KR102056689B1 - Method for manufacture of sulfonated polysulfone-based polymer - Google Patents

Abstract

The present invention relates to a method for producing sulfonated polysulfone-based polymer. More specifically, provided is sulfonated polysulfone-based polymer which has excellent ion conductivity, ion exchange capacity, and water content characteristics when used as a film, and excellent heat resistance and chemical resistance. In addition, when sulfonated polysulfone-based polymer is mass-produced, the method for producing sulfonated polysulfone-based polymer can reduce excessive solvent usage and increase productivity.

Description

Method for manufacture of sulfonated polysulfone-based polymer

The present invention relates to a process for the preparation of sulfonated polysulfone polymers. More specifically, the present invention provides a polysulfone polymer having excellent ion conductivity, ion exchange capacity and water content characteristics, and excellent heat resistance and chemical resistance when applied to a membrane. Furthermore, the present invention provides a method for producing a sulfonated polysulfone polymer that can reduce the use of excessive solvents in mass production of the polysulfone polymer and improve productivity.

Nafion (Nafion) as a perfluorine-based membrane, including hydrophilic sulfonic acid (SO ₃ H) functional groups in the hydrophobic perfluorine-based backbone is excellent in ion conductivity and thermal stability. However, they are expensive, have high water and fuel permeability, and have problems such as crossover and voltage loss as electrolyte membranes. In addition, it is required to be applied at high temperatures due to the reduction in ion conductivity.

Accordingly, ionomer-type polymers in which sulfonic acid groups are introduced into non-fluorine-based heat-resistant polymers such as polysulfone, polyethersulfone, polyether ketone, and polyether ether ketone are developed as hydrocarbon-based polymers. They have high ion conductivity and thermal stability, but the crossover phenomenon is severe when sulfonation is high.

Meanwhile, methods for improving physical properties using crosslinking or block copolymers have been sought. However, low ionic conductivity, heat resistance, dimensional stability, and the like are relatively inferior.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a sulfonated polysulfone polymer having excellent ion conductivity, ion exchange performance and water content properties.

In addition, an object of the present invention is to provide a method for producing a sulfonated polysulfone polymer that can further improve productivity while significantly reducing the cost in producing the sulfonated polysulfone polymer.

In addition, the problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention is prepared by dissolving the copolymer of the aromatic first monomer represented by the following formula (1) and the aromatic second monomer represented by the following formula (2) at 20 to 40 ℃ in the presence of a halogenated hydrocarbon solvent Preparing a second solution by adding and stirring a trimethylchlorosilane-containing halogenated hydrocarbon solvent to the first solution, and preparing a second solution by adding and stirring a chlorosulfonic acid-containing halogenated hydrocarbon solvent to the second solution. (3) preparing a solution, mixing, precipitating, and filtering the third solution with a precipitant to obtain a reactant, adding the reactant to an aqueous sodium chloride solution, stirring the solution, and neutralizing it with a basic solution to obtain a product; and Preparation of sulfonated polysulfone polymer comprising the step of filtering, washing and drying the product It provides.

[Formula 1]

[Formula 2]

In the method for producing a sulfonated polysulfone polymer according to an embodiment of the present invention, the aqueous sodium chloride solution may be 10 to 40% by weight sodium chloride.

In the method for producing a sulfonated polysulfone polymer according to an embodiment of the present invention, the step of obtaining the product may be performed for 12 to 18 hours of stirring.

In the method for preparing a sulfonated polysulfone polymer according to an embodiment of the present invention, the halogenated solvent may be any one or more selected from dichloroethane, chloroform, trichloroethane and mixtures thereof.

In the method for preparing a sulfonated polysulfone polymer according to an embodiment of the present invention, the precipitating agent is polyalkylene glycol, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, methyl alcohol, It may be one or more selected from ethyl alcohol, isopropyl alcohol, butyl alcohol and mixtures thereof.

In the method for producing a sulfonated polysulfone polymer according to an embodiment of the present invention, the precipitant may be used in a volume ratio of 10 to 30 times the copolymer.

Another aspect of the present invention is to provide a sulfonated polysulfone-based polymer prepared by the above-described production method. In this case, the sulfonated polysulfone polymer may have a weight average molecular weight of 10,000 to 500,000g / mol.

