KR20170113232A - Method of manufacturing ion-exchange membrane and ion-exchange membrane produced by the same method - Google Patents

Abstract

The present invention relates to a method for preparing a polymer electrolyte membrane, comprising the steps of: (a) treating a basement membrane with a swelling solution to increase a distance between polymer chains of a hydrophilic region or a hydrophobic region of the basement membrane; (b) applying a solution containing a monomer having an ion exchanger to the swollen base film to perform a polymerization reaction; And (c) stabilizing the basement membrane into which the ion exchanger has been introduced by treating it with a swollen solution to stabilize the ion exchange membrane. The present invention also relates to an ion exchange membrane prepared by the method. , It is possible to provide an ion exchange membrane having improved ion exchange performance and improved chemical stability and mechanical stability.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ion exchange membrane,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing an ion exchange membrane and an ion exchange membrane manufactured thereby, and a new ion exchange system can be introduced into a conventional ion exchange membrane to selectively perform an ion exchange function. An ion exchange membrane having improved stability can be obtained.

The ion exchange membrane refers to a polymer film that selectively passes anions or cations. Ion exchange membranes are classified into cation exchange membranes and anion exchange membranes depending on surface charge characteristics. The cation exchange membrane has negatively charged functional groups, which pass only positive ions by electrical attraction, and block the movement of negative ions by electrical repulsion. In addition, the anion exchange membrane has a positively charged functional group, and moves the anion by electrical attraction and blocks the movement of the cation by an electrical repulsive force.

The above-described ion exchange membrane is applied to various fields such as fuel cell, diffusion dialysis, desalination of sea water, electrolysis of water, and brine electrolysis. Particularly, the ion exchange membrane used in the field of fuel cells includes a fluorine-based cation exchange membrane, a hydrocarbon-based membrane, and a partially fluorinated cation exchange membrane.

The fluorine-based cation exchange membrane, which is widely used and commercially available, has fluorinated alkylene in the main chain and a sulfonic acid group at the end of the side chain. As the thickness increases, the dimensional stability and mechanical properties are improved, but the film resistance is increased. On the contrary, when the thickness is reduced, the resistance is lowered but the mechanical properties are deteriorated and there is a problem that the performance of the battery is deteriorated due to the loss of the fuel.

In order to solve this problem, a method of coating an ion exchange solution on a base film or a support is proposed. Korean Patent Laid-Open Publication No. 2014-0126199 discloses a method for preparing an ion exchange membrane by immersing a porous substrate in a monomer mixture liquid to prepare a base membrane and coating the polymer base coat on the prepared base membrane.

In this patent, monomers are first immersed in a porous substrate to form a basement membrane first. Thereafter, the polymer is immersed in a polymer solution having an anion exchanger or a cation exchanger to coat the polymer. Further, the polymer mixture solution having an ion exchanger has an aspect in which it is fixed to the basement membrane through photo-crosslinking or thermal crosslinking. Since the impregnation method is used in the patent, the thickness control of the polymer including the ion exchanger at the time of coating can be changed according to conditions, and is not suitable for mass production. Also, since the surface coating method is used, the lifetime of the ion exchange membrane may become a problem in terms of reliability. That is, an ion exchanger existing only in a crosslinked state on the surface may deteriorate the bonding structure or deteriorate the characteristics due to continuous use in a fuel cell or the like.

Korean Patent Publication No. 2012-0059585 discloses a method for producing an ion exchange membrane having a thin thickness by using a porous substrate as a base membrane. Korean Patent Publication No. 2012-0057750 discloses a specific polymer having a cation exchanger or anion exchanger Discloses a method for producing an ion exchange membrane having improved mechanical properties for ion exchange by coating it on a carbon material electrode.

However, since such a polymer material is applied to a general carbon material electrode, when it is used for the surface coating of an ion exchange membrane using a porous substrate as a base film, it can not provide an optimum effect and is difficult to apply to an actual process .

