KR20170096973A - Compound including aromatic ring, polymer including the same and polymer electrolyte membrane using the same - Google Patents

Abstract

The present invention relates to a compound including an aromatic ring, a polymer including the same, a polymeric electrolyte membrane including the same, a membrane-electrode assembly including the polymeric electrolyte membrane, a fuel cell including the membrane-electrode assembly, and a redox flow battery including the polymeric electrolyte membrane. According to an embodiment of the present invention, the polymeric electrolyte membrane produced by using the polymer containing monomers derived from the compound of the present invention shows excellent ion conductivity.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound containing an aromatic ring, a polymer containing the same and a polymer electrolyte membrane using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

This application claims the benefit of Korean Patent Application No. 10-2016-0018432 filed on February 17, 2016, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present invention relates to a compound containing an aromatic ring, a polymer containing the aromatic ring, and a polymer electrolyte membrane using the same.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electric power by using electrons generated during the oxidation and reduction reactions thereof. The membrane electrode assembly (MEA) of a fuel cell is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane, as a portion where an electrochemical reaction of hydrogen and oxygen takes place.

Redox Flow Battery (Redox Flow Battery) is a system in which an active substance contained in an electrolyte is oxidized and reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active substance directly as electric energy to be. The unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).

Fuel cells and redox flow cells are being researched and developed as a next generation energy source because of their high energy efficiency and eco - friendly characteristics with low emission of pollutants.

The most important components of the fuel cell and the redox flow cell are cation exchange polymer electrolyte membranes, which are: 1) excellent proton conductivity 2) cross-over of the electrolyte 3) strong chemical resistance 4) mechanical Physical properties and / or 5) low swelling ratio. The polymer electrolyte membrane is classified into a fluorine system, a partial fluorine system, and a hydrocarbon system. In the case of a partially fluorinated polymer electrolyte membrane, the polymer electrolyte membrane has an excellent physical and chemical stability and a high thermal stability due to its fluorine main chain. Also, like the fluorinated polymer electrolyte membrane, the partial fluorinated polymer electrolyte membrane has the advantages of the hydrocarbon-based polymer electrolyte membrane and the fluorinated polymer electrolyte membrane because the cation-transfer functional group is attached to the end of the fluorinated chain.

In the case of a fuel cell and / or a redox flow battery, there are various advantages such as improving the reactivity of the anode when operating under low humidification conditions, reducing water film phenomenon and catalyst contamination. However, the polymer electrolyte membranes generally used have a problem that their physical properties such as cation conductivity are lowered under low humidification conditions, leading to a rapid deterioration in cell performance. Therefore, it is necessary to study to solve this problem.

Korean Laid-Open Publication No. 2003-0076057

The present invention provides a compound containing an aromatic ring and a polymer electrolyte membrane using the same.

According to one embodiment of the present invention, there is provided a compound comprising an aromatic ring represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R1 and R3 to R5 are the same or different from each other, and each independently hydrogen, a hydroxy group or a halogen group,

R6 is ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - is selected from the group consisting of M ⁺ and -PO ₃ ^2- 2M ⁺ ,

또는

이고, R2 is _{O, S, NH, SO 2} ,

or

ego,

L1 is a direct bond; Or O,

n is an integer of 1 to 10, structures in parentheses of 2 to 10 are the same or different from each other,

M is a Group 1 element.

One embodiment of the present disclosure provides a polymer comprising a monomer derived from the compound of formula (1).

The present disclosure provides a polymer electrolyte membrane comprising a polymer comprising a monomer derived from the compound of Formula 1 in one embodiment.

In addition, one embodiment of the present disclosure relates to an anode; Cathode; And the above-described polymer electrolyte membrane provided between the anode and the cathode.

In addition, one embodiment of the present disclosure includes two or more of the above-described membrane-electrode assemblies; A stack including a bipolar plate disposed between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack.

In addition, one embodiment of the present disclosure includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer electrolyte membrane provided between the anode cell and the cathode cell.

The polymer electrolyte membrane prepared using a polymer containing a monomer derived from a compound according to one embodiment of the present specification has excellent ionic conductivity.

