KR102256124B1 - Anion exchange material having chain extension group and preparation method thereof - Google Patents

Abstract

The present invention relates to an anion exchange material having a chain extender and a method for preparing the same. More specifically, 2,2,6,6-tetramethylpiperidine-N-oxide as a chain extender in addition to an anion exchanger in the side chain of a polymer. The present invention relates to an anion exchange material containing a group (TEMPO), a method for manufacturing the same, a polymer electrolyte membrane formed with an anion exchange material produced therefrom, and an electrochemical device including the polymer electrolyte membrane. The anion exchange material according to the present invention is a polymer electrolyte membrane, as well as a fuel cell, redox flow battery, electrodialysis (ED), reverse electrodialysis (RED), capacitive deionization (CDI). ), etc., can be used in various electrochemical devices.

Description

Anion exchange material having chain extension group and preparation method thereof

The present invention relates to an anion exchange material having a chain extender and a method of manufacturing the same.

More specifically, an anion exchange material containing 2,2,6,6-tetramethylpiperidine-N-oxide group (TEMPO) as a chain extender in addition to an anion exchanger in the side chain of the polymer, and a method for producing the same, and from The present invention relates to a polymer electrolyte membrane in which an anion exchange material is formed and an electrochemical device including the polymer electrolyte membrane.

The depletion of fossil fuels due to the recent population increase, pollution, and increasing demand for electric energy necessitate the development of alternative energy sources. Therefore, many researchers are attempting to invent a new system capable of producing and storing electric energy. Among them, in renewable energy such as proton exchange membrane fuel cell (PEMFC) and energy storage system such as redox flow battery (RFB), ion conductive polymer membranes influence the performance and durability of the battery. It is a core material.

Polymer electrolyte membranes developed up to now can be divided into fluorinated polymer electrolytes and hydrocarbon polymer electrolytes. Fluorinated polymer electrolytes have strong carbon-fluorine (CF) bonding and masking, which is a characteristic of fluorine atoms. It is chemically stable due to the (shielding) effect, has excellent mechanical properties, and has high conductivity as a hydrogen ion exchange membrane, so it is currently commercialized as a polymer membrane of a polymer electrolyte fuel cell. Nafion (perfluorinated sulfonic acid polymer), a product of Du Pont in the United States, is a representative example of a commercially available hydrogen ion exchange membrane, and is currently the most widely used because of its excellent ionic conductivity, chemical stability, and ion selectivity. However, fluorinated polymer electrolyte membranes have disadvantages of low industrial use due to their high price, as opposed to excellent performance, high methanol crossover through which methanol passes through the polymer membrane, and the efficiency of the polymer membrane decreases at temperatures above 80°C. Therefore, researches on hydrocarbon-based ion exchange membranes that are competitive in terms of price are being actively conducted, but the electrolyte membranes that are mainly used up to now are the perfluorine-based cation exchange membrane materials represented by Nafion.

On the other hand, since the anion exchange material selectively moves only anions, the redox flow battery (RFB) system using a cationic active material can fundamentally prevent the crossover of the active material, and even when applied to a fuel cell system. Since the direction of movement of anions is opposite to the direction of movement of fuel, crossover of fuel can be prevented, and in the case of a fuel cell system with anion exchange membrane, inexpensive metal catalysts other than expensive platinum can be used. Accordingly, it is known that there is an advantage of reducing the cost of the overall battery system.

Currently, as representative materials of such anion exchange materials, FAP and VPX of German Pumatech are commercially available, but these are also very expensive and have very low ionic conductivity due to the characteristics specialized for redox flow batteries (RFB), so other materials such as fuel cells There is a disadvantage that it is difficult to apply it to an electrochemical device.

Accordingly, various attempts have been made to develop a hydrocarbon-based anion exchange material with improved price competitiveness and durability and to apply it to a redox flow battery. Such conventional techniques include Korean Patent No. 10-1543079 and Japanese Patent Laid-Open No. 2003-96219, which introduce an anion exchange group into a polyethersulfone copolymer, but this is a simple anion in the side chain of a polymer having a hydrocarbon-based main chain. It is just the level of the introduction of the exchanger and the application of it to the redox flow battery.

