KR101748484B1 - Poly(arylene ether sulfone) copolymer and polymer membranes comprising the same - Google Patents

Abstract

The present application relates to a poly (arylene ether sulfone) copolymer and a polymer electrolyte membrane containing the same. The crosslinked poly (arylene ether sulfone) copolymer according to the present invention includes a crosslinked structure containing a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (2) as a main chain and having a sulfonic acid group .

Description

TECHNICAL FIELD The present invention relates to a poly (arylene ether sulfone) copolymer and a polymer electrolyte membrane containing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a poly (arylene ether sulfone)

This application claims the benefit of Korean Patent Application No. 10-2014-0072423 filed on June 13, 2014, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. The present application relates to a poly (arylene ether sulfone) copolymer and a polymer electrolyte membrane containing the same.

Recently, as the exhaustion of existing energy resources such as oil and coal is predicted, interest in energy that can replace them is increasing. As one of such alternative energies, fuel cells have attracted particular attention due to their advantages such as high efficiency, no emission of pollutants such as NOx and SOx, and abundant fuel.

A fuel cell is a power generation system that converts the chemical reaction energy of a fuel and an oxidant into electric energy. Hydrogen, hydrocarbons such as methanol and butane are used as fuel, and oxygen is used as an oxidant.

BACKGROUND ART Fuel cells include a polymer electrolyte fuel cell (PEMFC), a direct methanol fuel cell (DMFC), a phosphoric acid fuel cell (PAFC), an alkaline fuel cell (AFC), a molten carbonate fuel cell (MCFC) And a battery (SOFC). Among them, polymer electrolyte fuel cells have been actively studied because they have high energy density and high output. Such a polymer electrolyte fuel cell differs from other fuel cells in that it uses a solid polymer electrolyte membrane instead of a liquid electrolyte.

Korean Patent Publication No. 10-2003-0076057

The present application aims to provide a polymer electrolyte membrane for a fuel cell excellent in hydrogen ion conductivity, mechanical properties, dimensional stability, and polymers for the same.

In one embodiment of the present application,

(1) and a repeating unit represented by the following formula (2) as a main chain,

(Arylene ether sulfone) copolymer comprising a crosslinked structure.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R 1 to R 3 and R 8 to R 10 are each independently -O-, -S-, -SO ₂ -, -C = O- or -C (CH ₃ ) ₂ -

R4 to R7 and R13 to R16 each independently represent hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms,

R11 and R12 are each independently a -SO ₃ R17,

R17 is H, Li, Na or K,

R18 and R19 are each independently -CH ₂ Cl or -CH ₂ N _3, and

A and A 'are each independently a direct bond or a straight or branched alkylene group having 1 to 10 carbon atoms,

m, o, p and q are each independently 0 to 4, n, r, s and t are each independently 0 to 3,

a and b are the molar ratios of formulas (1) and (2), each independently 0.1 to 0.99.

Further, another embodiment of the present application,

Forming a poly (arylene ether sulfone) copolymer comprising the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2)

A step of sequentially introducing a halogen alkylation reaction and an azidation reaction into the poly (arylene ether sulfone) copolymer to introduce the aziralkyl group into the poly (arylene ether sulfone) copolymer, and

A step of injecting a crosslinking agent to perform a crosslinking process of the poly (arylene ether sulfone) copolymer

(Arylene ether sulfone) copolymer comprising a crosslinked poly (arylene ether sulfone) copolymer.

In addition, another embodiment of the present application provides a polymer electrolyte membrane comprising the crosslinked poly (arylene ether sulfone) copolymer.

Further, another embodiment of the present application provides a fuel cell comprising the polymer electrolyte membrane.

The crosslinked poly (arylene ether sulfone) copolymer according to the present application can be more preferably applied to a polymer electrolyte membrane for a fuel cell. The polymer electrolyte membrane is characterized not only in hydrogen ion conductivity, but also in mechanical properties and dimensional stability.

In preparing the cross-linked poly (arylene ether sulfone) copolymer, the hydrogen ion conductivity, mechanical properties, and the like may vary depending on the composition of the monomer, the amount of the alkyl chain introduced into the main chain of the polymer for the introduction of the cross- , Dimensional stability, and so on.

In addition, in the present application, a cross-linking structure is introduced through a click reaction in a process of casting a polymer solution through a solution process and then heat-treating the solvent to evaporate the solvent. Thus, after the production of the polymer electrolyte membrane, It is possible to easily introduce a crosslinking structure into the membrane.