In addition, the polymer electrolyte membrane prepared using a polymer containing a monomer derived from a compound according to one embodiment of the present invention has a high ion exchange capacity (IEC) value at high humidification and / or low humidification conditions .

In addition, since a polymer containing a monomer derived from a compound according to an embodiment of the present invention has a multi acid having at least two acid units per unit structure, the acid dissociation constant (pK _a ) is low However, phase separation is easy and consequently ion conductivity is improved in the production of the polymer electrolyte membrane by using this.

Further, the fuel cell and / or the redox flow battery including the polymer electrolyte membrane are excellent in durability and efficiency.

1 is a schematic view showing an electricity generation principle of a fuel cell.
2 is a view schematically showing a general structure of a redox flow battery.
3 is a schematic view showing one embodiment of a fuel cell.
4 is a graph showing H-NMR values of Compound 6 according to one embodiment of the present invention.
5 is a graph showing F-NMR values of compounds 5 and 6 according to one embodiment of the present invention.
6 is a graph showing the FT-IR values of Polymer 1 according to one embodiment of the present disclosure.
7 is a graph showing molecular weight values measured by GPC for Polymer 1 according to one embodiment of the present disclosure.

Hereinafter, the present invention will be described in more detail.

Generally, the polymer electrolyte membranes used in the present invention exhibit excellent efficiency under a high humidifying condition, but have a problem in that their cationic conductivity is lowered under low humidifying conditions. However, in the present specification, the above-mentioned problems can be solved by using the compound represented by the above-mentioned formula (1).

Specifically, in the present specification, the aromatic ring-containing compound represented by Formula 1 is a benzene ring containing two disulfonamides (-SO ₂ NHSO ₂ -) capable of acting as a multi acid, Linker linking and an acid at the end. The acid (acid) is an ion transport functional ^{_{group, -SO 3 H, -SO 3 -}} M +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M + and -PO ₃ ^{2 -} 2M ⁺ . ^& Lt ^{; /} RTI > Therefore, the polymer containing the monomer derived from the compound represented by the formula (1) has an increased number of acid per unit unit, and the ion exchange capacity (IEC) value of the polymer electrolyte membrane containing the polymer is increased . As a result, the polymer electrolyte membrane can exhibit excellent cation conductivity not only under high humidification conditions but also under low humidification conditions.

According to one embodiment of the present invention, at least one of R1 and R3 to R5 is a halogen group and the rest is hydrogen, and the halogen group is fluorine (F) or chlorine (Cl).

According to one embodiment of the present invention, in Formula 1, R5 is fluorine (F), and R1, R3 and R4 are hydrogen.

According to one embodiment of the present invention, in the above formula (1), R ₂ is SO ₂ .

According to one embodiment of the present invention, in Formula 1, L1 is a direct bond.

According to one embodiment of the present invention, in the above formula (1), L1 is O.

According to an exemplary embodiment of the present disclosure, in the above-mentioned formula (I), wherein R6 is -SO ₃ H or -SO ₃ ^- M a ^+.

According to one embodiment of the present disclosure, the Group 1 element M can be Li, Na or K.

According to an exemplary embodiment of the present disclosure, in the above-mentioned formula (I), wherein R6 is a -SO ₃ H.

According to one embodiment of the present invention, the compound represented by the formula (1) is any one selected from the following structures.

One embodiment of the present invention provides a polymer comprising a monomer derived from the compound represented by Formula 1 above. The above monomers have the advantage of exhibiting improved reactivity during the polymerization reaction as described above.

As used herein, the term "monomer" means a structure in which a compound is contained in the polymer in a form of two or more groups by polymerization reaction. Specifically, the monomer derived from the compound represented by the formula (1) may have a structure represented by the following formula (2). However, it is not limited thereto.

(2)

In Formula 2, R 2, R 6, L 1 and n have the same definitions as in Formula 1.

As described above, the polymer according to one embodiment of the present invention includes a monomer derived from the compound represented by the formula (1). As a result, since the ion transfer functional group containing a partial fluorine group is present in the form of a pendant in the polymer, the ion transfer functional groups are easily gathered in the polymer to easily form an ion channel, thereby easily forming an ion channel. As a result, The ionic conductivity of the polymer electrolyte membrane can be improved. In addition, since it contains multi acid including two acid units per monomer unit structure, the effect of improving ionic conductivity is more excellent.