Further, another aspect of the present invention relates to a molded article formed of the resin composition containing the sulfonated polysulfone polymer described above, and may provide an electrolyte membrane or a water treatment membrane.

Furthermore, the present invention provides a battery, specifically a fuel cell or a redox flow cell, including the molded body.

The polysulfone polymer according to the present invention has excellent proton conductivity, ion exchange capacity and moisture content characteristics when applied to the membrane, and further has excellent heat resistance and chemical resistance.

In particular, the present invention has the effect of significantly reducing the use of excess solvent in the process of mass-producing the polysulfone polymer and maximizing productivity.

Hereinafter, the method for producing the sulfonated polysulfone polymer and the polysulfone polymer prepared therefrom will be described in detail. The invention can be better understood by the following examples. The following examples are for illustrative purposes of the invention and are not intended to limit the scope of protection defined by the appended claims. In this case, unless otherwise defined, the technical and scientific terms used have the meanings that are commonly understood by those of ordinary skill in the art.

The terms used in the description in the present invention are only for effectively describing specific embodiments. Also, the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

A method for producing a sulfonated polysulfone polymer according to an aspect of the present invention is obtained by sulfonating a copolymer of a specific aromatic monomer compound, using a specific combination of solvents, and simultaneously controlling the reaction conditions of these solvents. By further reducing the amount of precipitant used excessively in the post-treatment of the reactants, the production efficiency can be further improved.

Specifically, the method for producing a sulfonated polysulfone polymer according to one aspect of the present invention

Preparing a first solution by dissolving a copolymer of an aromatic first monomer represented by Chemical Formula 1 and an aromatic second monomer represented by Chemical Formula 2 at 20 to 40 ° C. in the presence of a halogenated hydrocarbon solvent;

Preparing a second solution by dropping and stirring a trimethylchlorosilane-containing halogenated hydrocarbon solvent into the first solution,

Preparing a third solution by dropping and stirring a chlorosulfonic acid-containing halogenated hydrocarbon solvent in the second solution;

Mixing, precipitating, and filtering the third solution with a precipitant to obtain a reactant,

Adding the reactant to an aqueous sodium chloride solution, stirring and neutralizing the solution using a basic solution to obtain a product, and

Filtering, washing and drying the product

It includes.

[Formula 1]

[Formula 2]

The copolymer of the aromatic first monomer represented by the formula (1) and the aromatic second monomer represented by the formula (2) is a polymer produced by cross-repeating hydrophilicity and hydrophobicity. It has a backbone comprising a benzene ring, and the hydrophobic portion introduces sulfonyl groups to impart flexibility. This is done by specific process conditions through the combination of specific trimethylchlorosilane and chlorosulfonic acid, which not only controls the content of sulfonic acid groups, but also reduces the amount of precipitant used in the post-treatment process. You can increase it.

The aromatic first monomer represented by Formula 1 contains an aromatic ether repeating unit, and the aromatic second monomer represented by Formula 2 contains an aromatic ether repeating unit containing a sulfonic acid group, and the molar ratio of these repeating units is It is not greatly limited. For example, the molar ratio of the repeating unit may be 90:10 to 10:90, preferably 85:15 to 20:80, and more preferably 75:25 to 40:60, but this is merely a non-limiting example. It is not limited to the above numerical range. This range is effective in terms of cationic conductivity and membrane resistance, permeability and efficiency when applied to the membrane.

Copolymers of the aromatic first monomer represented by the formula (1) and the aromatic second monomer represented by the formula (2) can be used without limitation the method used in the general polymer manufacturing process, in one embodiment may be prepared by a condensation polymerization process Can be.

According to one aspect of the invention, the step of preparing a first solution by dissolving the copolymer in a halogenated hydrocarbon solvent in a reactor.

In this case, the halogenated hydrocarbon solvent is not particularly limited, but may be any one or more selected from dichloroethane, chloroform, trichloroethane and mixtures thereof. Preferably, dichloroethane is mentioned.

The temperature range in the reactor at the time of dissolution is carried out at 20 to 40 ℃, preferably 25 to 35 ℃.

