KR20080109225A - Sulfonated monomer and use of the same - Google Patents

Abstract

A sulfonated monomer is provided to improve the stability of a sulfonated polymer due to a structure substituted with a salt of a sulfonic acid or a sulfonic acid on an aromatic ring. A compound is represented by the chemical formula 1. In the chemical formula 1, X is -F, -Cl, -Br or -I; Y is -H or -SO3M; one of Q1 and Q2 is the chemical formula A and another of Q1 and Q2 is H; E is - C(=O) - or - S(=O) 2-; and M is -H, -Na or -K.

Description

Sulfonated monomers and their use {SULFONATED MONOMER AND USE OF THE SAME}

1 is a graph showing hydrogen ion conductivity of each of the electrolyte membranes prepared in Examples 6 and 7 and the conventional Nafion 115.

The present invention relates to sulfonated monomers, more specifically monomers usable in the preparation of polymers by nucleophilic aromatic substitution polymerization, and polymers prepared using the same. The present invention also relates to an electrolyte membrane including the polymer and a fuel cell including the same.

Polyarylene ether polymers (poly (arylene ether) s) is a polymer that can be applied to many fields because of excellent thermal stability and chemical stability. In particular, the polyarylene ether-based polymer may be used as a material for forming a membrane for fuel cells, and sulfonated polyarylene ether-based polymer may be more preferably used.

In general, the sulfonated polyarylene ether-based polymer may be prepared directly by polymerization of the sulfonated monomer or by postsulfonation of a polymer obtained by polymerizing a monomer having no sulfonic acid group. .

For example, a method of preparing a sulfonated polyarylene ether-based polymer by phonation described below may be performed by reacting the polymer with butyllithium to form a carbon anion, and quenching the reaction with sultone. There is a method of producing the reaction by terminating the carbon anion to sulfur dioxide (sulfur dioxide).

At this time, the stability of the membrane in the fuel cell depends on the position of the sulfonic acid group of the polymer included in the membrane. Aromatic sulfonation, which introduces sulfonic acid groups into aromatic rings, is a reversible reaction, and consequently, the bond between the aromatic ring and the sulfonic acid group may be the weakest at the site where the sulfonic acid group is most easily introduced. In particular, in the case of sulfonation of a polyarylene ether-based polymer, this tendency is typically shown at the ortho site relative to the oxygen link (ether bond) on the aromatic ring, and thus ortho to the oxygen link (ether bond). The sulfonic acid groups present at the (ortho) site can fall off the aromatic ring well. Therefore, when a sulfonated polymer, particularly a sulfonated polyarylene ether polymer, is used as an electrolyte membrane, for example, a fuel cell is driven, a sulfonic acid group is separated from the polymer, resulting in a decrease in membrane performance. .

Due to this problem, there is a need for a monomer for preparing a sulfonated polyarylene ether polymer of a more stable form. In particular, there is a need for monomers in which sulfonated acid groups are introduced at the less activated sites of aromatic rings, avoiding the phonation of polymers later.

The present invention seeks to provide a new type of sulfonated monomer which can be used for the preparation of sulfonated polymers by nucleophilic aromatic substitution polymerization. In addition, in the polymer produced by the polymerization reaction using the sulfonated monomer, the stability of the sulfonated polymer can be improved by having a structure in which a sulfonic acid or a salt of sulfonic acid is substituted on an aromatic ring substituted with an electron withdrawing group. To provide a sulfonated monomer and a method for preparing the same.

In addition, the present invention is to provide a sulfonated polymer, preferably a sulfonated polyarylene ether-based polymer prepared using the sulfonated monomer.

The present invention also provides an electrolyte membrane including the sulfonated polymer and a fuel cell using the same.

The present invention provides a compound represented by the following Chemical Formula 1 as a sulfonated monomer in a new form.