Korean Patent Publication No. 2014-0126199 Korea Patent Publication No. 2012-0059585 Korea Patent Publication No. 2012-0057750

Disclosure of Invention Technical Problem [8] The present invention provides a method for preparing an ion exchange membrane having improved chemical stability and mechanical stability, which can improve ion exchange performance by introducing an optional ion exchanger through a simple process, and a method for producing an ion exchange membrane .

 In order to solve the above-mentioned problems, the present invention provides a method for manufacturing a polymer electrolyte membrane, comprising the steps of: (a) treating a basement membrane with a swelling solution to increase a distance between polymer chains in a hydrophilic region or a hydrophobic region of the basement membrane; (b) applying a solution containing a monomer having an ion exchanger to the swollen base film to perform a polymerization reaction; And (c) treating the basement membrane into which the ion exchanger has been introduced by treating it with a swollen solution to stabilize the ion exchange membrane, and an ion exchange membrane produced thereby. At this time, the monomer having an ion-exchange group used in the present invention may be a functional group containing an ethylenic unsaturated bond, a hydroxyl group, an amino group, an amino group, an amide group, a carboxyl group, a sulfuric acid group, a carbonic acid group, a phosphoric acid group, a tosyl group and an aldehyde group Or more of the reactive functional groups.

According to the present invention, various ion exchangers can be introduced into the swollen base membrane, and a stronger chemical stability can be maintained. In particular, since in-situ polymerization of various ion-exchange groups is carried out from the inside of the swollen basement membrane, electrochemical stability can be improved by forming a uniform coating layer, Stability and chemical stability can be secured.

1 is a transmission electron microscope (TEM) photograph of an ion exchange membrane according to Example 1 of the present invention.
FIG. 2 is a graph showing the chemical durability of an ion exchange membrane prepared according to Examples and Comparative Examples of the present invention. FIG.
FIG. 3 is a graph showing sodium ion conduction characteristics of ion exchange membranes prepared at different thicknesses according to Examples and Comparative Examples of the present invention. FIG.
4 is a graph showing current-voltage characteristics of an ion exchange membrane manufactured according to an embodiment of the present invention and a comparative example.
FIG. 5 is a graph showing electrochemical long term durability through the application of a constant current to the ion exchange membranes prepared according to Examples and Comparative Examples of the present invention. FIG.
FIG. 6 is a graph showing electrochemical characteristics of an RED system using an ion exchange membrane manufactured according to an embodiment of the present invention and a comparative example.

Hereinafter, the present invention will be described in more detail with reference to examples and drawings.

The method for preparing an ion exchange membrane according to the present invention comprises the steps of: (a) treating a basement membrane with a swelling solution to increase the interval between polymer chains in a hydrophilic region or a hydrophobic region of the basement membrane; (b) applying a solution containing a monomer having an ion exchanger to the swollen base film to perform a polymerization reaction; And (c) treating the basement membrane into which the ion exchanger has been introduced by treatment with a swelling solution to stabilize the basement membrane.

As the fluorine-based base membrane which can be used in the present invention, a copolymer of tetrafluoroethylene and fluorovinyl ether containing poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid) sulfonic acid group, And examples of usable hydrocarbon base membranes include sulfonated polyimide, sulfonated polyaryl ether sulfone, sulfonated polyether ether ketone, sulfonated polybenzimidazole, sulfonated polysulfone, sulfonated polystyrene, Sulfonated polyether ether sulfone, sulfonated polyether sulfone, sulfonated polyether benzimidazole, sulfonated polyarylene ether ketone, sulfonated polyether ketone, sulfonated polystyrene, sulfonated polyimide , Sulfonated polyether ketone ketone, polyaryl ether benzimidazole, and combinations thereof. It may include subtitles. Commercially available products include, but are not limited to, Nafion, Asiflex, Plemion, Dow ionomer, Solvay ionomer, 3M ionomer, and the like.

Also, as a solution for the swelling action, a first swelling solution for increasing the spacing between the polymer chains in the hydrophilic region, a second swelling solution for increasing the spacing between the polymer chains in the hydrophobic region, or a mixture thereof may be used. The first swelling solution may be, for example, water, methanol, ethanol, n-propanol, isopropanol or a mixture thereof. The second swelling solution may be toluene, xylene, benzene, ethylbenzene, .