The copolymer has a weight average molecular weight of 50,000 to 150,000 g / mol, preferably 90,000 to 140,000 g / mol.

When the copolymer is dissolved, it is reacted with trimethylchlorosilane (TMCS). At this time, trimethylchlorosilane is used diluted in a halogenated hydrocarbon solvent in the reactor. It is preferably used diluted in dichloroethane. The trimethylchlorosilane is diluted in dichloroethane to 10 to 80% by weight, preferably 25 to 75% by weight, and then reacted by dropwise addition to the reactor. The dropping speed can be adjusted as needed, but 0.1 g / sec to 10 g / sec, preferably 1 g / sec to 8 g / sec, more preferably 4 to 6 g / sec is effective.

The trimethylchlorosilane is reacted at 10 to 50 parts by weight, preferably 20 to 40 parts by weight, relative to 100 parts by weight of the copolymer.

When the addition of the diluent of trimethylchlorosilane is completed, stirring is further performed for 30 minutes or more.

Next, a solution obtained by diluting chlorosulfonic acid (CSA) in a halogenated hydrocarbon solvent is added dropwise to the solution in the reactor. At this time, chlorosulfonic acid is used after dilution in the halogenated hydrocarbon solvent in the reactor. It is preferably used diluted in dichloroethane. The chlorosulfonic acid is diluted in dichloroethane to 10 to 80% by weight, preferably 25 to 75% by weight, and then reacted by dropwise addition to the reactor. The dropping speed can be adjusted as needed, but 0.1 g / sec to 10 g / sec, preferably 1 g / sec to 8 g / sec, more preferably 4 to 6 g / sec is effective.

The chlorosulfone is reacted with 5 to 50 parts by weight, preferably 15 to 40 parts by weight, relative to 100 parts by weight of the copolymer.

The present invention can achieve the desired effect by dropping a diluent obtained by diluting the trimethylchlorosilane and chlorosulfone in a halogenated hydrocarbon solvent, preferably the same solvent, in a reactor, respectively.

Preferably, the trimethylchlorosilane and the chlorosulfone are effectively added in a weight ratio of 1: 1 to 1: 2, preferably 1: 2 to 1: 4, to effect the reaction. Furthermore, it is more effective to add the dropwise addition of the trimethylchlorosilane diluent and the dropwise addition of the chlorosulfone diluent sequentially.

When the reaction is complete, the mixture is mixed with the precipitant to obtain a precipitate, which is filtered to obtain a reactant.

It is effective to use a solvent that is easy to precipitate as the precipitant. Specifically, selected from alkylene glycol, polyalkylene glycol, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol and mixtures thereof It may be one or more. Preferably alkylene glycol, isopropyl alcohol, etc. may be mentioned, but is not limited thereto.

The amount of the precipitant may be 10 to 30 times (v / w), preferably 15 to 25 times (v / w) compared to the copolymer. It has the effect that the sulfonated polysulfone type polymer desired in the said range can be obtained efficiently with high purity.

According to the present invention, by dropwise reacting with a combination of specific compounds, i.e., a combination of trimethylchlorosilane and chlorosulfonic acid, the physical properties of the desired sulfonated polysulfone polymer can be ensured, and at the same time, the precipitation step can be easily performed. Bar not only can significantly reduce the amount of precipitant used to increase the purity of the precipitation process, but is also more effective in terms of increasing production efficiency.

The precipitate was added and stirred for 30 to 240 minutes to obtain a precipitate. The precipitate obtained is introduced into an aqueous sodium chloride solution and stirred sufficiently so that it can be replaced with Na ⁺ in H ⁺ . At this time, the aqueous sodium chloride solution is 10 to 40% by weight, preferably 20 to 30% by weight of sodium chloride as well as securing the physical properties of the sulfonated polysulfone-based polymer of the present invention, as well as the solvent consumed in the manufacturing process More effective in terms of savings and productivity.

Next, neutralization is carried out to obtain a product. The neutralizing agent is not particularly limited, but may be performed using a basic solution, and specifically, may be performed using sodium hydroxide. At this time, the concentration of sodium hydroxide may be used 15 to 45% by weight, preferably 20 to 40% by weight, but is not limited thereto.