[Formula 1]

In Formula 1, X is -F, -Cl, -Br, or -I;

Y is -H, or -SO ₃ M;

이고, Q¹ 및 Q² 중 나머지 하나는 -H이며;One of Q ¹ and Q ²

And the other of Q ¹ and Q ² is -H;

E is -C (= 0)-, or -S (= 0) _2- ;

M is -H, -Na or -K.

The present invention also provides a polymer prepared by using the compound represented by Chemical Formula 1 as a monomer for nucleophilic aromatic substitution polymerization.

The present invention also provides an electrolyte membrane including the polymer, preferably a sulfonated polyarylene ether-based polymer, and a fuel cell including the electrolyte membrane.

Hereinafter, the present invention will be described in detail.

The compound represented by Formula 1 according to the present invention is a benzophenone derivative or a diphenyl sulfone derivative having a benzophenone group or a diphenyl sulfone group at the center thereof; One benzene ring thereof is substituted with sulfonic acid or a salt of sulfonic acid; Two halogens are substituted in another benzene ring, and optionally, the halogen-substituted benzene ring has a structure in which a sulfonic acid or a salt of sulfonic acid is substituted. In particular, the compound represented by Chemical Formula 1 is characterized in that a salt of sulfonic acid or sulfonic acid is substituted on a benzene ring substituted with an electron withdrawing group such as a ketone group (C═O) or a sulfone group (S (═O) ₂ ) to be.

In this case, two parameters X in the compound represented by Chemical Formula 1 may be different from each other, and a compound corresponding thereto also belongs to the scope of the present invention.

When performing a nucleophile aromatic substitution reaction by a nucleophile using the compound represented by Formula 1 according to the present invention, a position where parameter X is substituted in the compound represented by Formula 1, that is, a position where halogen is substituted The substitution reaction may occur at, and the parameter X may be a leaving group.

In this case, since the compound represented by Formula 1 is substituted with two parameters X representing halogen on the aromatic ring, the reaction site attacked by the reactive functional group of the nucleophile in the nucleophilic aromatic substitution reaction may be two.

Therefore, when a nucleophilic aromatic substitution reaction is performed using a nucleophile having two or more reactive functional groups in a molecule and the compound represented by Chemical Formula 1, a polymerization reaction may proceed to produce a sulfonated polymer. In this case, non-limiting examples of the reactive functional group include a hydroxy group, an amine group, a thiol group, a carbanion, and the like, and the nucleophile may be a nucleophile in which these reactive functional groups are combined. For example, if the nucleophile having two or more reactive functional groups in the molecule is a diol compound such as HO-R-OH, wherein R is alkylene or arylene, then the sulfonated polymer, preferably sulfonated Polyarylene ether polymer may be prepared.

As such, sulfonated polymers, preferably sulfonated polyarylene ether-based polymers prepared from the compound represented by Chemical Formula 1 by a nucleophilic aromatic substitution polymerization reaction, may exhibit stability and ion exchange capacity (IEC). And ion density can be improved.

As mentioned in the prior art, in sulfonated polymers, sulfonic acid groups linked to the ortho site relative to the oxygen link (ether bond) on the aromatic ring tend to deviate well from the aromatic ring. As such, the sulfonic acid group may fall from the aromatic ring, thereby lowering the stability of the sulfonic acid group, which may cause a problem that the ion exchange capacity and the ion density of the sulfonated polymer are lowered.

However, when an electron withdrawing group is introduced on the aromatic ring, the bonding stability between the sulfonic acid group and the aromatic ring connected to the ortho site to the oxygen link (ether bond) on the aromatic ring is greatly improved, and thus the sulfonic acid group is aromatic The inventors have found that cleavage from the ring can be inhibited. It has also been found that this can improve ion exchange capacity and ion density through sulfonic acid groups in sulfonated polymers, preferably sulfonated polyarylene ether-based polymers. In this case, non-limiting examples of the electron withdrawing group include -C (= 0)-or -S (= 0) _2- .