In the present invention, it is preferable to mix the first swelling solution and the second swelling solution in order to enhance the swelling effect of the basement membrane. When the mixture of the first swelling solution and the second swelling solution is used as the swelling solution, the base membrane can be more effectively swelled by sequentially subjecting the base membrane to surface treatment while changing the mixing ratio of the first swelling solution and the second swelling solution. In addition, even when the basement membrane into which the ion exchanger is introduced is treated and stabilized by the swelling solution, a better ion exchange membrane can be obtained by varying the mixing ratio of the first swelling solution and the second swelling solution.

Next, the polymerization reaction is induced to introduce the ion exchanger into the swollen base membrane. For the polymerization according to the present invention, a solution containing a monomer having an ion-exchange group is used. The monomer having an ion-exchange group that can be used in the present invention is a polymer having a functional group containing an ethylenic unsaturated bond and at least one reactive group selected from a hydroxyl group, an amine group, an amino group, an amide group, a carboxyl group, a sulfuric acid group, a carbonic acid group, Functional group.

The monomers containing an amine group include all primary amines, secondary amines, tertiary amines, aromatic amines, and heterocyclic amines. Specific examples thereof include N, N-dimethylaniline, pyridine, DABCO (1,4- Diazabicyclo [2.2.2] octane, DMAP (4-Dimethylaminopyridine), trimethylamine, triethylamine, Hunig's base (N, N-Diisopropylethylamine), DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene ), Guanidine Base (Barton Base), Phosphazene Base (Verkade Base, Schwesinger Base). In addition, sulfide, phosphine and the like can be used.

Further, acrylic monomer, methacrylic monomer and olefin monomer can be used, and examples thereof include acrylic acid, methacrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl (Meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanate (Meth) acrylate, triethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, (Meth) acrylates such as methylene propane tri (meth) acrylate, trimethylene propane triacrylate, 1,3-butanediol (meth) acrylate, 1,6- 6-hexadiene, 1,4-butadiene, 2-hydroxy (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate, styrene, alpha methyl styrene, fluorostyrene, vinyl pyridine, acrylonitrile, methacrylonitrile, butyl acrylate, Ethylhexyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, 2-ethylhexylethyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, Acrylate, 1,6-hexane diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate Propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, amyl acrylate, dodecyl acrylate Acrylate, benzyl acrylate, phenyl acrylate, hydroxyphenyl acrylate, chlorophenyl acrylate, sulfamoyl phenyl acrylate, 2- (hydroxyphenylcarbamoylphenyl) acrylate, Butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl acrylate.

In the present invention, the solution containing the monomer used for the polymerization reaction may further include a crosslinking agent, a catalyst for reaction, a radical initiator, a solvent, and the like. At this time, the content of the monomer contained in the polymerization solution is preferably 5 to 80% by weight, and it is difficult to produce a crosslinked polymer having a uniform thickness when irradiated with UV at 5% by weight or less.

The crosslinking agent, the reaction catalyst, the radical initiator and the solvent which can be used in the present invention can be used without limitation as long as they are usually used in the polymerization reaction. Specifically, the crosslinking agent includes divinyl sulfone, divinyl sulfoxide, butadiol divinyl ether, (Ethylene glycol) vinyl ether, and vinyl acrylate. Examples of the reaction catalyst include benzoyl peroxide, acetyl peroxide, potassium persulfate, dilauryl peroxide, ditetrabutyl peroxide and the like. . The photoinitiator may also be acylphosphine oxide, (1-hydroxycyclohexyl) phenylmethanone, (1-hydroxycyclohexyl) phenylketone, 2-hydroxy- (2-hydrohexyl-2-methylpropyl) ketone, and the like. Examples of the solvent include water, methanol, isopropyl alcohol and normal propanol. The content of the crosslinking agent, the reaction catalyst, the radical initiator and the solvent contained in the polymerization solution is preferably 2 to 30% by weight, 2 to 30% by weight, 2 to 30% by weight and 20 to 90% by weight, When the amount of the radical initiator is less than 2% by weight, the radical reaction by UV irradiation is not smoothly performed, and it is difficult to form a crosslinked polymer electrolyte membrane.

