KR20160046464A - Method for preparing sulfonated multi-block copolymer - Google Patents

Abstract

The present invention relates to a process for the preparation of sulfonated multiblock copolymers.

Description

METHOD FOR PREPARING SULFONATED MULTI-BLOCK COPOLYMER [0002]

The present invention relates to a process for the preparation of branched sulfonated multiblock copolymers.

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

 A fuel cell is a power generation system that converts the chemical reaction energy of a fuel and an oxidant into electric energy. Hydrogen, hydrocarbons such as methanol and butane are used as fuel, and oxygen is used as an oxidant. In a fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is composed of an anode and a cathode formed on both surfaces of an electrolyte membrane and an electrolyte membrane. Referring to the following reaction formula (a reaction formula of a fuel cell when hydrogen is used as a fuel) showing the principle of electricity generation of a fuel cell, in the anode electrode, oxidation reaction of fuel occurs and hydrogen ions and electrons are generated. And moves to the cathode electrode. At the cathode electrode, hydrogen ions and electrons transferred through the oxygen (oxidizing agent) and the electrolyte membrane react with each other to generate water. This reaction causes electrons to migrate to the external circuit.

[Reaction Scheme]

The ^{_{anode: H 2 → 2H + + 2e}} -

Cathode electrode: 1 / 2O ₂ + 2H ⁺ + 2e ^- & gt ^{; -} & gt ^; H ₂ O

Overall Scheme: H ₂ + 1 / 2O _{2 -} > H ₂ O

Polymer electrolyte fuel cells (PEFC) in fuel cells have high energy efficiency, high current density and power density, short driving time, and fast response to load changes. Electrolyte membranes used in polymer electrolyte fuel cells should have characteristics such as high hydrogen ion conductivity and chemical stability, thermal stability at operating temperature, low gas permeability, especially excellent mechanical strength as a separator. Even if a film satisfying these conditions is developed, commercialization of the film requires cost-competitive and environment-friendly manufacturing technology. Studies on non-fluorinated polymers, which have been developed by Du Pont as well as perfluorinated sulfonic acid-based fluoropolymers as well as heat-resistant polymers as basic skeletons and polar groups introduced thereinto as functional polymers, have been actively studied.

 Of these, poly (arylene ether) -based polymers having an aromatic derivative and an ether bond structure are excellent in not only heat resistance but also mechanical strength, durability, chemical resistance, and low manufacturing cost.

The most common method for the preparation of such block copolymers is to use an aromatic nucleophilic aromatic substitution (SNAr) which forms an ether bond by substituting a phenate ion-activated leaving group. For an effective reaction, polar aprotic solvents such as dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF) are mainly used.

The Canadian patent CA 847963 produced poly (arylene ether) based polymers using weak bases such as sodium carbonate and potassium carbonate.

R. Viswanathan et al. (Polymer, Vol. 25, 1984, pp. 1827-1836) conducted in-depth studies on the polymerization reaction with potassium carbonate in the solvent DMAc. Korean Patent Publication No. 2006-0071690 also discloses sulfonated multiblock copolymers using potassium carbonate.

Meanwhile, in the conventional method for preparing a multi-block copolymer, an excess amount of purified water was required to remove potassium carbonate, which was used as a reactant, in at least 8 washing steps. This process not only causes an excessive amount of wastewater but also takes a long time, and the whole process time is long.

The conventional process for producing a block copolymer has a problem of washing with excess of purified water. This causes not only an excessive amount of wastewater but also a long process time.

Accordingly, it is an object of the present invention to provide a method for producing a block copolymer capable of improving cleaning efficiency. In other words, it is an object of the present invention to provide a method for producing a block copolymer in which the number of times of washing and the time are shortened.

Accordingly, it is an object of the present invention to provide a method for producing a block copolymer in which the amount of wastewater is reduced and the processing time is extremely shortened.

In order to achieve the above object, the present invention provides a method for producing a sulfonated multiblock copolymer, comprising the steps of: 1) precipitating a sulfonated multiblock copolymer in a sulfonated multiblock copolymer solution; 2) diluting the precipitated solution with water and adjusting the pH with acid; 3) filtering the sulfonated multiblock copolymer in the pH controlled solution; And 4) washing the filtered sulfonated multiblock copolymer. The present invention also provides a method for producing a sulfonated multiblock copolymer.

According to a preferred embodiment of the present invention, the step 1) may be performed by adding a non-solvent. The non-solvent being acetone; At least one alcohol selected from methanol, ethanol, isopropyl alcohol and n-butanol; One or more alkanes selected from hexane, cyclohexane and heptane; And a mixture thereof.