1 schematically shows the structure of a crosslinked poly (arylene ether sulfone) copolymer according to one embodiment of the present application.
2 is a schematic view showing a photograph of the polymer electrolyte membrane of Example 1 according to one embodiment of the present application.
3 is a schematic view of a photograph of a polymer electrolyte membrane of Example 2 according to one embodiment of the present application.
4 is a schematic view showing a photograph of a polymer electrolyte membrane of Example 3 according to one embodiment of the present application.
5 is a schematic view showing a photograph of the polymer electrolyte membrane of Example 4 according to one embodiment of the present application.
6 is a schematic view showing a photograph of a polymer electrolyte membrane of Example 5 according to one embodiment of the present application.
7 is a schematic view showing a photograph of the polymer electrolyte membrane of Example 6 according to one embodiment of the present application.
8 is a diagram schematically showing a photograph of a polymer electrolyte membrane of Comparative Example 1 according to one embodiment of the present application.

The present application will be described in more detail below.

Generally, a hydrocarbon-based polymer electrolyte membrane applied to a fuel cell has excellent heat and oxidation stability, mechanical properties, processability, and the like, but has a disadvantage that its hydrogen ion conductivity is lower than that of Nafion. If the content of sulfonic acid groups in the polymer is increased to increase the hydrogen ion conductivity, if the sulfonation degree is excessively increased, the water stability may be lowered because the water content increases and the polymer has a large expansion coefficient. In order to improve the dimensional stability of the polymer electrolyte membrane, approaches such as the manufacture of a composite membrane with an inorganic substance, the introduction of fluorine, and the introduction of crosslinking have been made.

In the present application, a crosslinking is intended to be introduced into a polymer electrolyte membrane containing a poly (arylene ether sulfone) copolymer. Particularly, in the present application, by introducing a crosslinking structure containing a sulfonic acid group and a triazole group into the main chain of a poly (arylene ether sulfone) copolymer, it is possible to improve the hydrogen ion conductivity of the polymer electrolyte membrane and improve the mechanical properties and dimensional stability .

The crosslinked poly (arylene ether sulfone) copolymer according to one embodiment of the present application is a copolymer comprising a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) as a main chain and having a crosslinked structure .

In the present application, the term "including a crosslinked structure" means that the copolymer has a crosslinked form by a crosslinking agent.

In the present application, the repeating unit represented by the formula (1) is a monomer not containing a sulfonic acid group, and the repeating unit represented by the formula (2) is a monomer containing a sulfonic acid group. Can be adjusted.

In the present application, when the molar ratio of the repeating unit represented by the above-mentioned formula (2) is too low, the hydrogen ion conductivity may not be sufficiently secured, so that the molar ratio of the repeating unit represented by the above formula (2) is preferably maximized. When the molar ratio of the repeating unit containing no sulfonic acid group to the repeating unit containing a sulfonic acid group is 1: 1, it may have a hydrogen ion conductivity similar to or slightly lower than that of Nafion. In addition, when the molar ratio of the repeating unit containing the sulfonic acid group is higher than that, it is difficult to increase the degree of polymerization of the copolymer, and the dimensional stability of the electrolyte membrane produced using the polymer may be drastically lowered. Accordingly, the molar ratio of the repeating unit represented by Formula 1 to the repeating unit represented by Formula 2 is preferably about 1: 1, but is not limited thereto.

In the present application, the formula (2) may be represented by the following formula (2-1).

[Formula 2-1]

R 8 to R 16, R 19, A ', q, r, s, t and b are the same as defined in the above formula (2).

In the present application, the copolymer containing the repeating units represented by the above-mentioned formulas (1) and (2) as a main chain can be produced by using a dihydroxy monomer, a difluoromonomer or the like.

In the present application, the cross-linking structure can be introduced into the poly (arylene ether sulfone) copolymer by the cross-linking agent described later. In addition, the crosslinking structure may further include a triazole-based functional group.

The crosslinked poly (arylene ether sulfone) copolymer according to the present application can be more preferably applied to a polymer electrolyte membrane for a fuel cell. The polymer electrolyte membrane is characterized not only in hydrogen ion conductivity, but also in mechanical properties and dimensional stability.

In the present application, the viscosity of the crosslinked poly (arylene ether sulfone) copolymer may be, but is not limited to, 1.23 dL g ^-1 .

Further, in the present application, the degree of sulfonation of the crosslinked poly (arylene ether sulfone) may be more than 0 and not more than 0.6, but is not limited thereto.

