support is performed by at least one method selected from the group consisting of organic coating, inorganic coating, ozone treatment, ultraviolet treatment, plasma, atomic layer deposition, chemical vapor deposition, and chemical oxidation treatment.

5. In paragraph 3, The hydrophilic treatment of the above porous support is performed by an organic coating method, and the organic coating method comprises ethylene vinyl alcohol, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polydopamine, polyacrylic acid, polymethacrylic acid, polyetherimide, tannic acid, polyvinyl amine, poly(4-styrene sulfonic acid), poly(vinylsulfonic acid), polyethylenimine, polyaniline, polybenzimidazole, polyvinyl pyrrolidone, cellulose, cellulose acetate, Ploxamer, ploxamine, polyoxyethylene alkyl ether, polyoxyalkyl benzyl ether, polyoxyalkyl phenyl ether, polysorbate, sorbitan ester, alkyl ether surfate, alkyl benzene sulfonate, alkyl ammonium bromide, alkyl ammonium chloride,An anion exchange membrane characterized by a method for coating an organic material comprising at least one component selected from the group consisting of benzalkonium bromide and benzalkonium chloride.

6. In paragraph 5, An anion exchange membrane, characterized in that the organic coating method is performed including a step of coating an organic material and then crosslinking the coated organic material.

7. In paragraph 1, An anion exchange membrane, characterized in that the above multifunctional alkyl halide monomer has two or more alkyl halide groups and has a weight average molecular weight of 50 g / mol to 1,000,000 g / mol.

8. In paragraph 1, The above multifunctional alkyl halide monomers are 1,3,5-tris(bromomethyl)benzene, 1,3,5-tris(chloromethyl)benzene, 1,3,5-tris(iodomethyl)benzene, 1,2-dibromoethane, 1,2-dichloroethane, 1,2-diiodoethane, 1,3-dibromopropane, 1,3-dichloropropane, 1,3-diiodopropane, 1,4-dibromobutane, 1,4-dichlorobutane, 1,4-diiodobutane, 1,6-dibromohexane, 1,6-dichlorohexane, 1,6-diidohexane, 1,2-bis(bromomethyl)benzene, 1,2-bis(chloromethyl)benzene, 1,2-bis(iodomethyl)benzene, 1,3-bis(bromomethyl)benzene, 1,3-bis(chloromethyl)benzene, 1,3-bis(iodomethyl)benzene, 1,4-bis(bromomethyl)benzene, 1,4-bis(chloromethyl)benzene, 1,4-bis(iodomethyl)benzene, 1,4-bis(2-bromoethyl)benzene(1,4-bis(2-bromoethyl)benzene), 1,4-bis(2-chloroethyl)benzene, 1,4-bis(2-iodoethyl)benzene, 2,6-bis(bromomethyl)naphthalene, 2,6-bis(chloromethyl)naphthalene, 2,6-bis(iodomethyl)naphthalene, 1,4-bis(1,2-dibromoethyl)benzene, An anion exchange membrane characterized by at least one selected from the group consisting of 1,4-bis(1,2-dichloroethyl)benzene and 1,4-bis(1,2-diiodoethyl)benzene.

9. In paragraph 1, An anion exchange membrane, characterized in that the above-mentioned polyfunctional tertiary amine monomer has two or more tertiary amine groups and has a weight average molecular weight of 50 g / mol to 1,000,000 g / mol.

10. In paragraph 1, The above polyfunctional tertiary amine monomers are 4,4'-trimethylenebis(1-methylpiperidine), N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, tris[2-(dimethylamino)ethyl]amine, Tris(dimethylamino)methane, tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N,N',N'-tetramethylhexamethylenediamine, 1,4-dimethylpiperazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacylcotetradecane, N,N,N',N'-tetramethyl-1,4-phenylenediamine, N,N,N',N'-tetramethyl-1,3-phenylenediamine, 1,An anion exchange membrane characterized by at least one selected from the group consisting of 1,4-bis(diphenylamino)benzene, 4,4'-bipyridyl, 4,4'-trimethylenedipyridine, hexamine, altretamine, 2,4,6-tris(dimethylaminomethyl)phenol, and polyethyleneimine.

11. In paragraph 1, An anion exchange membrane characterized in that the distribution coefficient (LogP) value of the polar protic solvent is -2.00 or more, and the dielectric constant value of the polar aprotic solvent is 2.0 or more.

12. In paragraph 1, The polar protic solvents are water, glycerol, ethylene glycol, diethylene glycol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, acetic acid, formic acid, formamide, 2,2,2-trifluoroethanol, lactic acid. acid), phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, salicylic acid, benzyl alcohol and 2-methoxyethanol, wherein the polar aprotic solvent comprises at least one selected from the group consisting of 1,4-dioxane, butyl acetate, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, acetone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Acetonitrile, sulfolane, sulfolene,An anion exchange membrane characterized by comprising at least one selected from the group consisting of dimethyl sulfoxide, nitrometane, dimethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dimethyl sulfate, hexamethylphosphoramide, dichloromethane, chloroform, nitrobenzene, methyl formate, and ethyl formate. 13.(a) A step of preparing a single liquid phase based on a mixed solvent of a polar protic solvent and a polar aprotic solvent including a polyfunctional alkyl halide monomer and a polyfunctional tertiary amine monomer; and (b) A method for manufacturing an anion exchange membrane, characterized by including a step of forming a quaternary ammonium polymer having a three-dimensional cross-linked structure on or inside a porous support through a Menshkin polymerization reaction in the single liquid phase.

14. In paragraph 13, A method for manufacturing an anion exchange membrane, characterized in that in the step (a), the concentration of the polyfunctional alkyl halide monomer in the single liquid phase is 2 (w / v)% to 40 (w / v)%, and the concentration of the polyfunctional tertiary amine monomer in the single liquid phase is 2 (w / v)% to 40 (w / v)%.

15. In paragraph 13, A method for producing an anion exchange membrane, characterized in that the Menshkin polymerization reaction in the single liquid phase of the above step (b) is carried out at 10°C to 120°C for 1 minute to 5 hours.

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