For example, in the polymer represented by the following Chemical Formula 2, the sulfonic acid group on the aromatic ring to which SO ₂ is connected to the electron withdrawing group is improved, so that the sulfonic acid group on the aromatic ring to which the electron withdrawing group is not connected is hardly separated from the aromatic ring. Degradation of stability can lead to desulfonation.

[Formula 2]

Therefore, in the sulfonated polymer, preferably sulfonated polyarylene ether-based polymer prepared from the compound represented by Formula 1 according to the present invention, all sulfonic acid (salt) groups are directly substituted with an aromatic ring having an electron withdrawing group. As such, the acidity and hydrolytic stability associated with hydrogen ion conductivity can be improved. In addition, this may also improve the ion exchange capacity and ion density of the sulfonated polymer.

The preparation method of the compound represented by Chemical Formula 1 is as follows. However, the following schemes are merely exemplary, and the method for preparing the compound according to the present invention is not limited by the following schemes.

The compound represented by Chemical Formula 1 may be prepared by the following Scheme 1.

Scheme 1

In Scheme 1, X, Y, E and M are as defined in formula (1).

In Scheme 1, the first step is to perform a Friedel Craft reaction (Lewis acid) is not particularly limited and can be used a conventional Lewis acid known in the art.

In addition, in Scheme 1, the second step is a step of sulfonation; And the use of metal halides to convert the sulfonic acid into a salt of sulfonic acid.

First, the sulfonation is not particularly limited, and may be performed according to conventional methods known in the art. As a non-limiting example, the benzophenone or diphenyl sulfone synthesized in the first step may be mixed with sulfuric acid, followed by reaction at 10 to 100 ° C., whereby the sulfonic acid group may be introduced onto the aromatic ring. That is, a compound in which M is H in Formula 1 may be prepared. The sulfuric acid may be concentrated sulfuric acid and / or fuming sulfuric acid, the fuming sulfuric acid is preferably 60% fuming sulfuric acid.

In addition, the number of sulfonic acid groups introduced into the aromatic ring in the sulfonation step may be adjusted according to the reaction conditions. Specifically, the sulfonic acid group by sulfonation may be introduced primarily on the aromatic ring in which no parameter X is present among the two aromatic rings in the benzophenone or diphenyl sulfone synthesized in the first step. At this time, further sulfonation may occur as the concentration of sulfuric acid as a reactant, reaction temperature and / or reaction time increases, whereby a second sulfonic acid group may be additionally introduced on the aromatic ring in which parameter X is present.

In addition, a compound in which M is Na or K in Formula 1 may be prepared by converting sulfonic acid to a salt of sulfonic acid using a metal halide in a second step. Thus, the step of using a metal halide in the second step may be an optional step that can be further proceeded if the desired final compound is a compound in the form of a salt of sulfonic acid. In this case, the metal halide may be sodium halide or potassium halide, and the halide may be -F, -Cl, -Br or -I.

In addition, the compound represented by Formula 1 may be prepared by the following Scheme 2.

Scheme 2

In Scheme 2, X, E and M are as defined in Formula 1, X ¹ is -Cl, -Br or -I.

The first step in Scheme 2 is to prepare or lithiation Grignard reagent, and then react with benzoyl halide or benzenesulfonyl halide to synthesize benzophenone or diphenyl sulfone.

In addition, the second step in Scheme 2 is the step of sulfonating (sulfonation) as in Scheme 1; And the use of metal halides to convert the sulfonic acid into a salt of sulfonic acid.

In addition, in Schemes 1 and 2, the first and second steps may be performed in the presence of a solvent or may be performed without a solvent. The solvent is not particularly limited, and conventional organic solvents and / or water known in the art may be used.

In addition, the method for preparing a compound represented by Chemical Formula 1 includes a method of using a reactant similar to the reactants of Schemes 1 and 2 or by a similar route to the schemes.

The polymer according to the present invention is not particularly limited as long as it is a polymer produced by using the compound represented by Formula 1 of the present invention as a monomer for a nucleophilic aromatic substitution polymerization reaction.