These materials have the advantage of being easy to manufacture, but their chemical durability is very weak, and the fact that they cannot be used in actual applications is considered to be the biggest disadvantage, and such low chemical stability is the low oxidation stability of the ammonium ion group capable of ion exchange. It is known to originate from. As a method to overcome this, it is known that it is very effective to introduce a substituent that can cause steric hindrance adjacent to the ammonium ion in order to minimize the attack from various radicals that oxidize the material. It is typical to introduce a spacer and to induce steric hindrance by directly introducing a large extender to the ion exchanger. However, these methods are also auxiliary methods that can improve the oxidation stability of materials and are not fundamental countermeasures. Therefore, the stability of materials can be improved by improving steric hindrance and removing radicals more radically generated. Development is being demanded.

Korean Patent Registration No. 10-1543079. Japanese Unexamined Patent Application Publication No. 2003-96219.

The present invention has been developed to solve the above problems, and it is an object of the present invention to provide an anion exchange material having improved durability as well as price competitiveness by using a hydrocarbon-based polymer, and a method of manufacturing the same.

In addition, in the present invention, not only fuel cells, but also various electrochemical devices such as redox flow cells, electrodialysis (ED), reverse electrodialysis (RED), capacitive deionization (CDI), etc. It is intended to provide an anion exchange material with improved utility.

In the present invention, in order to solve the above problems, an anion exchange material in which 2,2,6,6-tetramethylpiperidine-N-oxide groups (TEMPO) are simultaneously introduced into the side chain of a hydrocarbon-based polymer as an anion exchanger and a chain extender. And it provides a method of manufacturing the same.

In addition, the present invention provides a polymer electrolyte membrane manufactured by molding an anion exchange material in which an anion exchanger and a chain extender are simultaneously introduced into a side chain of a hydrocarbon-based polymer.

In addition, the present invention provides an electrochemical device comprising, as a polymer electrolyte membrane, an anion exchange material in which an anion exchanger and a chain extender are simultaneously introduced into a side chain of a hydrocarbon-based polymer.

The anion exchange material according to the present invention includes a hydrocarbon-based polymer as a main chain, and in terms of price competitiveness, such as Nafion, a product of Du Pont, a cation ion exchange material, and FAP and VPX of Pumatech, Germany, an anion exchange material. Not only is it advantageous compared to this commercially available product, it can also be used as an electrolyte membrane for various electrochemical devices such as fuel cells and redox flow cells.

The anion exchange material according to the present invention has the advantage of increasing the stability of the material from radicals generated during operation of the electrochemical device by acting as a radical scavenger with the chain extender introduced into the side chain at the same time as the anion exchanger. have.

In addition, it is not introduced as a covalent defect in an independent part of the main chain, but is introduced into the chain extender of the chain into which an ion exchange group is introduced, thereby causing steric hindrance, thereby further improving the stability of the material from various radicals.

In addition, the anion exchange material according to the present invention can improve the stability of the ion exchanger by increasing steric hindrance by the chain extender introduced into the side chain at the same time as the anion exchanger, as well as promoting the fine phase separation of the anion exchange material to improve ionic conductivity. It works.

In addition, the 2,2,6,6-tetramethylpiperidine-N-oxide group (TEMPO), which is a chain extender introduced into the anion exchange material according to the present invention, is reversible during the redox reaction and is thermodynamically very stable. It is effective as an electrolyte membrane for a dox flow battery.

1 shows a method of manufacturing an anion exchange material having a chain extender according to an embodiment of the present invention.
^{Figure 2 shows the 1} H-NMR spectrum of the anion exchange material and precursor having a chain extender according to an embodiment of the present invention.
Figure 3 shows the FR-IR spectrum of the anion exchange material and precursor having a chain extender according to an embodiment of the present invention.
Figure 4 shows the results of the oxidation stability test of the anion exchange material having a chain extender according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The "chain extender" described throughout the specification of the present invention refers to a unit capable of causing steric hindrance by lengthening the length of the side chain into which the ion exchange group is introduced, as well as 2,2,6,6- It refers to a substituent introduced for the purpose of improving chemical stability against oxidation by introducing a tetramethylpiperidine-N-oxide group (TEMPO).

In the present invention, in order to solve the above problems, a polymer manufacturing step of preparing a hydrocarbon-based polymer having a chemical structure of the following formula 1 as a main chain; Halogenated polymer manufacturing step of halogenating the hydrocarbon-based polymer; A step of preparing a polymer having an anionic conductive group through quaternization of the halogenated polymer using N,N,2,2,6,6-hexamethylpiperidin-4-amine; And oxidizing the piperidine group of the polymer having the anion conductive group.