According to one embodiment of the present disclosure, the polymer may be a random polymer. In this case, a polymer having a high molecular weight can be obtained by a simple polymerization method.

At this time, the monomer derived from the compound represented by the formula (1) plays a role of controlling the ionic conductivity of the polymer electrolyte membrane including the polymer, and the remainder of the comonomer polymerized in random form has a role of improving the mechanical strength do.

According to one embodiment of the present invention, the monomer derived from the compound represented by the formula (1) may be contained in an amount of 0.1 to 100 mole% of the whole polymer. Specifically, the polymer includes only a monomer derived from the compound represented by the formula (1). In another embodiment, the polymer may further comprise a second monomer other than the monomer derived from the compound represented by the formula (1). In this case, the content of the monomer derived from the compound represented by the formula (1) is preferably 0.5 mol% to 65 mol%. , More preferably from 5 mol% to 65 mol%. Polymers comprising monomers derived from compounds within this range have mechanical strength and high ionic conductivity.

As the second monomer, those known in the art can be used. At this time, one kind or two or more kinds of the second monomers may be used.

Examples of the second monomer include perfluorosulfonic acid polymer, hydrocarbon polymer, polyimide, polyvinylidene fluoride, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyphosphazine, polyethylene naphthalate, polyester, Doped polybenzimidazole, polyether ketone, polysulfone, an acid thereof, or a monomer constituting the base thereof may be used.

According to one embodiment of the present invention, the polymer may include a repeating unit represented by the following formula (3).

(3)

In Formula 3,

A is represented by the above formula (2)

B comprises a unit derived from the following formula (4)

C comprises a unit derived from the following formula 5,

u: v is from 1: 100 to 100: 1,

[Chemical Formula 4]

In Formula 4,

X is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -,

[Chemical Formula 5]

In Formula 5,

Y is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -,

Z1 and Z2 are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group.

According to one embodiment of the present invention, the formula (4) may be represented by any one of the following formulas.

According to one embodiment of the present disclosure, X is a direct bond.

According to one embodiment of the present invention, the formula (5) may be represented by any one of the following structural formulas.

According to an exemplary embodiment of the present disclosure, wherein Y is -SO ₂ - it is a.

According to one embodiment of the present disclosure, the content of the second monomer in the polymer may be more than 0 wt% but not more than 99.9 wt%.

According to one embodiment of the present invention, the molar ratio of A in the repeating unit represented by Formula 3 may be 0.1 to 0.5, the molar ratio of B may be 0.5 to 2.0, and the molar ratio of C may be 0.5 to 1.0. More preferably, the molar ratio of A may be 0.1 to 0.3, the molar ratio of B may be 0.8 to 1.2, and the molar ratio of C may be 0.7 to 0.9.

According to one embodiment of the present disclosure, when the polymer comprises the second monomer, the polymer may be a random polymer.

An embodiment of the present disclosure also provides a polymer electrolyte membrane comprising the above polymer. The polymer electrolyte membrane can exhibit the above-described effects.

As used herein, the term "electrolyte membrane" is a membrane capable of ion exchange, and includes a membrane, an ion exchange membrane, an ion transport membrane, an ion conductive membrane, a membrane, an ion exchange membrane, A transfer electrolyte membrane, an ion conductive electrolyte membrane, and the like.

The polymer electrolyte membrane according to the present specification can be produced by using materials and / or methods known in the art, except that the membrane includes monomers derived from the compound represented by the formula (1).

According to another embodiment, the weight average molecular weight of the polymer contained in the polymer electrolyte membrane may be 500 to 5,000,000 (g / mol), and may be 20,000 to 2,000,000 (g / mol) More specifically from 50,000 to less than 1,000,000 (g / mol).

When the weight average molecular weight of the copolymer is not less than 500 and not more than 5,000,000 (g / mol), the mechanical properties of the electrolyte membrane are not deteriorated and the solubility of the appropriate polymer is maintained, thereby facilitating the production of the electrolyte membrane.