In the present application, the weight average molecular weight of the copolymer is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, and even more preferably 50,000 to 300,000. When in the above range, it can have high solubility and excellent mechanical properties.

In general, the aromatic hydrocarbon-based polymer electrolyte membrane is excellent in dimensional stability and mechanical properties, but has a low hydrogen ion conductivity. If the degree of sulfonation is increased to overcome this problem, the dimensional stability and mechanical properties of the electrolyte membrane deteriorate. Since the crosslinked poly (arylene ether sulfone) copolymer according to one embodiment of the present application contains a crosslinked structure containing a sulfonic acid group, it is possible to increase the degree of sulfonation of the entire electrolyte membrane, And at the same time, the dimensional stability and the mechanical properties of the electrolyte membrane can be prevented from deteriorating through crosslinking. That is, the crosslinked electrolyte membrane according to one embodiment of the present application can exhibit improved performance not only in hydrogen ion conductivity, but also in dimensional stability and mechanical properties.

The method for producing a crosslinked poly (arylene ether sulfone) copolymer according to an embodiment of the present application is a method for producing a crosslinked poly (arylene ether sulfone) copolymer comprising a poly (arylene ether sulfone) copolymer comprising a repeating unit represented by the above- (Arylene ether sulfone) copolymer is subjected to a halogen alkylation reaction and an azidation reaction sequentially to introduce an aziralkyl group into the poly (arylene ether sulfone) copolymer , And a step of introducing a crosslinking agent to carry out a crosslinking process of the poly (arylene ether sulfone) copolymer.

In the present application, the halogenalkylation reaction and the azidation reaction are processes for introducing an azido alkyl group for performing a crosslinking process on the poly (arylene ether sulfone) copolymer.

In one embodiment of the present application, the halogenalkylation reaction is carried out by reacting 1.5 mol of chloromethyl methyl ether (ClCH ₂ OCH ₃ ) and 1 mol of tin chloride (Sn (IV) Cl ₄ ) per mole of poly (arylene ether sulfone) For 24 hours at < RTI ID = 0.0 > 50 C. < / RTI > At this time, the pressure condition can proceed at normal pressure without any adjustment. According to this reaction, a chloromethyl group may be introduced into the poly (arylene ether sulfone) copolymer.

As an embodiment of the present application, the azidination reaction is carried out by using 0.6 mol of sodium azide (NaN3) per 1 mol of a poly (arylene ether sulfone) copolymer into which chloromethyl groups have been introduced at 100 DEG C for 12 hours But the present invention is not limited thereto. The sodium azide can react with the chloromethyl group on a one-to-one basis and can be added in an excess amount. According to such a reaction, a poly (arylene ether sulfone) copolymer into which an azimethyl group has been introduced can be produced.

In the present application, the number of azimethyl groups may be about 0.05 per repeating poly (arylene ether sulfone) unit. That is, about five poly (arylene ether sulfone) repeating units may exist within 100 repeating units. The number of methyl groups on the azimethyl group can be controlled by the equivalence of reactants, time, and the like. If the number of methyl groups is too small, the effect of crosslinking may deteriorate. If too much, the stability of the polymer may increase, but the hydrogen ion conductivity may decrease or decrease while the fluidity decreases greatly.

In the present application, the crosslinking agent is selected from the group consisting of 1,4-diethynylbenzene (DEB), 4,4'-diazido-2,2'-stilbene disulfonic acid disodium (DSDA) But it should not be construed that the invention is limited thereto.

In the present application, the crosslinking step may be carried out by a cyclic addition reaction of an aziralkyl group and an ethynyl group.

The mass ratio of the poly (arylene ether sulfone) copolymer to the crosslinking agent may be 1: 0.1 to 1: 3, but is not limited thereto.

In one embodiment of the present application, the crosslinking step comprises reacting a poly (arylene ether sulfone) copolymer having an azimethyl group introduced thereinto with 1,4-diethynylbenzene (DEB) and 4,4'- And dissolving 2,2'-stilbene disulfonic acid disodium (DSDA) in DMF (N, N-dimethylformamide) at various mass ratios. In this solution, CuBr (copper (Ⅰ) bromide) / PMDETA (N, N, N ', N ", N" -pentamethyldiethylenetriamine) The solution thus prepared is cast on a glass plate and then treated at 60 ° C for 12 hours and at 120 ° C for 12 hours to evaporate the solvent and to perform crosslinking through a click reaction. At this time, the pressure can be advanced at normal pressure without any adjustment.