<Formula 1>

In Formula 1, M, M', M'' are each a single bond or as an electron donor group -O-, -S-, -NR'- (In this case, R'is a hydrogen atom or a C ₁ ~ C ₁₂ alkyl group One), or any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )- , R ₁ to R ₈ are each hydrogen atom or an alkyl group, aryl group, allyl group, fluorine atom, aryl group including fluorine atom, cyano group, perfluoroalkyl group, oxygen, nitrogen, sulfur atom in the chain Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group including one or more may be the same or different in each repeating unit or per repeating unit,

N, the number of repeating units, is an integer of 1 or more and 100,000 or less,

Ar is the same as the following formula (2),

<Formula 2>

In Formula 2, M''' is a single bond or an electron donor group -O-, -S-, -NR'- (where R'is a hydrogen atom or _{any one of a C 1} to C ₁₂ alkyl group), or an electron As a drag, any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )-, and R ₉ to R ₂₀ is a hydrogen atom or an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group including a fluorine atom, a cyano group, a perfluoroalkyl group, and a chain containing at least one of oxygen, nitrogen, and sulfur atoms. It is any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and may be the same or different within each repeating unit or per repeating unit.

In the manufacturing method according to an embodiment of the present invention, the manufacturing step of the halogenated polymer may be to prepare a halogenated polymer having the chemical structure of Formula 3 through a chloromethylation reaction, a bromination reaction, or an iodination reaction.

<Formula 3>

_{Z 1} in Formula 3 is a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, and a chain containing at least one of oxygen, nitrogen, and sulfur atoms. Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and X is a halogen atom among chlorine (Cl), bromine (Br), and iodine (I). And R ₂₁ to R ₂₃ are each hydrogen atom or an alkyl group, aryl group, allyl group, fluorine atom, aryl group including a fluorine atom, cyano group, perfluoroalkyl group, oxygen, nitrogen, Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group containing at least one sulfur atom, and R ₂₄ to R ₂₇ are each Z ₁ X, or Like R ₂₁ to R ₂₃ , each is a hydrogen atom or an alkyl group, aryl group, allyl group, fluorine atom, aryl group including fluorine atom, cyano group, perfluoroalkyl group, oxygen, nitrogen, sulfur atom in the chain Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group including one or more, and Ar' is the same as Ar in Formula 1 or each phenyl of Ar The ring may have at least one substituent represented by _{Z 1 X.}

In the manufacturing method according to an embodiment of the present invention, the anion exchange material having the chain extender may have a chemical structure represented by the following formula (4).

<Formula 4>

Q'in Formula 4 is an ammonium group derived from an amine group as a cationized ion-exchange functional group, a sulfonium group, a phosphonium group, a pyridinium group, a carbazolium group and an imidazolium group, or both selected from betaine and sulfobetaine. An ion exchanger selected from a sexual ion exchange functional group and a combination thereof or an anion exchange functional group in a salt state thereof, and Z ₂ is a single bond or a C ₁ to C ₁₂ alkyl group, aryl group, allyl group, fluorine The group consisting of an aryl group containing an atom, a perfluoroalkyl group, a perfluoroalkylaryl group containing at least one of oxygen, nitrogen, and sulfur atoms in the chain, a perfluoroaryl group, and an -O-perfluoroaryl group is one selected from, R _'24 ~ R' ₂₇ are each Z ₁ Q'X ^- or substituents represented by Z ₂ (2,2,6,6- tetramethyl-piperidine), R ₂₁ ~ R ₂₃ Likewise, each is a hydrogen atom or contains at least one of an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group containing a fluorine atom, a cyano group, a perfluoroalkyl group, and at least one of oxygen, nitrogen, and sulfur atoms in its chain. Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and Ar'' in Formula 4 is the same as Ar in Formula 1 or each phenyl of Ar ring is at least one Z ₁ Q'X ^- may have a substituent represented by Z ₂ (2,2,6,6- tetramethyl-piperidine).

In the manufacturing method according to an embodiment of the present invention, the step of oxidizing the piperidine group of the polymer may be to prepare an anion exchange material having the chemical structure of the following formula (5) through oxidation of the piperidine group.