12 to 18 hours of stirring to obtain the product is effective in terms of improving final physical properties, but is not limited thereto.

Once neutralization is complete, wash and dry. It is efficient to use water for washing, and it is effective to adjust the pH of the filtrate at this time. pH is preferable within the range of 6-7. Drying can be performed using a vacuum oven. Drying temperature is 70 ℃ to 100 ℃, preferably 80 ℃ to 90 ℃, but is not limited thereto.

According to one aspect of the present invention, the sulfonated polysulfone polymer prepared by the method as described above may have an ion exchange capacity of 0.9 meq / g or more, preferably 1.3 meq / g or more, but is not limited thereto. In addition, the sulfonated polysulfone-based polymer is not particularly limited in the scope of application, but is preferably included in the resin composition for film formation can be implemented as a molded article.

The molded body may be applied to a water treatment device such as an energy storage device (ESS) or a RO membrane. Specific embodiments include, but are not limited to, an electrolyte membrane or a water treatment membrane. The types of matrix resins used in the membrane are not limited in kind, but sulfonated polyetheretherketone (SPEEK), sulfonated polyetherethersulfone (SPEES), sulfonated polyimide (SPI), polyimide And polybenzimidazole.

In addition, it is possible to provide a battery including the molded body. In this case, the battery may include a fuel cell, a redox flow battery, or a vanadium flow battery, but is not limited thereto.

According to the present invention, the sulfonated polysulfone-based polymer, when applied to the membrane, for example, when the membrane is prepared by impregnating a support such as polyethylene or polypropylene, the membrane is excellent insolubility in water, low water content, excellent It can impart dimensional stability and has high ion conductivity. Furthermore, it has an effect which can give a better battery performance.

Hereinafter, a method for preparing a sulfonated polysulfone polymer and a sulfonated polysulfone polymer prepared therefrom according to the present invention will be described in more detail. However, the following examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto and may be implemented in various forms.

(Example 1)

1,2-dichloroethane (DCE) was added to the reactor, and a copolymer of the monomer of Formula 1 and the monomer of Formula 2 (Mw 85,000, Tg = 194 ° C.) was added and dissolved while maintaining 25 ° C. As the copolymer, a molar ratio of the monomer of Formula 1 and the monomer of Formula 2 was 7: 3. The DCE was equivalent ratio of 2.5 based on the copolymer. After the copolymer was dissolved in DCE, a solution of trimethylchlorosilane (TMCS) diluted in DCE was added dropwise to the reactor at a rate of 5 g / sec. At this time, the trimethylchlorosilane was added in an amount of 24 parts by weight relative to 100 parts by weight of the copolymer, and when the addition was completed, the mixture was further stirred for 30 minutes. Then, a solution obtained by diluting chlorosulfonic acid (CSA) in DCE was added dropwise to the reactor at a rate of 4 g / sec. At this time, the chlorosulfonic acid was added in an amount of 16 parts by weight relative to 100 parts by weight of the copolymer. When the dropping was completed, the mixture was stirred at 35 ° C. at 70 rpm for 1 hour. Next, upon completion of the reaction, the reactant was precipitated using 20 times (v / w) isopropyl alcohol compared to the copolymer introduced into the reactor. Then, isopropyl alcohol was added again, and stirred for 1 hour to obtain a precipitate. The obtained precipitate was added to a 20% by weight aqueous sodium chloride solution and then sufficiently stirred. Next, neutralized with 20 wt% sodium hydroxide solution, filtered, washed with water, and dried. At this time, the pH of the filtrate was 7.0, and drying was performed for 24 hours in a vacuum oven (80 ℃) to prepare a sulfonated polysulfone polymer.

The prepared sulfonated polysulfone polymer had an ion exchange capacity of 1.1 meq / g, and a weight average molecular weight measured using gel permeation chromatography was 135,000 g / mol. At this time, the ion exchange capacity was measured using an automatic titrator (848 titrino plus).