Specifically, as described above, the polymer of the present invention may be prepared by reacting a compound represented by Chemical Formula 1 and a nucleophile having two or more reactive functional groups in the molecule together. In this case, non-limiting examples of the reactive functional group include a hydroxy group, an amine group, a thiol group, a carbanion, and the like.

Preferably, the nucleophile having two or more reactive functional groups in the molecule may be a compound represented by the formula HO-R-OH, wherein R is alkylene or arylene, and thus the polymer of the present invention may be It may be a sulfonated polyarylene ether polymer including a repeating unit represented by (sulfonated poly (arylene ether) s).

[Formula 3]

In Formula 3, Y is -H, or -SO ₃ M;

이고, Q¹ 및 Q² 중 나머지 하나는 -H이며;One of Q ¹ and Q ²

And the other of Q ¹ and Q ² is -H;

E is -C (= 0)-, or -S (= 0) _2- ;

M is -H, -Na or -K;

R is arylene or alkylene.

In this case, R is preferably C ₆ ~ C ₁₀₀ Arylene (arylene) or C ₁ ~ C ₁₀₀ Alkylene (alkylene), or may be a hybrid functional group thereof.

In addition, the compound represented by the formula (1) and the nucleophile compound represented by the formula HO-R-OH (wherein R is alkylene or arylene) are reacted together sulfonated containing a repeating unit represented by the formula (3) When preparing a polyarylene ether-based polymer can be represented by the following reaction scheme 3.

Scheme 3

이고, Q¹ 및 Q² 중 나머지 하나는 -H이며; E는 -C(=O)-, 또는 -S(=O)₂-이며; M은 -H, -Na 또는 -K이며; R은 아릴렌(arylene) 또는 알킬렌(alkylene)이며; n은 1~5000 이다. In Scheme 3, X is -F, -Cl, -Br, or -I; Y is -H, or -SO ₃ M; One of Q ¹ and Q ²

And the other of Q ¹ and Q ² is -H; E is -C (= 0)-, or -S (= 0) _2- ; M is -H, -Na or -K; R is arylene or alkylene; n is 1-5000.

According to the present invention, since the compound represented by the formula (1) has already introduced a sulfonic acid group (or sulfonate) and an electron withdrawing group at a specific position on the aromatic ring, the compound represented by the formula (1) for the nucleophilic aromatic substitution reaction monomer Similarly, the polymer of the present invention prepared by using a sulfonic acid group (or sulfonate) and an electron withdrawing group are introduced at a specific position on the aromatic ring. Therefore, as mentioned above, the sulfonic acid group (or sulfonate) in the polymer according to the present invention may be stably bonded to the aromatic ring by the electron withdrawing group.

Meanwhile, when preparing the polymer of the present invention according to Scheme 3, a base and / or a solvent may be used. The base and the solvent are not particularly limited, and conventional materials known in the art may be used. As a non-limiting example, a base such as K ₂ CO ₃ and a solvent such as dimethylsulfoxide (DMSO) or DMAc (N, N-dimethylacetamide) may be used.

In addition, in said Scheme 3, the reaction temperature is not particularly limited. As a non-limiting example, the polymer preparation according to Scheme 3 may be performed at 20 to 250 ° C.

The polymer according to the invention, preferably the sulfonated polyarylene ether based polymer, can be used in the fuel cell art. Specifically, it may be used as a material of the electrolyte membrane which is one component of the membrane electrode assembly included in the fuel cell.

Accordingly, the present invention provides an electrolyte membrane including the polymer according to the present invention, preferably a sulfonated polyarylene ether polymer. In addition to the polymer of the present invention, the electrolyte membrane may further include conventional polymers and / or inorganic materials known as materials for electrolyte membranes in the art.

The electrolyte membrane of the present invention can be prepared according to conventional methods known in the art using the polymer according to the present invention. Non-limiting examples thereof may be prepared by coating a polymer or a solution thereof according to the invention on a substrate and then separating the electrolyte membrane from the substrate.