In a preferred embodiment of the present invention, the water in the step 2) may include 1 to 15 parts by weight based on 100 parts by weight of the solution in which the sulfonated multiblock copolymer is precipitated. In the step 2), the acid may include at least one selected from sulfuric acid, nitric acid, hydrochloric acid (HCl), and carboxylic acid, and the carboxylic acid includes formic acid and acetic acid. And the pH of the controlled solution in step 3) may be 6-8.

According to a preferred embodiment of the present invention, the step 4) may be performed one or more times, preferably 1 to 7 times.

The present invention can provide a method for producing a block copolymer capable of increasing the cleaning efficiency. That is, the present invention can provide a method for producing a block copolymer with reduced number of times of cleaning and shortened time.

Accordingly, the method of producing a block copolymer according to the present invention can provide a method of producing a block copolymer in which the amount of wastewater is reduced and the processing time is shortened.

Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

The conventional process for producing a block copolymer has a problem of washing with excess of purified water. This causes not only an excessive amount of wastewater but also a long process time.

Therefore, the inventors of the present invention have found that it is possible to improve the efficiency of the washing step by carrying out the pretreatment with an effort to make efficient washing. Therefore, the present inventors have found a method for producing a sulfonated multiblock copolymer which not only reduces the amount of wastewater but also has a very short processing time, and completed the present invention.

That is, the present invention provides a method for preparing a sulfonated multiblock copolymer, comprising: 1) precipitating a sulfonated multiblock copolymer in a sulfonated multiblock copolymer solution; 2) diluting the solution in which the sulfonated multiblock copolymer is precipitated with water and adjusting the pH with acid; 3) filtering the sulfonated multiblock copolymer in the pH controlled solution; And 4) washing the filtered sulfonated multiblock copolymer. The present invention also provides a method for producing a sulfonated multiblock copolymer.

The present invention relates to a method for producing a sulfonated multiblock copolymer, wherein, in the polymerization of a branched hydrophilic block and a branched hydrophobic block, the hydrophilic block and the minor block are blocked by block copolymerization in one reactor . This method makes the chemical bonding alternately between a small number of blocks which maintain the mechanical densities of the thin film and a hydrophilic block which gives the ion conductivity to the thin film.

Hereinafter, a method for producing a sulfonated multiblock copolymer of the present invention will be described.

First, the sulfonated multiblock copolymer solution of the present invention will be described.

The sulfonated multiblock copolymer solution of the present invention can be used in any conventional manner, and preferably, the following three methods can be used.

First, according to a preferred embodiment of the present invention, the sulfonated multiblock copolymer solution comprises: a) a bisphenol-based monomer or aromatic dihalide-based monomer; An aromatic dihalogen monomer having an acid substituent or a bisphenol monomer having an acid substituent; Carbonate anhydride catalyst; Adding a first organic solvent and a second organic solvent and polymerizing them to prepare a hydrophilic block; And b) adding bisphenol-based monomer, aromatic dihalide-based monomer, carbonate anhydride catalyst, first organic solvent and second organic solvent in the reactor comprising the hydrophilic block and the first organic solvent, and polymerizing And preparing a multi-block copolymer at the same time as producing a small number of blocks.

Secondly, according to another embodiment of the present invention, the sulfonated multi-block copolymer solution is prepared by a process comprising the steps of: a) introducing a bisphenol-based monomer, an aromatic dihalide-based monomer, a carbonate anhydride catalyst, a first organic solvent and a second organic solvent And polymerizing to prepare a small number of blocks; And b) a bisphenol-based monomer or an aromatic dihalide-based monomer in the reactor comprising the prepared minor block, the first organic solvent; An aromatic dihalogen monomer having an acid substituent or a bisphenol monomer having an acid substituent; Carbonate anhydride catalyst; Adding a first organic solvent and a second organic solvent and polymerizing them to prepare a hydrophilic block and simultaneously preparing a multi-block copolymer.