(Example 2)

1,2-dichloroethane (DCE) was added to the reactor, and a copolymer of a monomer of Formula 1 and a monomer of Formula 2 (Mw 85,000, Tg = 194 ° C.) was added and dissolved while maintaining 25 ° C. The DCE was equivalent ratio of 2.5 based on the copolymer. As the copolymer, a molar ratio of the monomer of Formula 1 and the monomer of Formula 2 was 7: 3. After the copolymer was dissolved in DCE, a solution of trimethylchlorosilane (TMCS) diluted in DCE was added dropwise to the reactor at a rate of 6 g / sec. At this time, the trimethylchlorosilane was added in an amount of 24 parts by weight relative to 100 parts by weight of the copolymer, and when the addition was completed, the mixture was further stirred for 30 minutes. Subsequently, a solution obtained by diluting chlorosulfonic acid (CSA) in DCE was added dropwise to the reactor at a rate of 5 g / sec. At this time, the chlorosulfonic acid was added in an amount of 16 parts by weight relative to 100 parts by weight of the copolymer. When the dropping was completed, the mixture was stirred at 35 ° C. at 70 rpm for 1 hour. Next, upon completion of the reaction, the reactant was precipitated using 25 times (v / w) isopropyl alcohol compared to the copolymer introduced into the reactor. Then, isopropyl alcohol was added again, and stirred for 1 hour to obtain a precipitate. The obtained precipitate was introduced into a 30% by weight aqueous sodium chloride solution and then stirred sufficiently. Next, neutralized with 20 wt% sodium hydroxide solution, filtered, washed with water, and dried. At this time, the pH of the filtrate was 7.0, and drying was performed for 24 hours in a vacuum oven (80 ℃) to prepare a sulfonated polysulfone polymer.

The prepared sulfonated polysulfone polymer had an ion exchange capacity of 1.4 meq / g, and a weight average molecular weight measured using gel permeation chromatography was 97,000 g / mol. At this time, the ion exchange capacity was measured using an automatic titrator (848 titrino plus).

(Example 3)

1,2-dichloroethane (DCE) was added to the reactor, and a copolymer of a monomer of Formula 1 and a monomer of Formula 2 (Mw 85,000, Tg = 194 ° C.) was added and dissolved while maintaining 25 ° C. The DCE was equivalent ratio of 2.5 based on the copolymer. As the copolymer, a molar ratio of the monomer of Formula 1 and the monomer of Formula 2 was 7: 3. After the copolymer was dissolved in DCE, a solution of trimethylchlorosilane (TMCS) diluted in DCE was added dropwise to the reactor at a rate of 5 g / sec. At this time, the trimethylchlorosilane was added in an amount of 24 parts by weight relative to 100 parts by weight of the copolymer, and when the addition was completed, the mixture was further stirred for 30 minutes. Then, a solution obtained by diluting chlorosulfonic acid (CSA) in DCE was added dropwise to the reactor at a rate of 4 g / sec. At this time, the chlorosulfonic acid was added in an amount of 16 parts by weight relative to 100 parts by weight of the copolymer. When the dropping was completed, the mixture was stirred at 35 ° C. at 70 rpm for 1 hour. Next, upon completion of the reaction, the reactant was precipitated using 20 times (v / w) isopropyl alcohol compared to the copolymer introduced into the reactor. Then, isopropyl alcohol was added again, and stirred for 1 hour to obtain a precipitate. The obtained precipitate was introduced into an aqueous 31 wt% sodium chloride solution and then stirred sufficiently. Next, neutralized with 20 wt% sodium hydroxide solution, filtered, washed with water, and dried. At this time, the pH of the filtrate was 7.0, and drying was performed for 24 hours in a vacuum oven (80 ℃) to prepare a sulfonated polysulfone polymer.

The prepared sulfonated polysulfone polymer had an ion exchange capacity of 0.9 meq / g, and a weight average molecular weight measured using gel permeation chromatography was 113,000 g / mol. At this time, the ion exchange capacity was measured using an automatic titrator (848 titrino plus).