According to one embodiment of the present invention, the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g. When the ion exchange capacity value is in the range, the ion channel in the polymer electrolyte membrane is formed, and the polymer can exhibit ion conductivity.

According to one embodiment of the present invention, the thickness of the electrolyte membrane may be 1 탆 to 500 탆, specifically, 10 탆 to 200 탆. When the thickness of the electrolyte membrane is 1 占 퐉 to 500 占 퐉, electric short and cross-over of the electrolyte material can be reduced, and excellent cation conductivity characteristics can be exhibited.

According to one embodiment of the present invention, the ionic conductivity of the polymer electrolyte membrane may be 0.001 S / cm or more and 0.5 S / cm or less, and may be 0.01 S / cm or more and 0.5 S / cm or less.

According to another embodiment, the ion conductivity of the polymer electrolyte membrane can be measured under a humidifying condition. The humidifying condition may mean a full humidifying condition, may mean a relative humidity (RH) of 10% to 100%, and may mean a relative humidity (RH) of 30% to 100%.

According to one embodiment of the present invention, the ionic conductivity of the polymer electrolyte membrane may be 0.001 S / cm or more and 0.5 S / cm or less, and may be measured at a relative humidity (RH) of 10% to 100%. According to another embodiment, the ionic conductivity of the polymer electrolyte membrane may be 0.01 S / cm or more and 0.5 S / cm or less, and may be measured at a relative humidity (RH) of 30% to 100%.

According to one embodiment of the present disclosure, at least a portion of the polymer may be in the form of a metal salt. In addition, the metal salt may be substituted in the form of an acid.

Specifically, R6 is -SO ₃ in the formula ^{1 - M +, -COO - M} +, -PO 3 H - M +, or -PO ₃ ^2- 2M ⁺ is a metal added to the acid solution in place of Polymer M H ( Hydrogen) may be formed on the surface of the electrolyte membrane.

According to one embodiment of the present disclosure, it may be a general acid solution used in the acid treatment, specifically hydrochloric acid or sulfuric acid.

According to one embodiment of the present invention, the concentration of the acid solution may be 0.1 M or more and 10 M or less, and specifically 1 M or more and 2 M or less. When the concentration of the acid solution is 0.1 M or more and 10 M or less, the metal membrane M can be easily replaced with hydrogen without damaging the electrolyte membrane.

An embodiment of the present disclosure also includes an anode; Cathode; And the above-described polymer electrolyte membrane provided between the anode and the cathode.

The membrane-electrode assembly (MEA) means a junction body of an electrode (cathode and anode) where an electrochemical catalytic reaction of fuel and air takes place and a polymer membrane in which hydrogen ions are transferred, and the electrode (cathode and anode) It is a single integral unit.

The membrane-electrode assembly of the present invention can be produced by a conventional method known in the art, such that the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane. For example, the cathode; Anode; And an electrolyte membrane positioned between the cathode and the anode in close contact with each other at a temperature of 100 to 400.

The anode electrode may include an anode catalyst layer and an anode gas diffusion layer. The anode gas diffusion layer may again include an anode microporous layer and an anode electrode substrate.

The cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer. The cathode gas diffusion layer may again include a cathode microporous layer and a cathode electrode substrate.

FIG. 1 schematically shows an electricity generating principle of a fuel cell. In a fuel cell, a basic unit for generating electricity is a membrane electrode assembly (MEA), which includes an electrolyte membrane 100 and an electrolyte membrane 100, And an anode 200a and a cathode 200b electrodes formed on both sides of the cathode 200a. 1 showing the principle of electricity generation of a fuel cell, in the anode 200a, oxidation reaction of a fuel such as hydrogen or hydrocarbons such as methanol or butane occurs to generate hydrogen ions (H ⁺ ) and electrons (e ^- ) , The hydrogen ions move to the cathode 200b through the electrolyte membrane 100. [ In the cathode 200b, hydrogen ions transferred through the electrolyte membrane 100 react with an oxidizing agent such as oxygen and electrons to generate water. This reaction causes electrons to migrate to the external circuit.