<Formula 5>

R'' ₂₄ to R'' ₂₇ of Formula 5 are each _{a substituent represented by Z 1} Q'X ^- Z ₂ (2,2,6,6-tetramethylpiperidine-N-oxide), or R _{Like 21} to R ₂₃ , each is a hydrogen atom or a perfluoro containing at least one of oxygen, nitrogen, and sulfur atoms in its chain, such as an alkyl group, aryl group, allyl group, fluorine atom, aryl group, cyano group, perfluoroalkyl group. Is any one selected from the group consisting of a roalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and Ar''' is the same as Ar in Formula 1, or each phenyl ring of Ar is at least one It _{may have a substituent represented by Z 1} Q'X ^- Z ₂ (2,2,6,6-tetramethylpiperidine-N-oxide).

In addition, the present invention provides an anion exchange material having a chain extender, characterized in that it has a chemical structure of the following formula (5).

<Formula 5>

In Formula 5, M, M', M'' are each a single bond or as an electron donor group -O-, -S-, -NR'- (In this case, R'is a hydrogen atom or a C ₁ ~ C ₁₂ alkyl group One), or any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )- ,

N, the number of repeating units, is an integer of 1 or more and 100,000 or less,

Ar '''are the same or to the formula Ar 2' each phenyl ring of the "" is at least one of Z ₁ Q'X ^- Z P ₂ (2,2,6,6- tetramethyl-piperidine oxide -N- Seed) may have a substituent represented by,

<Formula 2>

In Formula 2, M''' is a single bond or an electron donor group -O-, -S-, -NR'- (where R'is a hydrogen atom or _{any one of a C 1} to C ₁₂ alkyl group), or an electron As a drag, any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )-, and R ₉ to R ₂₀ is a hydrogen atom or an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group including a fluorine atom, a cyano group, a perfluoroalkyl group, and a chain containing at least one of oxygen, nitrogen, and sulfur atoms. Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group may be the same or different within each repeating unit or per repeating unit,

R ₂₁ to R ₂₃ are each a hydrogen atom or a perfluoro containing one or more of an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group, a cyano group, a perfluoroalkyl group, and an oxygen, nitrogen, and sulfur atom in its chain. It is any one selected from the group consisting of a roalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,

R'' ₂₄ to R'' ₂₇ are each the _{same as R 21} to R ₂₃ or represented by Z ₁ Q'X ^- Z ₂ (2,2,6,6-tetramethylpiperidine-N-oxide) May be a substituent,

Z ₁ is a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, a perfluoroalkyl containing at least one of oxygen, nitrogen, and sulfur atoms in its chain Any one selected from the group consisting of an aryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,

Q'is an ammonium group derived from an amine group as a cationized ion exchange functional group, a sulfonium group, a phosphonium group, a pyridinium group, a carbazolium group and an imidazolium group, or an amphoteric ion exchange functional group selected from betaine and sulfobetaine And an ion exchanger selected from a combination thereof or an anion exchange functional group in a salt state thereof,

Z ₂ is a single bond or a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, and a purple containing one or more of oxygen, nitrogen, and sulfur atoms in the chain It is any one selected from the group consisting of a luoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,

X is a halogen atom and is any one of chlorine (Cl), bromine (Br), and iodine (I).

In addition, the present invention provides a polymer electrolyte membrane, characterized in that produced by molding the anion exchange material.

In the polymer electrolyte membrane manufactured by molding the anion exchange material according to the present invention, the chain extender introduced into the side chain at the same time as the anion exchanger acts as a radical scavenger, so the stability of the material from the radicals generated during operation of the electrochemical device. Not only has the advantage of increasing the anion exchanger, but also the chain extender introduced into the side chain at the same time as the anion exchanger increases steric hindrance, thereby improving the stability of the ion exchanger and promoting the fine phase separation of the anion exchange material, thereby improving the ion conductivity.

In addition, the present invention provides a membrane electrode assembly including an anode, a cathode, and the polymer electrolyte membrane provided between the anode and the cathode.

In addition, the present invention provides a fuel cell including the membrane electrode assembly.

In addition, the present invention provides an electrochemical device including the polymer electrolyte membrane, wherein the electrochemical device may be any one of a redox flow battery, an electrodialysis device, a reverse electrodialysis device, and a capacitive desalination device. In particular, 2,2,6,6-tetramethylpiperidine-N-oxide group (TEMPO), which is a chain extender introduced into the anion exchange material according to the present invention, is reversible during redox reaction and is very thermodynamically stable. It is effective as an electrolyte membrane for a dox flow battery.