The method of applying the monomer-containing solution to the base film may be selected from a spray coating method, an impregnation method, a casting method, and a brush method, but is not limited thereto.

After the solution containing the monomer, the crosslinking agent, the catalyst, the radical initiator and the solvent is applied to the swollen base film, the polymerization reaction of the monomer is induced to introduce the ion exchanger into the base film. The photopolymerization reaction can be carried out by irradiating UV rays using a UV irradiation apparatus generally used in the case of the photocuring method.

Next, a step of stabilizing the basement membrane into which the ion exchanger has been introduced through the polymerization reaction is processed again as a swollen solution. At this time, the solution used for the stabilization can be used in a different swelling solution or mixing ratio used for the surface treatment of the basement membrane, and the swollen basement membrane can be stabilized and unreacted at the surface of the basement membrane can be removed.

According to the method for producing an ion exchange membrane of the present invention, a polymer membrane having a cation or anion exchange property is polymerized and stabilized in a state of being permeated into a base membrane, and thereby a stable multilayer ion exchange membrane can be produced without being separated from the surface of the base membrane . Also, it can be confirmed that various ion exchange groups can be introduced into the polymer membrane according to the production method of the present invention, and mass production of the ion exchange membrane using the coating process is possible.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the following examples are provided to illustrate the present invention and should not be construed as limiting the scope of the present invention.

≪ Example 1 >

Nafion 212 membranes with a thickness of 50 um were prepared as the base membrane used for the preparation of the ion exchange membrane. The basement membrane was cleaned with ultrapure water and methanol and dried naturally to remove contaminants or foreign substances that could adhere to the surface of the basement membrane. Four types of swelling solutions were also prepared in which methanol and toluene were 67:33 (primary), 100: 0 (secondary), 33:67 (tertiary) and 0: 100 Prepared. Methanol swells the hydrophilic region of the basement membrane, and toluene swells the hydrophobic region of the basement membrane. Each of the four mixed solutions was stored in a glass container.

(A) swelling the surface of the basement membrane using (a) a swelling solution, the basement membrane is fixed to a glass container containing a mixed solution of methanol and toluene in a ratio of 67:33, and the surface of the basement membrane is shaken for 12 hours with a shaker After the treatment, the surface treatment was repeated by replacing the mixed solution at a ratio of 100: 0.

When primary and secondary surface treatments were carried out with a mixed solution of methanol and toluene at a volume ratio (vol%) of 67:33 and 100: 0, the ratio of hydrophilic and hydrophobic solution The swelling action progresses at a slower rate, stabilizing the basement membrane and inducing the polymer chain spacing of the basement membrane to increase at a slow rate. In the second surface treatment, the polymer chain is swollen at a high speed due to the hydrophilic solution. Loses. This allowed the hydrophilic and hydrophobic regions of the basement membrane to swell and provide an environment for the introduction of monomers with ion exchangers.

Then, (b) applying a solution containing a monomer having an ion exchanger to the swollen base film to carry out a polymerization reaction was proceeded as follows. Acrylic acid (C ₃ H ₄ O ₂ ) serving as a monomer and divinylbenzene (C ₁₀ H ₁₀ ) serving as a crosslinking agent were prepared in a weight ratio of 1: 1 and stirred at 80 ^° C for 12 hours to prepare a mixed solution . Then, 5 wt% of azobisisobutyronitrile (C ₈ H ₁₂ N ₄ ) serving as a catalyst and 2 wt% of benzoin isobutyl ether serving as a photoinitiator ) (C ₈ H ₂₀ O ₂ ) was added thereto, and the mixture was stirred for 5 minutes. Finally, ethanol (C ₂ H ₅ OH) as a solvent was added to dilute the concentration five times. Through this process, a mixed solution for the polymerization reaction was prepared.