Generally, when the crosslinking structure is introduced into the copolymer, the hydrogen ion conductivity is lowered. However, in the present application, sulfonic acid group and triazole group are contained in the crosslinking structure, whereby the hydrogen ion conductivity can be improved.

In the present application, in the production of the crosslinked poly (arylene ether sulfone) copolymer, the hydrogen ion conductivity, the degree of hydrogen ion conductivity, and the amount of the cross-linking agent, depending on the composition of the monomer, the amount of the aziralkyl group introduced into the main chain of the polymer, Mechanical properties, dimensional stability, and the like.

The polymer electrolyte membrane according to one embodiment of the present application includes the cross-linked poly (arylene ether sulfone) copolymer.

Particularly, in the present application, a cross-linking structure is introduced through a click reaction in a process of casting a polymer solution through a solution process and then heat-treating the solvent to evaporate the solvent. Thus, after the production of the polymer electrolyte membrane, It is possible to easily introduce a crosslinking structure into the membrane.

The present application provides a membrane electrode assembly including the above polymer electrolyte membrane. More specifically, the membrane electrode assembly may further include a cathode provided on one surface of the polymer electrolyte membrane and an anode provided on the other surface of the polymer electrolyte membrane.

The cathode and the anode may each include a catalyst layer and a gas diffusion layer, and the polymer electrolyte membrane may be provided between the cathode catalyst layer and the anode catalyst layer. The polymer electrolyte membrane may be provided in contact with the cathode catalyst layer and the anode catalyst layer.

In the present application, the polymer electrolyte membrane may be provided between the cathode catalyst layer and the anode catalyst layer, and may serve as a medium through which hydrogen ions pass and also serve as a separator between air and hydrogen gas. The higher the hydrogen ion mobility of the polymer electrolyte membrane, the higher the performance of the membrane electrode assembly.

In the present application, the cathode and the anode may be an electrode for a fuel cell of the present specification.

The oxidation reaction of the fuel occurs in the catalyst layer of the anode, and the reduction reaction of the oxidant occurs in the catalyst layer of the cathode.

The catalyst layer may comprise a catalyst.

The catalyst may be one of platinum, a transition metal, and a platinum-transition metal alloy, although the type of the catalyst is not limited as long as it can serve as a catalyst in a fuel cell.

Here, the transition metal is an element of Group 3 to Group 11 in the periodic table, and may be any one of ruthenium, osmium, palladium, molybdenum and rhodium.

Specifically, the catalyst may be selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-molybdenum alloy and platinum-rhodium alloy. .

The catalysts of the catalyst layers themselves can be used not only as a catalyst layer but also as a carbon carrier.

Examples of the carbon-based support include graphite, carbon black, acetylene black, denka black, cacao black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon nano ring, A mixture of two or more selected from the group consisting of fullerene (C60) and Super P black (Super P black) is a preferred example.

The catalyst layer may further comprise an ionomer.

The ionomer serves to provide a passage for transferring ions generated by the reaction between the fuel and the catalyst, such as hydrogen or methanol, to the polymer electrolyte membrane.

The ionomer may specifically be a sulfonated polymer such as Nafion ionomer or sulfonated polytrifluorostyrene.

In one embodiment of the present invention, the electrode for a fuel cell may further include a gas diffusion layer provided on one side of the catalyst layer. The gas diffusion layer serves as a current conductor and serves as a passage for reacting gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive base material.

As the conductive base material, any conventional materials known in the art can be used. For example, carbon paper, carbon cloth or carbon felt can be preferably used. It does not.

The present application provides a fuel cell comprising the above polymer electrolyte membrane.

One embodiment of the present application includes a stack comprising a separator provided between the at least two membrane electrode assemblies and the membrane electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply part for supplying the oxidant to the stack.

The stack includes one or more of the membrane electrode assemblies described above and includes a separator interposed therebetween when the membrane electrode assembly includes two or more membrane electrode assemblies. The separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer the fuel and oxidant supplied from the outside to the membrane electrode assembly.

The oxidant supply part serves to supply the oxidant to the stack. As the oxidizing agent, oxygen is typically used, and oxygen or air can be injected by pumping.

The fuel supply part serves to supply the fuel to the stack, and can be constituted by a fuel tank for storing the fuel and a pump for supplying the fuel stored in the fuel tank to the stack. As the fuel, gas or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following embodiments are intended to illustrate the present disclosure and are not intended to limit the present disclosure.