In addition, it is possible to apply the anion fuel cell as a solid electrolyte membrane, as well as the electrode layer as a binder material.

Hereinafter, implementation examples and examples of the present application will be described in detail so that those with general knowledge in the technical field to which the present application pertains can be easily implemented, as shown in the accompanying drawings. In particular, the technical idea of the present invention and its core configuration and operation are not limited by this. In addition, the content of the present invention may be implemented in various different types of equipment, and is not limited to the implementation examples and examples described herein.

1 shows a method of manufacturing an anion exchange material having a chain extender according to an embodiment of the present invention.

According to an embodiment of the present invention, a halogenated polymer (Chloromethylated Udel) is prepared through a chloromethylation reaction of polysulfone as a hydrocarbon-based polymer, and the prepared halogenated polymer is N,N,2,2,6,6-Hexamethylpiperidin-4. A polymer (TEMP-Quaterinized Udel) having an anionic conductive group was prepared through quaternization using -amine. Thereafter, an anion exchange material (TEMPO-Quaternized Udel) having a chain extension group was prepared by oxidizing the piperidine group of the polymer having an anionic conductive group.

^{Figure 2 shows the 1} H-NMR spectrum of the anion exchange material and precursor having a chain extender according to an embodiment of the present invention.

When the halogenated polymer (Chloromethylated Udel) according to an embodiment of the present invention was ^{analyzed by 1} H-NMR spectroscopy, a chloromethyl functional group was observed at 4.5 ppm, and the chloromethylation degree of polysulfone was confirmed to be 0.956 ( ¹ H NMR ( 400 Hz, CDCl ₃ ), δ (ppm): 1.73 (s, 6H), 4.56 (s, 2H), 6.83-7.00 (m, 3H), 7.04 (m, 4H), 7.17-7.29 (m, 3H) , 7.39 (s, 1H), 7.88 (m, 4H)).

When the polymer (TEMP-Quaterinized Udel) having an anionic conductive group according to an embodiment of the present invention was ^{analyzed by 1} H-NMR spectroscopy, as the halogen of the chloromethyl group present at 4.5 ppm was substituted with an ammonium group, the methyl group was It was confirmed that it was shifted to 4.4ppm, and it was confirmed that the synthesis was well done by checking the proton of TEMP appearing at 2.8, 1.7 and 1.1ppm ( ¹ H NMR (400 Hz, DMSO), δ (ppm): 1.13 (d, 12H), 1.39(s, 2H), 1.69 (m, 6H), 2.1 (s, 2H), 2.8 (d, 6H), 4.2 (s, 1H), 4.4 (s, 2H), 6.9-7.10 (m , 6H), 7.25-7.40 (m, 4H), 7.6 (s, 1H), 7.88 (s, 1H), 7.9-8.02 (m, 4H)).

When an anion exchange material (TEMPO-Quaternized Udel) having a chain extender according to an embodiment of the present invention was ^{analyzed by 1} H-NMR spectroscopy, a broad peak at 6.5 to 8 ppm in the presence of NO radicals Was observed.

Figure 3 shows the FR-IR spectrum of the anion exchange material and precursor having a chain extender according to an embodiment of the present invention.

By FT-IR analysis of the polymer (TEMP-Quaterinized Udel) having an anion conductive group according to an embodiment of the present invention, 938, 830 cm ^-1 NH peak could be identified, and an anion exchange material having a chain extender (TEMPO-Quaternized Udel). Udel) did not show an absorption peak at the NH position, and it was confirmed that oxidation was performed by confirming the absorption peak by the NO radical at ^{3034 to 3059 cm -1.}

<Preparation Example 1> Chloromethylated Udel of polysulfone

After completely dissolving 34 g of polysulfone (Udel Polysulfone, P-3500 LCD MB, Solvay Advanced Polymers) in 140 ml of 1,1,2,2-tetrachloroethane, zinc chloride ( ZnCl ₂ ) 2.97 g and 23 ml of chloromethyl methyl ether were added and reacted at 40° C. for 3.5 hours. After the reaction was completed, it was precipitated in an excess of methanol and washed several times with methanol and tertiary distilled water. The washed chloromethylated polysulfone (Chloromethylated Udel) was vacuum dried at 80° C. for 24 hours.