(Example 4)

1,2-dichloroethane (DCE) was added to the reactor, and a copolymer of a monomer of Formula 1 and a monomer of Formula 2 (Mw 85,000, Tg = 194 ° C.) was added and dissolved while maintaining 25 ° C. The DCE was to have an equivalent ratio of 2 based on the copolymer. As the copolymer, a molar ratio of the monomer of Formula 1 and the monomer of Formula 2 was 7: 3. After the copolymer was dissolved in DCE, a solution of trimethylchlorosilane (TMCS) diluted in DCE was added dropwise to the reactor at a rate of 6 g / sec. At this time, the trimethylchlorosilane was added in an amount of 24 parts by weight relative to 100 parts by weight of the copolymer, and when the addition was completed, the mixture was further stirred for 30 minutes. Subsequently, a solution obtained by diluting chlorosulfonic acid (CSA) in DCE was added dropwise to the reactor at a rate of 5 g / sec. At this time, the chlorosulfonic acid was added in an amount of 16 parts by weight relative to 100 parts by weight of the copolymer. When the dropping was completed, the mixture was stirred at 35 ° C. at 70 rpm for 1 hour. Next, upon completion of the reaction, the reactant was precipitated using 25 times (v / w) isopropyl alcohol compared to the copolymer introduced into the reactor. Then, isopropyl alcohol was added again, and stirred for 1 hour to obtain a precipitate. The obtained precipitate was introduced into a 30% by weight aqueous sodium chloride solution and then stirred sufficiently. Next, neutralized with 20 wt% sodium hydroxide solution, filtered, washed with water, and dried. At this time, the pH of the filtrate was 7.0, and drying was performed for 24 hours in a vacuum oven (80 ℃) to prepare a sulfonated polysulfone polymer.

The prepared sulfonated polysulfone polymer had an ion exchange capacity of 1.1 meq / g, and a weight average molecular weight measured using gel permeation chromatography was 115,000 g / mol. At this time, the ion exchange capacity was measured using an automatic titrator (848 titrino plus).

(Example 5)

1,2-dichloroethane (DCE) was added to the reactor, and a copolymer of a monomer of Formula 1 and a monomer of Formula 2 (Mw 85,000, Tg = 194 ° C.) was added and dissolved while maintaining 25 ° C. The DCE was to have an equivalent ratio of 2 based on the copolymer. As the copolymer, a molar ratio of the monomer of Formula 1 and the monomer of Formula 2 was 7: 3. After the copolymer was dissolved in DCE, a solution of trimethylchlorosilane (TMCS) diluted in DCE was added dropwise to the reactor at a rate of 6 g / sec. At this time, the trimethylchlorosilane was added in an amount of 24 parts by weight relative to 100 parts by weight of the copolymer, and when the addition was completed, the mixture was further stirred for 30 minutes. Subsequently, a solution obtained by diluting chlorosulfonic acid (CSA) in DCE was added dropwise to the reactor at a rate of 5 g / sec. At this time, the chlorosulfonic acid was added in an amount of 16 parts by weight relative to 100 parts by weight of the copolymer. When the dropping was completed, the mixture was stirred at 50 ° C. at 70 rpm for 1 hour. Next, upon completion of the reaction, the reactant was precipitated using 25 times (v / w) isopropyl alcohol compared to the copolymer introduced into the reactor. Then, isopropyl alcohol was added again, and stirred for 1 hour to obtain a precipitate. The obtained precipitate was introduced into a 30% by weight aqueous sodium chloride solution and then stirred sufficiently. Next, neutralized with 20 wt% sodium hydroxide solution, filtered, washed with water, and dried. At this time, the pH of the filtrate was 7.0, and drying was performed for 24 hours in a vacuum oven (80 ℃) to prepare a sulfonated polysulfone polymer.

The prepared sulfonated polysulfone polymer had an ion exchange capacity of 1.2 meq / g, and a weight average molecular weight measured using gel permeation chromatography was 125,000 g / mol. At this time, the ion exchange capacity was measured using an automatic titrator (848 titrino plus).