In addition, a membrane electrode assembly including the electrolyte membrane and the electrode of the present invention and a fuel cell including such a membrane electrode assembly are included in the scope of the present invention, and these may each be prepared according to conventional methods known in the art, Description of the description is omitted herein. In addition, since the membrane electrode assembly and other specific details for the configuration of the fuel cell including the same in the present invention are known in the art, even if there is no separate description in the present specification can be sufficiently reproduced.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

EXAMPLE

Example 1 Preparation of 2,4-Difluorophenylsulfonyl-benzene

9.63 g (84.4 mmol) 1,3-difluorobenzene and 17.6 g (99.4 mmol) benzenesulfonylchloride were mixed with 1 g iron (III) -chloride. The reaction mixture was reacted at 75 ° C. for 2.5 hours, again at 90 ° C. for 18 hours, and finally at 140 ° C. for 1 hour. The reaction product was distilled under reduced pressure. The first fraction came out at 90-120 ° C. and the product was distilled at 160-170 ° C. to give 13.22 g. The product obtained by distillation under reduced pressure was recrystallized with 20 ml of ethanol and dried under reduced pressure to give 2,4-difluorophenylsulfonyl-benzene as a white solid in 46% yield (9.79 g, 38.5 mmol).

¹ H-NMR (500 MHz, CDCl ₃ ): δ 8.11-8.16 (m, 1H), 8.00 (d, 2H, J = 8.3 Hz), 7.61-7.65 (m, 1H), 7.54 (t, 2H, J = 7.6-7.9 Hz), 7.03-7.07 (m, 1H), 6.83-6.88 (m, 1H).

Example 2 Preparation of Potassium 3- (2,4-difluorophenylsulfonyl) -benzenesulfonate

9.8 g 2,4-difluorophenylsulfonyl-benzene was dissolved in 20 ml concentrated sulfuric acid and 10 ml 60% fuming sulfuric acid at 60 ° C. The solution was cooled to room temperature and overnight reacted. The reaction mixture was poured into water, and the precipitate was extracted with chloroform (<2.7 g), 15 g potassium chloride was added to the extracted organic solution and stored in a freezer. The precipitated product was recrystallized from water (5.9 g), dissolved again, neutralized with potassium carbonate, and recrystallized to give a white solid of potassium 3- (2,4-difluorophenylsulfonyl) -benzenesulfonate in 20% yield (2.9 g, 7.8). mmol).

¹ H-NMR (500 MHz, D ₂ O): δ 8.21 (s, 1H), 7.98-8.03 (m, 3H), 7.64 (t, 1H, J = 7.9 Hz), 7.08-7.12 (m, 1H) , 6.97-7.01 (m, 1 H).

Example 3 Preparation of Dipotassium 3- (2,4-difluorophenyl-5-sulfonyl-sulfonate) -benzenesulfonate

13 g (51 mmol) 2,4-difluorophenylsulfonyl-benzene was dissolved in 10 ml concentrated sulfuric acid and 20 ml 60% fuming sulfuric acid at 50 ° C. and stirred for 18 hours. The reaction mixture was poured into water, neutralized with calcium carbonate and treated with amberlite IR 120 (H). Then 15 g potassium chloride was added and stored in the freezer. The precipitated product was recrystallized from water (5.9 g), dissolved again, neutralized with potassium carbonate and recrystallized to give 40% of white solid dipotassium 3- (2,4-difluorophenyl-5-sulfonyl-sulfonate) -benzenesulfonate. Yield (10 g, 20.4 mmol) was obtained.

¹ H-NMR (500 MHz, D ₂ O): δ 8.41 (t, 1H, J = ca. 7.8 Hz), 8.29 (s, 1H), 8.03-8.07 (m, 2H), 7.68 (t, 1H, J = ca. 8 Hz), 7.20 (t, 1H, J = 9.7 Hz).