<Preparation Example 2> Ion exchange of chloromethylated polysulfone (TEMP-Quaterinized Udel)

After completely dissolving 1 g of chloromethylated polysulfone (Chloromethylated Udel) at a concentration of 5 wt% of dimethyl sulfoxide (DMSO) according to Preparation Example 1, 3eq. of N,N,2,2,6,6-Hexamethylpiperidin-4-amine. Was slowly added and reacted at 25° C. for 24 hours. After the reaction was completed, it was precipitated in an excess of distilled water and washed several times with third distilled water. The washed ion-exchanged polysulfone (TEMP-Quaterinized Udel) was vacuum dried at 60° C. for 24 hours.

<Preparation Example 3> Oxidation of polysulfone having an ion exchange group (TEMPO-Quaternized Udel)

1 g of ion-exchanged polysulfone (TEMP-Quaterinized Udel) according to Preparation Example 2 was completely dissolved in a concentration of 5 wt% of dimethyl sulfoxide (DMSO), and then formed into a film and dried at 60° C. for 24 hours. _{The dried ion exchange membrane was loaded in a solution in which Na 2} WO ₄ was dissolved in an excess of 30 wt% hydrogen peroxide and reacted at room temperature for 72 hours. The reacted anion exchange membrane was washed again with distilled water several times, and the washed anion exchange membrane. (TEMPO-Quaternized Udel) was vacuum dried at 60° C. for 24 hours.

<Examples and Comparative Examples>

A radical scavenger of TEMPO-Quaternized Udel oxidizing polysulfone having a chain-extending ion-exchange group prepared according to Preparation Example 3 of the present invention using polysulfone having only an ion exchange group as a comparative example Accelerated oxidation stability evaluation was conducted to evaluate the stability against ^OH- radicals according to the presence or absence of.

Experimental conditions for the oxidation stability evaluation were observed changes in ion conductivity over time by supporting two types of anion exchange materials prepared in 1M NaOH soulution at a temperature ^{of 80 o C, and the ion conductivity was determined by EIS (electrochemical impedance spectroscopy) method.} In a nitrogen atmosphere with a relative humidity of 100%, measurements were made in the plane direction in a frequency range of 0.1-20 kHz using a standard four prove cell, and a Solatron 1280 instrument was used as the measurement equipment.

The ionic conductivity was calculated using the following equation 1.

ionic conductivity (mS cm ^-1 ) = l/R × S (Equation 1)

In Equation 1, l is the distance between electrodes, S is the thickness of the ion exchange membrane, and R is the impedance value of the ion exchange material.

Figure 4 shows the results of the oxidation stability test of the anion exchange material having a chain extender ion exchange group according to an embodiment of the present invention, the results of the oxidation stability test in 80 ^o C 1M NaOH aqueous solution, polysulfone having only an ion exchange group In (Comparative Example), the film was fractured in about 4 days under the accelerated oxidation stability evaluation conditions. On the other hand oxidation of polysulfone having a chain extending the ion exchange group (Example) was maintaining the ionic conductivity for 30 days under the evaluation conditions, after 30 days showed a good oxidation stability, to maintain the ion conductivity of about 40%, OH ^- radical It can be seen that the stability is excellent.

Claims (10)

A polymer production step of preparing a hydrocarbon-based polymer having a chemical structure represented by the following Formula 1 as a main chain;
Halogenated polymer manufacturing step of halogenating the hydrocarbon-based polymer;
A step of preparing a polymer having an anionic conductive group through quaternization of the halogenated polymer using N,N,2,2,6,6-hexamethylpiperidin-4-amine; And
Including the step of oxidizing the piperidine group (piperidine group) of the polymer having the anionic conductive group,
A method for producing an anion exchange material having a chain extender, characterized in that to prepare an anion exchange material having a chemical structure of the following formula (5):
<Formula 1>

In Formula 1, M, M', M'' are each a single bond or as an electron donor group -O-, -S-, -NR'- (In this case, R'is a hydrogen atom or a C ₁ ~ C ₁₂ alkyl group One), or any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )- , R ₁ to R ₈ are each hydrogen atom or an alkyl group, aryl group, allyl group, fluorine atom, aryl group including fluorine atom, cyano group, perfluoroalkyl group, oxygen, nitrogen, sulfur atom in the chain Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group including one or more may be the same or different within each repeating unit or per repeating unit,
N, the number of repeating units, is an integer of 1 or more and 100,000 or less,
Ar is the same as in Formula 2 below,
<Formula 2>