(Example 6)

1,2-dichloroethane (DCE) was added to the reactor, and a copolymer of a monomer of Formula 1 and a monomer of Formula 2 (Mw 85,000, Tg = 194 ° C.) was added and dissolved while maintaining 25 ° C. The DCE was equivalent ratio of 2.5 based on the copolymer. As the copolymer, a molar ratio of the monomer of Formula 1 and the monomer of Formula 2 was 7: 3. After the copolymer was dissolved in DCE, a solution of trimethylchlorosilane (TMCS) diluted in DCE was added dropwise to the reactor at a rate of 6 g / sec. At this time, the trimethylchlorosilane was added in an amount of 24 parts by weight relative to 100 parts by weight of the copolymer, and when the addition was completed, the mixture was further stirred for 30 minutes. Subsequently, a solution obtained by diluting chlorosulfonic acid (CSA) in DCE was added dropwise to the reactor at a rate of 5 g / sec. At this time, the chlorosulfonic acid was added in an amount of 16 parts by weight relative to 100 parts by weight of the copolymer. When the dropping was completed, the mixture was stirred at 50 ° C. at 70 rpm for 1 hour. Next, upon completion of the reaction, the reactant was precipitated using 25 times (v / w) isopropyl alcohol compared to the copolymer introduced into the reactor. Then, isopropyl alcohol was added again, and stirred for 1 hour to obtain a precipitate. The obtained precipitate was introduced into a 30% by weight aqueous sodium chloride solution and then stirred sufficiently. Next, neutralized with 20 wt% sodium hydroxide solution, filtered, washed with water, and dried. At this time, the pH of the filtrate was 7.0, and drying was performed for 24 hours in a vacuum oven (80 ℃) to prepare a sulfonated polysulfone polymer.

The prepared sulfonated polysulfone polymer had an ion exchange capacity of 1.5 meq / g, and a weight average molecular weight measured by gel permeation chromatography was 99,000 g / mol. At this time, the ion exchange capacity was measured using an automatic titrator (848 titrino plus).

(Comparative Example 1)

In Example 1, the same procedure as in Example 1 was carried out except that chlorosulfonic acid was not used. The prepared sulfonated polysulfone polymer had an ion exchange capacity of 0.41 meq / g, and a weight average molecular weight measured using gel permeation chromatography was 46,000 g / mol. In addition, the amount of isopropyl alcohol used in the precipitation process was increased by about 150% compared to Example 1, which was confirmed to be very disadvantageous in terms of mass production process.

(Comparative Example 2)

In Example 1, the same procedure as in Example 1 was carried out except that trimethylchlorosilane was not used. The prepared sulfonated polysulfone-based polymer was attached to the wall of the reactor and difficult to process such as precipitation and washing.

As described above in the present invention has been described by a limited embodiment, which is provided only to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, it is to be understood that the general knowledge in the field Those having a variety of modifications and variations are possible from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all of the equivalents or equivalents of the claims as well as the claims to be described later belong to the scope of the present invention.

Claims (10)

In a solution in which a copolymer of the aromatic first monomer represented by the following formula (1) and the aromatic second monomer represented by the following formula (2) was dissolved at 20 to 40 ° C. in the presence of dichloroethane,
Trimethylchlorosilane diluent was added dropwise at a rate of 0.1g / sec to 10g / sec, and a chlorosulfone diluent was added dropwise at a rate of 0.1g / sec to 10g / sec to prepare a reaction solution,
The trimethylchlorosilane diluent and the chlorosulfonic acid diluent each contain 10 to 80% by weight of trimethylchlorosilane and chlorosulfonic acid in dichloroethane,
The prepared reaction solution is mixed with 10 to 30 times (v / v) of the precipitating agent, precipitated and filtered,
After the sodium chloride was added to an aqueous solution of sodium chloride of 10 to 40% by weight and stirred for 12 to 18 hours,
Neutralization with a basic solution to obtain the product, and
Filtering, washing and drying the product
Method for producing a sulfonated polysulfone polymer having a weight average molecular weight of 10,000 to 500,000g / mol comprising a.
[Formula 1]

[Formula 2]

delete delete delete The method of claim 1,
The precipitant may be any one or more selected from polyalkylene glycol, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and mixtures thereof. Method for producing fonated polysulfone polymer. delete delete To be formed of a resin composition comprising a sulfonated polysulfone polymer prepared by the method of claim 1,
A molded article which is an electrolyte membrane or a water treatment membrane. A battery comprising the molded body according to claim 8. The method of claim 9,
The cell is a fuel cell or a redox flow cell.