< Example >

< Example  1 to 6>

One) Poly ( Arylene  ether Sulphone ) Copolymer Production

The poly (arylene ether sulfone) polymer is a copolymer of 4,4'-dihydroxybiphenyl monomer and 3,3'-disulfonate-4,4'-difluorodiphenyl sulfone, 4,4-difluorodi Nucleophilic substitution reaction between phenylsulfone monomers. In this application, 3,3'-disulfonate-4,4'-difluorodiphenylsulfone and 4,4-difluorodiphenylsulfone were used in a 1: 1 molar ratio. The synthesized polymer had a sulfonation degree of 50% and was named "PAES-50".

2) Reformed Poly ( Arylene  ether Sulphone ) Copolymer Production

The chloromethylation reaction and the azidization reaction were carried out on PAES-50 to introduce azide groups capable of participating in the click reaction. In the chloromethylation reaction, one equivalent of SnCl ₄ and 1.5 equivalents of ClCH ₂ OCH ₃ were used for the reaction at 50 ° C. for 2 days, compared to the monomer of PAES-50. After purification, the reaction was carried out at 100 ° C. for 12 hours using an excess amount of NaN ₃ in the azidization reaction. As a result of the reaction, the azido group attached to the unit was about 0.05, and the polymer modified through the above reaction was named "N ₃ -PAES-50".

3) Bridged Poly ( Arylene  ether Sulphone ) Copolymers and Polymers Electrolyte membrane  Produce

The azido group forms a 1,2,3-triazole ring through a cycloaddition reaction with an ethynyl group, and this reaction is called a click reaction because it occurs easily. 1 is a schematic diagram for introducing a crosslinking structure into N ₃ -PAES-50 using a click reaction. Was dissolved in benzene (DEB), 4,4'- diamine map 2,2' steel bendayi acid disodium (DSDA) ethynyl N ₃ -PAES-50 and a cross-linking agent is 1,4 to DMF, CuBr catalyst And the ligands N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) were added. Using a doctor blade, the glass plate was cast to 450 mu m, and then heat-treated in an oven at 60 DEG C for 12 hours and at 120 DEG C for 12 hours. The polymer electrolyte membrane thus prepared was impregnated with distilled water, peeled off from the glass plate, and rinsed with methanol. Then, acid treatment with 1M sulfuric acid aqueous solution was performed to convert the sodium ion of the sulfonic acid group into hydrogen ion, and washed with distilled water.

The cross-linked polyelectrolyte membrane thus obtained was named C-PAES-50 X: Y, and X: Y was a mixture of N ₃ -PAES-50 used in the production of C-PAES- , DSDA).

[Table 1]

< Experimental Example  1> Measurement of mechanical properties

Mechanical properties were measured using a universal testing machine (UTM). The specimen was cut into a dog-bone shape using an ASTM standard D639 electrolyte membrane. The measurement conditions were 25 ° C and 40% humidity.

In general, it has been reported that tensile strength and modulus increase with the introduction of crosslinking, and this trend has been shown when the amount of crosslinking agent is small in the present application. However, in the case of the present invention, the content of the crosslinking agent decreased to some extent. Considering the characteristics of the hydrophilic cross-linking agent, DEB and DSDA cause the chain structure resulting from the click reaction to aggregate to form a non-uniform membrane, or the cross-linking agent is increased, The resulting chain structure may not be attached to N ₃ -PAES-50 or may be attached to only one side, which may be because the free volume of the polymer is increased. However, almost all of the samples showed improved mechanical strength compared to PAES-50 (non-crosslinked electrolyte membrane).

The decrease of percentage elongation as the amount of crosslinking agent increased was consistent with the general trend of crosslinking.

[Table 2]

< Experimental Example  2> Water absorption characteristics

The water content and the expansion coefficient were measured by immersing the polymer electrolyte membrane in distilled water at 30 ° C for 24 hours.

It is generally known that the water content and expansion rate decrease with the introduction of crosslinking. In this application, as the content of the crosslinking agent increases, the water content increases, because the crosslinked structure having a sulfonic acid group is hydrophilic. The expansion coefficients of the PAES-50 membranes increased with increasing crosslinking agent content. The C-PAES-50 3: 1, 2: 1 and 1.5: 1 samples showed lower expansion values than the PAES-50 membrane without crosslinking. These three samples showed a lower expansion rate despite a higher water content than the PAES-50 membrane, which is an indication of improved dimensional stability resulting from the introduction of crosslinking.