In Formula 2, M''' is a single bond or an electron donor group -O-, -S-, -NR'- (where R'is a hydrogen atom or _{any one of a C 1} to C ₁₂ alkyl group), or an electron As a drag, any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )-, and R ₉ to R ₂₀ is a hydrogen atom or an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group including a fluorine atom, a cyano group, a perfluoroalkyl group, and a chain containing at least one of oxygen, nitrogen, and sulfur atoms. It is any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and may be the same or different within each repeating unit or per repeating unit,
<Formula 5>

R'' ₂₄ to R'' ₂₇ of Formula 5 are each _{a substituent represented by Z 1} Q'X ^- Z ₂ (2,2,6,6-tetramethylpiperidine-N-oxide), or R _{Like 21} to R ₂₃ , each is a hydrogen atom or a perfluoro containing at least one of oxygen, nitrogen, and sulfur atoms in its chain, such as an alkyl group, aryl group, allyl group, fluorine atom, aryl group, cyano group, perfluoroalkyl group. Is any one selected from the group consisting of a roalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and Ar''' is the same as Ar in Formula 1, or each phenyl ring of Ar is at least one May have a substituent represented by Z ₁ ^Q'X- Z ₂ (2,2,6,6-tetramethylpiperidine-N-oxide) ,
Z ₁ is a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, a perfluoroalkyl containing at least one of oxygen, nitrogen, and sulfur atoms in its chain It is any one selected from the group consisting of an aryl group, a perfluoroaryl group and an -O-perfluoroaryl group,
Q'is an ammonium group derived from an amine group as a cationized ion exchange functional group, a sulfonium group, a phosphonium group, a pyridinium group, a carbazolium group and an imidazolium group, or an amphoteric ion exchange functional group selected from betaine and sulfobetaine And an ion exchanger selected from a combination thereof or an anion exchange functional group in a salt state thereof,
Z ₂ is a single bond or a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, and a purple containing one or more of oxygen, nitrogen, and sulfur atoms in the chain It is any one selected from the group consisting of a luoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,
X is a halogen atom and is any one of chlorine (Cl), bromine (Br), and iodine (I). The method according to claim 1,
The manufacturing step of the halogenated polymer is a method for producing an anion exchange material having a chain extender, characterized in that the halogenated polymer having the chemical structure of the following formula (3) is prepared through a chloromethylation reaction, a bromination reaction, or an iodination reaction:
<Formula 3>

_{Z 1} in Formula 3 is a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, and a chain containing at least one of oxygen, nitrogen, and sulfur atoms. Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and X is a halogen atom among chlorine (Cl), bromine (Br), and iodine (I). And R ₂₁ to R ₂₃ are each hydrogen atom or an alkyl group, aryl group, allyl group, fluorine atom, aryl group including a fluorine atom, cyano group, perfluoroalkyl group, oxygen, nitrogen, Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group containing at least one sulfur atom, and R ₂₄ to R ₂₇ are each Z ₁ X, or Like R ₂₁ to R ₂₃ , each is a hydrogen atom or an alkyl group, aryl group, allyl group, fluorine atom, aryl group including fluorine atom, cyano group, perfluoroalkyl group, oxygen, nitrogen, sulfur atom in the chain Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group including one or more, and Ar' is the same as Ar in Formula 1 or each phenyl of Ar The ring may have at least one substituent represented by _{Z 1 X.} The method according to claim 1,
The method for producing an anion exchange material having a chain extender, characterized in that the anion exchange material having a chain extender has a chemical structure represented by the following formula (4):
<Formula 4>