Example 4 Preparation of Polymer Using Potassium 3- (2,4-difluorophenylsulfonyl) -benzenesulfonate

25 g of potassium 3- (2,4-difluorophenylsulfonyl) -benzenesulfonate synthesized in Example 2 and 9,9-bis (4-) in a 2 L round flask equipped with a dean-stark device and a condenser 23.5 g of hydroxyphenyl) fluorene was added, and 150 mL of dimethyl sulfoxide (DMSO) and 200 mL of benzene were used to start the reaction using 9.3 g of potassium carbonate as a catalyst in a nitrogen atmosphere.

The reaction mixture was then stirred for 4 hours in an oil bath at 140 ° C. to remove the azeotrope by adsorption of the azeotrope to the molecular sieves of the Dean-Stark apparatus while the benzene was refluxed, and then the reaction temperature was decreased. It heated up at 180 degreeC and made it polycondensate for 20 hours.

The reaction product was cooled to room temperature, poured into excess methanol to separate the polymer from the solvent, and the polymer obtained by filtration was dried in a vacuum oven at 80 ° C. for 12 hours or more to prepare a polymer.

10 g of the polymer prepared above was added to an aqueous 10% (w / V) sulfuric acid solution and stirred at 80 ° C. for 4 hours to replace the sulfonate in the polymer with sulfonic acid, followed by distilled water until the filtrate became neutral. After repeated washing and filtration, the filtered sulfonic acid type sulfonated polymer was dried in a vacuum oven at 80 ℃ for 12 hours to prepare a hydrotreated sulfonated polymer.

Example 5 Preparation of Polymer for Electrolyte Membrane Using Dipotassium 3- (2,4-difluorophenyl-5-sulfonyl-sulfonate) -benzenesulfonate

20 g of dipotassium 3- (2,4-difluorophenyl-5-sulfonyl-sulfonate) -benzenesulfonate synthesized in Example 3 in a 2 L round flask equipped with a dean-stark device and a condenser 30 g of 9-bis (4-hydroxyphenyl) fluorene, 10 g of 4,4'-difluorobenzophenone, 150 mL of dimethyl sulfoxide (DMSO) and 200 mL of benzene were used to catalyze 12 g of potassium carbonate in a nitrogen atmosphere. The reaction was initiated.

Thereafter, the sulfonated polymer was hydrotreated through the same polymer polymerization reaction and sulfuric acid aqueous solution treatment as in Example 4.

Examples 6 to 7 Preparation of Sulfonated Polymer Electrolyte Membrane

5 g of each of the hydrotreated sulfonated polymers prepared in Examples 4 to 5 were dissolved in 45 g of N, N-dimethylacetamide, and then the solution was filtered through a BORU glass filter (pore size 3) to remove dust and the like. Removed. A vacuum of 10% (w / V) of the filtrate was simultaneously heated to 120 ° C. to remove N, N-dimethylformamide in the filtrate, thereby preparing a solution of about 20% (w / V).

Pour the solution onto a PYREX glass substrate, adjust the thickness of the copolymer solution on the glass plate with a film applicator, and dry the copolymer solution on the glass plate for at least 12 hours in a vacuum oven at 80 ° C. A fonned multiblock copolymer electrolyte membrane was prepared.

Experimental Example

Using the sulfonated polymer electrolyte membranes prepared in Examples 6 to 7, IEC (ion exchange capacity) and hydrogen ion conductivity were measured in the following manner.

Experimental Example 1 Measurement of IEC (ion exchange capacity)

After completely drying the sulfonated polymer electrolyte membranes prepared in Examples 6 to 7, each of 0.5 g was hydrated in ultrapure water at 100 ° C. for 2 hours, and then immersed in 100 mL solution of supersaturated NaCl for at least one day to obtain hydrogen ions (H ⁺ ). Was substituted with sodium ions (Na ⁺ ). The substituted hydrogen ions (H ⁺ ) were titrated with 0.1 N NaOH standard solution to measure the number of moles of sufonic acid per gram of the electrolyte membrane, and the IEC value of the polymer membrane was calculated according to Equation 1 below. The measurement results are summarized in Table 1 below in comparison with Nafion 115 manufactured by DuPont.