IECv (wet) is a value indicating the number of mmol of sulfonic acid group per unit volume of the polymer in the state that the electrolyte membrane is wetted with water. As the content of the crosslinking agent increased, the IECv (wet) value increased because the increase rate of the expansion rate was smaller than the increase amount of the absolute amount of the sulfonic acid group, and then decreased from the point of time when the expansion rate rapidly increased.

[Table 3]

< Experimental Example  3> Hydrogen ion conductivity characteristics

In the present application, improvement of dimensional stability by introduction of a crosslinking structure and improvement of hydrogen ion conductivity by hydrophilicity of a crosslinked structure into which a sulfonic acid group is introduced are simultaneously achieved.

All samples except C-PAES-50 1: 2 showed higher conductivity than Nafion212 at 80 ° C and 90% humidity and C-PAES-50 3: 1, 2: Conductivity improved by 8 ~ 29% compared to electrolyte membrane.

Similar trend was observed at 80 ℃ and 50% humidity condition.

[Table 4]

A photograph of the polymer electrolyte membrane according to Examples 1 to 6 and Comparative Example 1 is schematically shown in Figs. 2 to 8. Fig.

The crosslinked poly (arylene ether sulfone) copolymer according to the present application can be more preferably applied to a polymer electrolyte membrane for a fuel cell. The polymer electrolyte membrane is characterized not only in hydrogen ion conductivity, but also in mechanical properties and dimensional stability.

In preparing the cross-linked poly (arylene ether sulfone) copolymer, the hydrogen ion conductivity, mechanical properties, and the like may vary depending on the composition of the monomer, the amount of the alkyl chain introduced into the main chain of the polymer for the introduction of the cross- , Dimensional stability, and so on.

In addition, in the present application, a cross-linking structure is introduced through a click reaction in a process of casting a polymer solution through a solution process and then heat-treating the solvent to evaporate the solvent. Thus, after the production of the polymer electrolyte membrane, It is possible to easily introduce a crosslinking structure into the membrane.

Claims (9)

(1) and a repeating unit represented by the following formula (2) as a main chain,
A crosslinked poly (arylene ether sulfone) copolymer including a crosslinked structure,
Wherein the crosslinked structure comprises a sulfonic acid group and a triazole-based functional group:
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R 1 to R 3 and R 8 to R 10 are each independently -O-, -S-, -SO ₂ -, -C = O- or -C (CH ₃ ) ₂ -
R4 to R7 and R13 to R16 each independently represent hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms,
R11 and R12 are each independently a -SO ₃ R17,
R17 is H, Li, Na or K,
R18 and R19 are each independently -CH ₂ Cl or -CH ₂ N _3, and
A and A 'are each independently a direct bond or a straight or branched alkylene group having 1 to 10 carbon atoms,
m, o, p and q are each independently 0 to 4, n, r, s and t are each independently 0 to 3,
a and b are the molar ratios of formulas (1) and (2), each independently 0.1 to 0.99. delete (Arylene ether sulfone) copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and
(Arylene ether sulfone) copolymer, which comprises the step of introducing a crosslinking agent to carry out a crosslinking step of the poly (arylene ether sulfone) copolymer,
Wherein the cross-linking structure of the cross-linked poly (arylene ether sulfone) copolymer comprises a sulfonic acid group and a triazole-based functional group, wherein the crosslinked poly (arylene ether sulfone)
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R 1 to R 3 and R 8 to R 10 are each independently -O-, -S-, -SO ₂ -, -C = O- or -C (CH ₃ ) ₂ -
R4 to R7 and R13 to R16 each independently represent hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms,
R11 and R12 are each independently a -SO ₃ R17,
R17 is H, Li, Na or K,
R18 and R19 are each independently -CH ₂ Cl or -CH ₂ N _3,
A and A 'are each independently a direct bond or a straight or branched alkylene group having 1 to 10 carbon atoms,
m, o, p and q are each independently 0 to 4, n, r, s and t are each independently 0 to 3,
a and b are the molar ratios of formulas (1) and (2), each independently 0.1 to 0.99. delete delete [4] The method according to claim 3, wherein the weight ratio of the poly (arylene ether sulfone) copolymer to the crosslinking agent is 1: 0.1 to 1: 3. A polymer electrolyte membrane comprising the crosslinked poly (arylene ether sulfone) copolymer of claim 1. The polymer electrolyte membrane according to claim 7, wherein the electrolyte membrane is for a fuel cell. A fuel cell comprising the polymer electrolyte membrane of claim 7.

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