Q'in Formula 4 is an ammonium group derived from an amine group as a cationized ion-exchange functional group, a sulfonium group, a phosphonium group, a pyridinium group, a carbazolium group and an imidazolium group, or both selected from betaine and sulfobetaine. An ion exchanger selected from a sexual ion exchange functional group and a combination thereof or an anion exchange functional group in a salt state thereof, and Z ₂ is a single bond or a C ₁ to C ₁₂ alkyl group, aryl group, allyl group, fluorine The group consisting of an aryl group containing an atom, a perfluoroalkyl group, a perfluoroalkylaryl group containing at least one of oxygen, nitrogen, and sulfur atoms in the chain, a perfluoroaryl group, and an -O-perfluoroaryl group is one selected from, R _'24 ~ R' ₂₇ are each Z ₁ Q'X ^- or substituents represented by Z ₂ (2,2,6,6- tetramethyl-piperidine), R ₂₁ ~ R ₂₃ Likewise, each is a hydrogen atom or contains at least one of an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group containing a fluorine atom, a cyano group, a perfluoroalkyl group, and at least one of oxygen, nitrogen, and sulfur atoms in its chain. Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group, and Ar'' in Formula 4 is the same as Ar in Formula 1 or each phenyl of Ar ring is at least one Z ₁ Q'X ^- may have a substituent represented by Z ₂ (2,2,6,6- tetramethyl-piperidine). delete It is manufactured by the manufacturing method according to any one of claims 1 to 3,
Anion exchange material having a chain extension group, characterized in that it has the chemical structure of the following formula (5):
<Formula 5>

In Formula 5, M, M', M'' are each a single bond or as an electron donor group -O-, -S-, -NR'- (In this case, R'is a hydrogen atom or a C ₁ ~ C ₁₂ alkyl group One), or any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )- ,
N, the number of repeating units, is an integer of 1 or more and 100,000 or less,
Ar '''are the same or to the formula Ar 2' each phenyl ring of the "" is at least one of Z ₁ Q'X ^- Z P ₂ (2,2,6,6- tetramethyl-piperidine oxide -N- Seed) may have a substituent represented by,
<Formula 2>

In Formula 2, M''' is a single bond or an electron donor group -O-, -S-, -NR'- (where R'is a hydrogen atom or _{any one of a C 1} to C ₁₂ alkyl group), or an electron As a drag, any one of -(C=O)-, -(P=O)-, -(SO ₂ )-, -CF ₂ -, -(C(CF ₃ ) ₂ )-, and R ₉ to R ₂₀ is a hydrogen atom or an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group including a fluorine atom, a cyano group, a perfluoroalkyl group, and a chain containing at least one of oxygen, nitrogen, and sulfur atoms. Any one selected from the group consisting of a perfluoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group may be the same or different within each repeating unit or per repeating unit,
R ₂₁ to R ₂₃ are each a hydrogen atom or a perfluoro containing one or more of an alkyl group, an aryl group, an allyl group, a fluorine atom, an aryl group, a cyano group, a perfluoroalkyl group, and an oxygen, nitrogen, and sulfur atom in its chain. It is any one selected from the group consisting of a roalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,
R'' ₂₄ to R'' ₂₇ are each the _{same as R 21} to R ₂₃ or represented by Z ₁ Q'X ^- Z ₂ (2,2,6,6-tetramethylpiperidine-N-oxide) May be a substituent,
Z ₁ is a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, a perfluoroalkyl containing at least one of oxygen, nitrogen, and sulfur atoms in its chain Any one selected from the group consisting of an aryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,
Q'is an ammonium group derived from an amine group as a cationized ion exchange functional group, a sulfonium group, a phosphonium group, a pyridinium group, a carbazolium group and an imidazolium group, or an amphoteric ion exchange functional group selected from betaine and sulfobetaine And an ion exchanger selected from a combination thereof or an anion exchange functional group in a salt state thereof,
Z ₂ is a single bond or a C ₁ to C ₁₂ alkyl group, an aryl group, an allyl group, an aryl group containing a fluorine atom, a perfluoroalkyl group, and a purple containing one or more of oxygen, nitrogen, and sulfur atoms in the chain It is any one selected from the group consisting of a luoroalkylaryl group, a perfluoroaryl group, and an -O-perfluoroaryl group,
X is a halogen atom and is any one of chlorine (Cl), bromine (Br), and iodine (I). A polymer electrolyte membrane manufactured by molding the anion exchange material according to claim 5. A membrane electrode assembly comprising an anode, a cathode, and the polymer electrolyte membrane of claim 6 provided between the anode and the cathode. A fuel cell comprising the membrane electrode assembly of claim 7. An electrochemical device comprising the polymer electrolyte membrane of claim 6. The method of claim 9,
The electrochemical device is an electrochemical device, characterized in that any one of a redox flow battery, an electrodialysis device, a reverse electrodialysis device, and a capacitive desalination device.

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