Thirdly, according to a preferred embodiment of the present invention, there is provided a method for producing a hydrophobic block, comprising the steps of: a) adding a bisphenol-based monomer, an aromatic dihalogen monomer, a carbonate anhydride catalyst, a first organic solvent and a second organic solvent into a reactor, step; b) An aromatic dihalide monomer having a bisphenol-based monomer or aromatic dihalogen monomer, an acid substituent, or an acid substituent, a carbonate anhydride catalyst, a first organic solvent and a second organic solvent are charged in a reactor and polymerized to prepare a hydrophilic Producing a block; And c) dissolving the hydrophobic block prepared in the step a) and the hydrophilic block prepared in the step b) in a first organic solvent and a second organic solvent, and reacting the resultant with a carbonate anhydride catalyst to prepare a multi-block copolymer ; ≪ / RTI >

According to a preferred embodiment of the present invention, a branching agent is further added in the step of preparing a hydrophilic block or a hydrophobic block to prepare a branched sulfonated multiblock copolymer, so that a hydrophilic block or a hydrophobic block Can be prepared.

As described above, in the manufacturing method of the present invention, as in the first and second methods, the order of manufacturing the hydrophilic block and the fractional block is optional. Therefore, a hydrophobic block can be prepared after the prime block is first prepared . And thirdly, in another embodiment of the present invention, polymerization of separately branched sulfonated multiblock copolymers may be performed after hydrophilic blocks and minor blocks, respectively, are prepared. In this case, since the monomer is not present, it is obvious that the addition amount of the anhydrous carbonic acid catalyst can be appropriately adopted by repeated experiments in consideration of the molecular weight of the copolymer to be obtained, reaction conditions, and the like. The hydrophobic block according to the present invention has the same range of reaction as the hydrophilic block except that the phenol-based monomer having an acid substituent, the bisphenol-based monomer having an acid substituent, or the aromatic dihalogen monomer having an acid substituent is not used Conditions and reaction processes.

The bisphenol-based monomer used in the above-mentioned production methods may be at least one selected from the group consisting of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-biphenol and 9,9-bis (4-hydroxyphenyl) (4-hydroxyphenyl) fluorene, and preferably 9,9-bis (4-hydroxyphenyl) fluorene.

The aromatic dihalide-based monomer may include at least one selected from 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone, preferably 4,4'-difluorobenzene May be a jaffe.

According to a preferred embodiment of the present invention, the bisphenol-based monomer having an acid substituent is selected from the group consisting of hydroquinone sulfonic acid potassium salt, 2,7-dihydroxynaphthalene-3,6-disulfonic acid disodium salt, Dihydroxynaphthalene-3-sulfonic acid monosodium salt, bis (4-fluorophenyl) sulfone, and 2,3-dihydroxynaphthalene-6-sulfonic acid monosodium salt. , Preferably a hydroquinone sulfonic acid potassium salt.

And aromatic dihalogen monomers having an acid substituent are selected from the group consisting of potassium 5,5'-carbonylbis (2-fluorobenzenesulfonate), 4,4'-difluorodiphenylsulfone and potassium 2,2 '- [9, 9-bis (4-hydroxyphenyl) fluorene] sulfonate, preferably 2,2 '- [9,9-bis (4-hydroxyphenyl) fluorene] ] Sulfonate.

Among the aromatic dihalo monomers having the above acid substituent, potassium 5,5'-carnovilbis (2-fluorobenzenesulfonate) is preferably used as the aromatic dihalo monomer having 4,4'-difluorobenzophenone and 4,4'-difluorodiphenyl The sulfones can be prepared by direct sulfonation with fuming sulfuric acid.

(4-hydroxyphenyl) fluorene sulfonyl chloride was prepared by reacting 9,9-bis (4-hydroxyphenyl) fluorene with chlorosulfuric acid (CIHSO ₄ ) Can be produced by sulfonation.

 In preparing the sulfonated multi-block copolymer, the monomer for producing the hydrophilic block is dissolved in the first organic solvent and the second organic solvent together with the carbonate anhydride (or the monomer for producing the hydrophobic block may be dissolved first ), The mixture is stirred at 90 to 150 ° C, preferably 100 to 140 ° C for 3 to 5 hours, and the azeotropic mixture is removed, and the mixture is reacted by stirring at 150 to 190 ° C for 6 to 24 hours.

According to a preferred embodiment of the present invention, the carbonate anhydride catalyst may be any generally usable catalyst, and preferably potassium carbonate (K ₂ CO ₃ ) is preferably used.

The first organic solvent and the second organic solvent may be used both as hydrophilic and hydrophobic blocks. The first organic solvent is a solvent which dissolves reactants and products well and has a high boiling point. The second organic solvent is a solvent used for removing an azeotropic mixture (particularly, water) in the initial reaction solution. That is, the second organic solvent is distilled off and only the first organic solvent may remain in the reaction solution after the reaction.

The first organic solvent is not particularly limited as long as it can dissolve reactants and products well, but it is preferable to use N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (N- methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), and N, N-dimethylformamide (DMF).