Then, through a spray coating the mixed solution on the base film surface Nafion 212 swell cm ² . The basement membrane containing the applied mixed solution was exposed to the air for 15 minutes at room temperature to absorb a portion of the polymer solution into the swollen basement membrane. Subsequently, the base film was placed in an ultraviolet irradiator having an irradiation intensity of about 1000 W and irradiated for 30 minutes to 12 hours.

The step of treating the basement membrane into which the ion exchanger was introduced through the polymerization reaction with the swollen solution to stabilize the solution was carried out as follows. The irradiated basement membrane was subjected to the same experimental conditions as in the above step (a) by using a swelling solution having a volume ratio (vol%) of methanol and toluene of 33:67 and 0: 100 in a stepwise manner. When the surface treatment is carried out in a tertiary or quaternary stepwise manner with a mixed solution of methanol and toluene at a volume ratio (vol%) of 33:67 and 0: 100, the first and second surface treatments of step (a) The swollen basement membrane induces the polymer chain spacing of the basement membrane to decrease at a slow rate by the ratio of the hydrophilic and hydrophobic solution. In the fourth surface treatment, since the hydrophobic solution only consists of the base membrane, the polymer chain spacing is rapidly reduced, A separate, stabilized multilayer ion exchange membrane can be produced.

Since the ion exchange membrane manufactured through the above process uses a Nafion 212 as a base membrane, a polymer membrane having a sulfate group (-SO ₃ H) in the bulk region and a carbonic acid group (-COOH) is formed on the surface of the ion exchange membrane. .

≪ Example 2 >

An ion exchange membrane was prepared in the same manner as in Example 1, except that the monomer charged into the mixed solution for polymerization was changed to methyl methacrylate (C ₅ H ₈ O ₂ ).

≪ Example 3 >

An ion exchange membrane was prepared in the same manner as in Example 1, except that the monomer charged into the mixed solution for polymerization was changed to butyl methacrylate (C ₈ H ₁₄ O ₂ ).

<Example 4>

The mixed solution for the polymerization 3.2mg per cm ² was prepared, except that the coating by spray coating in Example 1 and the ion exchange membrane in the same manner.

&Lt; Example 5 >

An ion exchange membrane was prepared in the same manner as in Example 1, except that 9.6 mg per cm ² of the mixed solution for polymerization was applied by spray coating.

&Lt; Example 6 >

An ion exchange membrane was prepared in the same manner as in Example 1, except that the membrane was used as a commercial Nafion 211 base membrane having a thickness of 25 mu m available from DuPont.

&Lt; Example 7 >

An ion exchange membrane was prepared in the same manner as in Example 1, except that a commercially available Selemion DSV having a thickness of 140 탆 commercially available from Asahi Glass Co., Ltd. was used as a base film and a monomer having a sulfonic acid salt was used as a mixed solution for polymerization reaction.

&Lt; Example 8 >

An ion exchange membrane was prepared in the same manner as in Example 1, except that a 45 mu m-thick bisphenol A-based hydrocarbon separator membrane was used as the base membrane.

&Lt; Example 9 >

An ion exchange membrane was prepared in the same manner as in Example 4, except that a 45 mu m-thick bisphenol A-based hydrocarbon separator membrane was used as the base membrane.

&Lt; Comparative Example 1 &

A commercially available Nafion 212 pure electrolyte membrane having a thickness of 50 mu m commercially available from DuPont was used.

&Lt; Comparative Example 2 &

A commercially available asiflex composite membrane having a thickness of 268 mu m and commercially available from Asahi Kasei Co., Ltd. was used.

&Lt; Comparative Example 3 &

A commercially available fumed film base film having a thickness of 125 mu m commercially available from Fuji Film Co., Ltd. was used.