The catalyst layer of the anode electrode is preferably a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum- Lt; / RTI > The catalyst layer of the cathode electrode is a place where a reduction reaction of an oxidizing agent occurs, and a platinum or platinum-transition metal alloy can be preferably used as a catalyst. The catalysts can be used not only by themselves but also by being supported on a carbon-based carrier.

The process of introducing the catalyst layer can be performed by a conventional method known in the art. For example, the catalyst ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer. The method of coating the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used. The catalyst ink may typically consist of a catalyst, a polymer ionomer and a solvent.

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, carbon paper, carbon cloth or carbon felt can be preferably used. The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive base. The microporous layer can be used to improve the performance of the fuel cell under low humidification conditions and serves to reduce the amount of water flowing out of the gas diffusion layer to make the electrolyte membrane sufficiently wet.

One embodiment of the present disclosure includes two or more of the above-described membrane-electrode assemblies; A stack including a bipolar plate disposed between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack.

When the electrolyte membrane according to one embodiment of the present invention is used as an ion exchange membrane of a fuel cell, the above-described effect can be obtained.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction.

The fuel cell can be manufactured according to a conventional method known in the art using the above-described membrane-electrode assembly (MEA). For example, the membrane-electrode assembly (MEA) and the bipolar plate manufactured as described above can be manufactured.

The fuel cell of the present invention comprises a stack, a fuel supply, and an oxidant supply.

3 schematically shows the structure of a fuel cell, which includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80. [

The stack 60 includes one or more of the membrane electrode assemblies described above and includes a separator interposed therebetween when two or more membrane electrode assemblies are included. 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 70 serves to supply the oxidant to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air can be injected into the oxidizing agent supplying portion 70 and used.

The fuel supply unit 80 serves to supply the fuel to the stack 60 and includes a fuel tank 81 for storing the fuel and a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 Lt; / RTI > 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.

The fuel cell may be a polymer electrolyte fuel cell, a direct liquid fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell, a direct ethanol fuel cell, or a direct dimethyl ether fuel cell.

In addition, one embodiment of the present disclosure includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer electrolyte membrane according to an embodiment of the present invention provided between the anode cell and the cathode cell.

Redox Flow Battery (Redox Flow Battery) is a system in which an active substance contained in an electrolyte is oxidized and reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active substance directly as electric energy to be. The redox flow battery utilizes the principle of charging and discharging electrons by receiving electrons when an electrolyte containing an active material having a different oxidation state meets the ion exchange membrane. Generally, a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occur, and a circulation pump circulating the electrolyte between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, Exchange membrane.

When the electrolyte membrane according to one embodiment of the present invention is used as the ion exchange membrane of the redox flow cell, the above-described effect can be obtained.

The redox flow cell of the present specification can be produced according to a conventional method known in the art, except that it includes a polymer electrolyte membrane according to one embodiment of the present specification.

2, the redox flow battery is divided into a positive electrode cell 32 and a negative electrode cell 33 by an electrolyte film 31. As shown in FIG. The anode cell 32 and the cathode cell 33 each include an anode and a cathode. The anode cell (32) is connected to the anode tank (10) for supplying and discharging the anode electrolyte (41) through a pipe. The cathode cell 33 is also connected to a cathode tank 20 for supplying and discharging the cathode electrolyte 42 through a pipe. The electrolytic solution is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) occurs in which the oxidation number of ions is changed, so that charging and discharging occur in the anode and the cathode.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

≪ Preparation Example 1 &

1) Synthesis of Compound 3

Compound 1 (Sodium 5,5'-sulfonylbis (2 -fluorobenzenesulfonate)) 10g (30.65 mmol) was dissolved in 100ml POCl ₃ was added PCl ₅ 15.32g (73.57 mmol) and heated to 120 ℃. The reaction mixture was stirred at 120 ° C for 1 hour, then heated again, and further stirred at 150 ° C for 2 hours and cooled to room temperature. The reaction was distilled under reduced pressure to remove excess POCl ₃ , dissolved in CH ₂ Cl ₂ and washed several times with water at 0 ° C. The organic layer was dried over MgSO ₄ and distilled under reduced pressure to obtain a crude sulfonyl chloride compound. The sulfonyl chloride compound was dissolved in CH ₂ Cl ₂ without further purification, and after cooling to 0 ° C, 100 ml of ammonia water was slowly added dropwise. The reaction temperature was slowly raised to react at room temperature for 16 hours and then distilled under reduced pressure under high pressure. The resulting compound was dissolved in ethyl acetate and washed several times with water. The organic layer was dried over MgSO ₄ and distilled under reduced pressure to obtain 4.58 g (yield: 45.9%) of the compound 3 (5,5'-sulfonylbis (2-fluorobenzenesulfonamide) ).