The second organic solvent may be any one selected from benzene, toluene and xylene, although it is not particularly limited as long as it can be removed by azeotropic distillation with water in the reactant.

In addition, the branching agent that is input to produce the branched sulfonated multiblock copolymers also plays a role in directly configuring the main chain of the sulfonated multiblock copolymer.

According to one preferred embodiment of the present invention, the branche is selected from the group consisting of [3,5-bis (4-fluorobenzoyl) phenyl] (4-fluorophenyl) 3,5-bis (4-fluorosulfonyl) phenyl] (4-fluorophenyl) methanone, 4-fluorophenyl) methanone, 3,5-difluoro-4'-fluorobenzophenone) and 3,5-difluoro-4'-fluorophenyl Sulfone ((3,5-difluoro-4'-fluorophenyl) sulfone).

The above [3,5-bis (4-fluorobenzoyl) phenyl] (4-fluorophenyl) methanone is obtained by reacting 1,3,5-benzenetricarbonyltrichloride, aluminum Aluminum chloride and fluorobenzene can be prepared by a friedel-crafts reaction. In addition, branche structures of other structures can also be prepared by a similar Friedel-Craft reaction.

Next, the temperature of the mixture is lowered to 80 캜 or lower, and then monomers for producing a minority block (or hydrophilic block) are added to the organic solvent together with the carbonate anhydride.

The organic solvent to be added may be the same as the organic solvent. The mixture is stirred at 90 to 150 ° C, preferably 100 to 140 ° C for 3 to 5 hours, and then the azeotropic mixture with toluene or benzene is removed through a dean-stark trap. At this time, the azeotropic mixture which is distilled off is removed through the dean-stark trap. After the azeotropic mixture is completely removed as described above, the reaction mixture is allowed to react at 150 to 190 ° C for 6 to 24 hours with continued stirring.

The following 1) step will be described.

In this step, a sulfonated multiblock copolymer is precipitated in a sulfonated multiblock copolymer solution. The method of precipitating the sulfonated multiblock copolymer is not particularly limited as long as it is usable in general, but it is preferably precipitated using a non-solvent.

More specifically, the sulfonated multiblock copolymer in the sulfonated multiblock copolymer solution can be precipitated by adding non-solvent to the sulfonated multiblock copolymer solution.

According to a preferred embodiment of the present invention, the non-solvent comprises acetone; At least one alcohol selected from methanol, ethanol, isopropyl alcohol and n-butanol; One or more alkanes selected from hexane, cyclohexane and heptane; And a mixture thereof. The non-solvent is not limited to the above-mentioned solvent, but may be mixed with the solvent used for preparing the sulfonated multi-block copolymer solution, and soluble if the solvent is available. In addition, if the solubility of the sulfonated multiblock copolymer is low, it can be used as a non-solvent for the present invention.

In step 1), the non-solvent may be added while stirring the sulfonated multi-block copolymer solution with a stirrer. The amount of the non-solvent may be 0.5 to 5 times the amount of the solvent in the sulfonated multi-block copolymer solution, and preferably 0.5 to 2 times. And the accelerating acceleration of the non-solvent can be less than 2000 kg / hr / kg of total sulfonated multi-block copolymer solution (kg).

The temperature for carrying out the step 1) may be -30 to 150 ° C. Preferably from 20 to 50 < 0 > C, which may be economically advantageous. And the precipitated sulfonated multi-block copolymer can be precipitated as spherical particles.

Next, the above 2) step will be described.

In this step, the solution in which the sulfonated multi-block copolymer is precipitated is diluted with water, and the pH is adjusted with acid, so that the carbonate anhydride reacts with the acid to be easily removed.

According to a preferred embodiment of the present invention, in the step 2), water may contain 1 to 15 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the solution in which the sulfonated multiblock copolymer has been precipitated have. If the amount is less than 1 part by weight, the carbonate anhydride may not be effectively removed. If the amount is more than 15 parts by weight, the working volume of the manufacturing process may become large, the productivity may be low and the waste liquid may be large. Range is preferred.

The acid may include at least one selected from sulfuric acid, nitric acid, hydrochloric acid (HCl), and carboxylic acid, preferably hydrochloric acid. And the carboxylic acid may include formic acid, acetic acid, and the like.

In the present invention, the solution in which the sulfonated multiblock copolymer is precipitated is diluted with water and the pH is adjusted so that the carbonate anhydride precipitated in crystals is effectively removed.