<Experimental Example>

<Transmission electron microscope photograph>

1 shows a transmission electron microscope (TEM) photograph of Example 1. Fig. The sulfate group (-SO ₃ ^- ) on the S-layer and the carbonate group (-COO ^- ) on the C-layer which are charged with anions are displayed in black through LiCl staining. Due to the difference in the internal distribution of the corresponding functional groups, It is possible to visually confirm that the film is effectively formed.

<Chemical Durability>

FIG. 2 is a graph showing a change in crosslinking rate according to chemical resistance characteristics of an ion exchange membrane prepared according to Examples and Comparative Examples. FIG. The electrolyte membranes prepared in the conditions of Example 1, Example 2 and Example 3 were immersed in a 30 wt.% NaOH solution and reacted at 90 ^° C. for 48 hours. Each electrolyte membrane was cleaned in ultrapure water and then dried in a drying oven at 60 ^° C. C, for 24 hours, and the crosslinking rate was calculated based on the change of the dry weight from the initial value. According to the results, it can be seen that the ion exchange membrane prepared according to the embodiment of the present invention has an excellent chemical durability as compared with the emulsion-based commercialized ion exchange membrane as in the comparative example.

&Lt; Sodium ion conductivity &

3 is a graph showing the sodium ion conductivity of the ion exchange membranes prepared according to Examples and Comparative Examples. The sodium ion conductivity was calculated by measuring the ohmic resistance or the bulk resistance using the four point probe AC impedance spectroscopic method and calculating the sodium ion conductivity according to the following equation (1).

 [Equation 1]

σ = L / RS

L is the distance (cm) between the electrodes, S is the area (cm 2) of the electrolyte in which a constant current flows, and S is the surface area of the electrolyte. ]

As shown in FIG. 3, the ion-exchange membranes prepared according to Example 1, Example 4 and Example 5 of the present invention have increased resistance through thickness control (about 1.6-45 μm) according to the amount of C-layer introduced , And Na ⁺ ion conductivity were changed. Na ⁺ when compared to the ion conductive property sulfuric acid group (-SO ₃ ^-) are jinyeo a high pH (acidity) in the hydrated state easily dissociated Na ⁺ ions passing through the S-layer which contains a relatively low pH (acidity ( ^- COO ^- ) with a carbonyl group ( ^- ). In comparison with the ionomer membrane of comparative example 2 based on the commercialized ionomer, it can be confirmed that the ion exchange membrane according to the present invention has a superior sodium ion conduction characteristic than the conventional membrane through the control of the thickness through the change of the introduction amount of the ion exchanger . These results confirm that the same tendency is observed as in Example 8 and Example 9 when introduced into a hydrocarbon-based base film as well as a fluorine based base film.

&Lt; Voltage and current application characteristics &

4 is a graph showing current-voltage characteristics of an ion-exchange membrane manufactured according to Comparative Examples and Examples. The ion exchange membrane prepared under the conditions of Example 1 was immersed in a 30 wt% NaOH solution and a 25 wt% NaCl solution under the CA driving conditions at a flow rate of 90 ^o C and a flow rate of 25 ml / min using VMP3B-20 (Biologic, France) lt; ² &gt; / cm &lt; ² &gt; As a result, it was confirmed that the ion exchange membrane prepared according to the embodiment of the present invention had better current voltage characteristics than Comparative Example 2, which is a commercial CA ion exchange membrane.

<Electrochemical durability through application of constant current>

The electrochemical durability of the ion exchange membranes prepared according to Examples and Comparative Examples was confirmed by applying a constant current. The electrochemical durability characteristics were confirmed by applying a constant current of 0.2 A / cm &lt; ² &gt; for 120 days in the same experimental manner as the voltage and current application characteristics. According to these results, it was confirmed that the ion exchange membrane manufactured according to the embodiment of the present invention is superior in electrochemical durability compared with the emulsion polymerization based commercialized ion exchange membrane, even though it is operated for a long period of time there was. Therefore, it is expected that the durability can be secured by increasing the chemical durability according to the use of the crosslinked polymer for preparing the C-layer of the present invention and by changing the properties of the intermolecular or intramolecular crosslinked polymer.