[Equation 1]

division IEC (meq./g) Example 6 1.37 Example 7 1.36 Nafion 115 0.91

IEC results of Examples 6 to 7 of Table 1 were found to be 0.45 or more higher than that of Nafion 115, which is a conventional electrolyte membrane.

Experimental Example 2 Measurement of Hydrogen Ion Conductivity

The hydrogen ion conductivity of each of the sulfonated polymer electrolyte membranes prepared in Examples 6 to 7 was determined by a complex impedance method using two-probe.

First, the carbon paper electrode of 1 × 1 (cm2) and 1.5 × 1.5 (cm2), respectively, was faced to both sides of the specimen having an area of 2 × 2 (㎠) at a constant pressure, and ultrapure water was flowed out of the specimen. An alternating voltage of 5 mA was applied to the polymer membrane to be measured in the frequency range of 2 MHz to 10 Hz. In this case, Nyquist plots were obtained by using an impedance analyzer (Imp6), and the resistance of each branched sulfonated multi-block copolymer electrolyte membrane was obtained using this. Then, the hydrogen ion conductivity of the electrolyte membrane was calculated according to Equation 2 below, and the results are shown in FIG. 1 in comparison with Nafion 115 of DuPont.

[Equation 2]

According to FIG. 1, the hydrogen ion conductivity results measured in the temperature range of 30 to 100 ° C. showed that the polymer electrolyte membranes of Examples 6 to 7 had a similar level of hydrogen ion conductivity as the conventional electrolyte membrane (Nafion 115).

The compound represented by Chemical Formula 1, which is a sulfonated monomer according to the present invention, may be used as a reactant of a nucleophilic aromatic substitution polymerization reaction. Therefore, when the compound represented by Formula 1 of the present invention is reacted with a nucleophile having two or more reactive functional groups in a molecule, a polymerization reaction may occur, and thus a polymer may be prepared. In addition, in the polymer prepared from the compound represented by Formula 1 according to the present invention, preferably all sulfonic acid (salt) groups in the sulfonated polyarylene ether-based polymer are substituted on the aromatic ring substituted with an electron withdrawing group, Acidity, which is related to hydrolytic stability and hydrogen ion conductivity, can be improved. In addition, this may also improve the ion exchange capacity and ion density of the polymer.

Claims (7)

A compound represented by the following formula (1). [Formula 1]

In Formula 1, X is -F, -Cl, -Br, or -I; Y is -H, or -SO ₃ M; One of Q ¹ and Q ²

And the other of Q ¹ and Q ² is -H; E is -C (= 0)-, or -S (= 0) _2- ; M is -H, -Na or -K. The compound of claim 1, wherein the compound is prepared by the following Scheme 1. Scheme 1

In Scheme 1, X, Y, E and M are as defined in claim 1. The compound of claim 1, wherein the compound is prepared by the following Scheme 2. Scheme 2

In Scheme 2, X, E and M are as defined in claim ¹ , X ¹ is -Cl, -Br or -I. A polymer prepared by using the compound of claim 1 as a monomer for a nucleophilic aromatic substitution polymerization reaction. The polymer according to claim 4, wherein the polymer is a sulfonated polyarylene ether polymer including a repeating unit represented by the following Chemical Formula 3. [Formula 3]

In Formula 3, Y is -H, or -SO ₃ M; One of Q ¹ and Q ²

And the other of Q ¹ and Q ² is -H; E is -C (= 0)-, or -S (= 0) _2- ; M is -H, -Na or -K; R is arylene or alkylene. An electrolyte membrane comprising the polymer of claim 4 or 5. A fuel cell comprising the electrolyte membrane of claim 6.

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