2) Synthesis of Compound 5

4.58 g (14.1 mmol) of the compound 3 (5,5'-sulfonylbis (2-fluorobenzenesulfonamide)) obtained in the above was dissolved in 40 ml of acetonitrile and the compound 4 (1,1,2,2-tetrafluoroethane- disulfonyl dichloride (8.52 g, 31 mmol) was added and the reaction was cooled to 0 < 0 > C. 11.3 ml (84 mmol) of Et ₃ N was slowly added dropwise to the reaction mixture at 0 ° C, the temperature was gradually raised to room temperature, and the mixture was stirred for 1 to 2 hours. After distilling off the solvent under reduced pressure, the crude product was dissolved in ethyl acetate and washed several times with 1N HCl to remove Et ₃ N. The organic layer was separated, dried over MgSO ₄ , distilled and purified by column chromatography using methylene chloride: methyl alcohol = 9: 1 to obtain the compound 5 (2,2 '- (5,5'-sulfonylbis 2-fluoro-5,1-phenylenesulfonyl)) bis (1,1,2,2-tetrafluoroethanesulfonyl chloride)) was obtained in a yield of 85%.

3) Synthesis of Compound 6

6.75 g (12.0 mmol) of the compound 5 (2,2 '- (5,5'-sulfonylbis (2-fluoro-5,1-phenylenesulfonyl)) bis (1,1,2,2-tetrafluoroethanesulfonyl chloride) After dissolving in 40 ml of 1,4-dioxane, 40 ml of 10% HCl was added and the mixture was heated to 100 ° C. The reaction was stirred at 100 < 0 > C for 16 hours, then cooled to room temperature and all solvents were removed by vacuum distillation. The crude compound thus obtained was dissolved in H ₂ O, washed several times with CH ₂ Cl ₂ to remove impurities, and the remaining water layer was distilled off again under reduced pressure. After the compound was dissolved in CH ₂ Cl ₂ , the solution was gradually added dropwise to n-hexane, and the resulting solid was filtered and dried under N ₂ gas to obtain the compound 6 (2,2 '- (sulfonylbis (6-fluoro-3 , 1-phenylenesulfonyl)) bis (1,1,2,2-tetrafluoroethane-1-sulfonic acid)) was obtained in a yield of 86.0%.

4 is a graph showing the 1 H-NMR value of the compound 6 synthesized in Preparation Example 1. Fig.

5 is a graph showing F-NMR values of the compounds 5 and 6 synthesized in Preparation Example 1. FIG.

PREPARATION EXAMPLE 2 Synthesis of Random Polymer 1

Each of the monomers and potassium carbonate (molar ratio 0.2: 1.0: 0.8, K ₂ CO ₃ : molar ratio 4) were mixed at a ratio of 20 wt% of dimethylsulfoxide (DMSO) and 20 wt% of benzene, Lt; 0 > C for 16 hours to prepare Polymer 1.

6 is a graph showing the FT-IR value of Polymer 1 synthesized in Production Example 2. FIG.

Table 1 below shows the molecular weight values measured by GPC for the Polymer 1 synthesized in Production Example 2. < tb > < TABLE >

Mn Mw MP (Daltons) PDI % Area 5.96 x 10 ⁴ 1.24 X 10 ⁵ 7.97 X 10 ⁴ 2.08 100.00

7 is a graph showing molecular weight values measured by GPC for Polymer 1 synthesized in Production Example 2. Fig.

< Manufacturing example  3> Synthesis of Random Polymer 2

Each of the monomers and potassium carbonate (molar ratio 0.2: 1.0: 0.8, K ₂ CO ₃ : molar ratio 4) were mixed at a ratio of 20 wt% of dimethylsulfoxide (DMSO) and 20 wt% of benzene, Lt; 0 &gt; C for 16 hours to prepare Polymer 2.