<Electrochemical characteristics through application of RED system>

The electrochemical characteristics of the RED system using the anion exchange membranes prepared according to Examples and Comparative Examples were confirmed. The electrochemical characteristics of the RED system using a commercially available anion exchange membrane and an anion exchange membrane prepared according to Example 7 were measured at a flow rate of 400 ml / min at intervals of 50 ml / min. According to the results, it was confirmed that the ion exchange membrane prepared according to the embodiment of the present invention is superior in electrochemical characteristics to the commercial anion exchange membrane like Comparative Example 3.

Claims (14)

(a) surface treatment of the basement membrane with a swelling solution to increase the spacing between the polymer chains of the hydrophilic region or the hydrophobic region of the basement membrane;
(b) applying a solution containing a monomer having an ion exchanger to the swollen base film to perform a polymerization reaction; And
(c) stabilizing the basement membrane into which the ion exchanger has been introduced by treating it with a swollen solution. The method according to claim 1,
The monomer having an ion-exchange group includes at least one functional group containing an ethylenically unsaturated bond, at least one reactive functional group selected from a hydroxyl group, an amine group, an amino group, an amide group, a carboxyl group, a sulfuric acid group, a carbonic acid group, Wherein the ion-exchange membrane is a membrane. 3. The method of claim 2,
Wherein the monomer containing an amine group is at least one selected from the group consisting of a primary amine, a secondary amine, a tertiary amine, an aromatic amine, and a heterocyclic amine. 3. The method of claim 2,
Wherein the monomer having an ion exchange group is at least one selected from the group consisting of an acrylic monomer, a methacrylic monomer and an olefin monomer. The method according to claim 1,
The base film may be a fluoropolymer film selected from the group consisting of a copolymer of tetrafluoroethylene and fluorovinyl ether including poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid) sulfonic acid group, and combinations thereof. Wherein the ion-exchange membrane has an ion-exchange characteristic. The method according to claim 1,
The base film may be formed of at least one of sulfonated polyimide, sulfonated polyaryl ether sulfone, sulfonated polyether ether ketone, sulfonated polybenzimidazole, sulfonated polysulfone, sulfonated polystyrene, sulfonated polyphosphazene, sulfonated polyether ether sulfone , Sulfonated polyether sulfone, sulfonated polyether benzimidazole, sulfonated polyarylene ether ketone, sulfonated polyether ketone, sulfonated polystyrene, sulfonated polyimidazole, sulfonated polyether ketone ketone, polyaryletherbenz Wherein the hydrocarbon-based polymer membrane is a hydrocarbon-based polymer membrane selected from the group consisting of imidazole and a combination thereof. The method according to claim 1,
Wherein the swelling solution is selected from a first swelling solution that increases the spacing between the polymer chains of the hydrophilic region, a second swelling solution that increases the spacing between the polymer chains of the hydrophobic region, or a mixture of the first swelling solution and the second swelling solution Wherein the ion exchange membrane is formed by a method comprising the steps of: 8. The method of claim 7,
Wherein the first swelling solution is selected from the group consisting of water, methanol, ethanol, n-propanol, isopropanol or mixtures thereof and the second swelling solution is selected from the group consisting of toluene, xylene, benzene, ethylbenzene, &Lt; / RTI &gt; 8. The method of claim 7,
Wherein the surface treatment of the base membrane is performed sequentially while changing the mixing ratio of the first swelling solution and the second swelling solution. The method according to claim 1,
Wherein the process of treating the surface of the basement membrane with the swelling solution of step (a) is performed for 1 to 24 hours. The method according to claim 1,
Wherein the solution containing the monomer of step (b) further comprises a crosslinking agent, a catalyst for reaction, a radical initiator, a solvent, or a mixture thereof. The method according to claim 1,
Wherein the method of applying the monomer-containing solution to the base film is performed by spray coating, impregnation, casting, or brushing. The method according to claim 1,
Wherein the polymerization reaction in step (b) is carried out through a photo-curing or thermosetting process. An ion exchange membrane produced according to the production method according to any one of claims 1 to 13.

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