&Lt; Example 1 >

A polymer electrolyte membrane was prepared using the polymer 1 obtained in Preparation Example 2, and its molecular weight was measured by GPC, and the cation conductivity and ion exchange capacity (IEC) of the pure membrane were measured.

&Lt; Comparative Example 1 &

A polymer electrolyte membrane was prepared using the polymer 2 obtained in Preparation Example 3, the molecular weight was measured by GPC, and the cation conductivity and the ion exchange capacity (IEC) of the pure membrane were measured.

Mn
(g / mol) Mw
(g / mol) PDI
(Mw / Mn) Ion conductivity (S / cm) Ion exchange capacity
IEC (mmol / g) Example 1 59,600 124,000 2.08 0.126 2.16 Comparative Example 1 62,000 486,000 7.8 0.11 1.91

When a polymer containing a monomer derived from a compound containing an aromatic ring represented by the formula (1) according to Example 1 was used as a polymer electrolyte membrane, the polymer electrolyte membrane of the present invention had at least two acid units per unit structure unit, it has been confirmed that phase separation is easy and consequently ion conductivity is improved and ion exchange capacity (IEC) value is high at high humidification and / or low humidification condition.

100: electrolyte membrane
200a: anode
200b: cathode
10, 20: tank
11, 21: pump
31: electrolyte membrane
32: anode cell
33: cathode cell
41: anode electrolyte
42: cathode electrolyte
60: Stack
70: oxidant supplier
80: fuel supply unit
81: Fuel tank
82: Pump

Claims (15)

1. A compound comprising an aromatic ring represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
R1 and R3 to R5 are the same or different from each other, and each independently hydrogen, a hydroxy group or a halogen group,
R6 is ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - is selected from the group consisting of M ⁺ and -PO ₃ ^2- 2M ⁺ ,
R2 is _{O, S, NH, SO 2} ,

or

ego,
L1 is a direct bond; Or O,
n is an integer of 1 to 10, structures in parentheses of 2 to 10 are the same or different from each other,
M is a Group 1 element. _{2. The} compound of claim 1, wherein R &lt; ₂ &gt; is SO2. The method according to claim 1, wherein R6 is -SO ₃ H or -SO ₃ ^- compound, characterized in that the M ^+. The compound according to claim 1, wherein the compound having an aromatic ring represented by the formula (1) is any one selected from the following structures:

A polymer comprising a monomer derived from the compound of claim 1. The polymer according to claim 5, wherein the polymer further comprises a second monomer other than the monomer derived from the compound having an aromatic ring represented by the formula (1). The polymer according to claim 5, wherein the polymer is a random polymer. 6. The polymer of claim 5, wherein the weight average molecular weight of the polymer is from 500 g / mol to 5,000,000 g / mol. A polymer electrolyte membrane comprising the polymer of any one of claims 5 to 8. The method of claim 9,
Wherein the polymer electrolyte membrane has an ion conductivity of 0.001 S / cm to 0.5 S / cm. The method of claim 9,
Wherein the polymer electrolyte membrane has an ion exchange capacity (IEC) value of 0.01 mmol / g to 5 mmol / g. The method of claim 9,
Wherein the polymer electrolyte membrane has a thickness of 1 占 퐉 to 500 占 퐉. Anode; Cathode; And a polymer electrolyte membrane according to any one of claims 9 to 12 provided between the anode and the cathode. At least two membrane-electrode assemblies; A stack including a bipolar plate disposed between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supplier for supplying an oxidant to the stack, wherein the membrane-electrode assembly comprises an anode; Cathode; And a polymer electrolyte membrane provided between the anode and the cathode, wherein the polymer electrolyte membrane comprises the polymer according to any one of claims 5 to 8. A polymer electrolyte fuel cell comprising: A positive electrode including a positive electrode and a positive electrode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer electrolyte membrane disposed between the anode cell and the cathode cell, wherein the polymer electrolyte membrane comprises the polymer according to any one of claims 5 to 8. The redox flow battery according to claim 1,

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