According to a preferred embodiment of the present invention, the adjusted pH may be 6 to 8, preferably 6.5 to 7.5. If the pH is less than 6, there may be a problem that the physical properties of the polymer are changed by reacting with the functional group of the copolymer, and if the pH is more than 8, the removal efficiency of the carbonate anhydride may be lowered.

The next step 3) will be described.

The step of filtering the sulfonated multiblock copolymer precipitated in the step 2) is a step of obtaining only a sulfonated multiblock copolymer in a sulfonated multiblock copolymer solution. The filtration step of the present invention is not particularly limited, but it is sufficient that a device having a pore to such an extent that a sulfonated multiblock copolymer, which is a spherical particle, can be filtered.

After step 3), the step 4) is performed.

This step can be washed with water and / or alcohol to remove any solvent or salt remaining in the filtered sulfonated multiblock copolymer. Considering the drying efficiency, it can be washed with hot deionized water (~ 80 ℃) and alcohol with low boiling point. The washed polymer can be dried at a temperature of from room temperature to 150 ° C, and the drying time can be shortened by using a reduced pressure or a vacuum condition.

In the prior art, however, the sulfonated multiblock copolymer was not pretreated before filtration, so that an excessive amount of purified water had to be used in the washing step. There is a problem in that the process time is long by performing the cleaning step 8 times or more.

However, in the present invention, the solution in which the sulfonated multiblock copolymer precipitates is diluted with water and the pH is adjusted, whereby the residual carbonate anhydride is effectively removed. Thus, after filtering the sulfonated multiblock copolymer, the efficiency of the washing step to be performed is improved. Therefore, according to a preferred embodiment of the present invention, the cleaning step may be performed one or more times, preferably one to seven times. More preferably less than 6 times, and most preferably less than 4 times. As a result, the process time is remarkably reduced, and the economical effect is also obtained.

In conclusion, the present invention can improve the cleaning efficiency of the sulfonated multiblock copolymer.

As a result, the amount of wastewater is remarkably reduced, and the process time is reduced, so that an economical effect can be obtained.

 Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Manufacturing example

In a 1 L reactor connected to a Dean stark apparatus, 14.82 g of 4,4'-difluorobenzophenone, 14.38 g of a hydroquinone sulfonic acid potassium salt, [3,5-bis (4-fluorobenzoyl) phenyl] Fluorophenyl) methanone and 17.41 g of potassium carbonate were placed, 101.00 g of dimethyl sulfoxide (DMSO) and 90.90 g of benzene were added in a nitrogen atmosphere. The reaction product was heated to 90-140 ° C for 4 hours and stirred to distill the benzene. The reaction temperature was raised to 170 ° C and condensation polymerization was carried out for 5 hours. After the completion of the reaction, the reaction temperature was lowered to 80 ° C, and then 2.29 g of 4,4'-difluorobenzophenone, 6.25 g of 9,9-bis (4-hydroxyphenyl) fluorene, 0.10 g of 5-bis (4-fluorobenzoyl) phenyl] (4-fluorophenyl) methanone and 4.93 g of potassium carbonate were charged and 101.60 g of dimethyl sulfoxide (DMSO) and 99.40 g of benzene Respectively. The reaction product was heated to 90-140 ° C. for 4 hours and stirred to distill the benzene. The reaction temperature was raised to 170 ° C., and the reaction mixture was allowed to undergo condensation polymerization for 14 hours. After completion of the reaction, the reaction product was warmed to room temperature.

Example

To the branched sulfonated multiblock copolymer reaction solution prepared in Production Example, 246.60 g of acetone was gradually added dropwise over 1 hour. The stirring speed of the precipitation was 250 rpm. When about 220 g of acetone was added, the polymer began to precipitate slowly. After completion of the acetone addition, 246.60 g of methanol was added dropwise over 30 minutes. A spherical precipitate formed after completion of the methanol addition. Then, 246.60 g of purified water was added thereto, and the pH of the reaction solution was adjusted to 7 using 1 N HCl aqueous solution. The polymer slurry was then filtered, washed with 105.69 g of methanol, and then washed four times with 211.38 g of purified water.

Comparative Example

To the branched sulfonated multiblock copolymer reaction solution prepared in Production Example, 246.60 g of acetone was gradually added dropwise over 1 hour. The stirring speed of the precipitation was 250 rpm. When about 220 g of acetone was added, the polymer began to precipitate slowly. After completion of the acetone addition, 246.60 g of methanol was added dropwise over 30 minutes. A spherical precipitate formed after completion of the methanol addition. The polymer slurry was then filtered, washed with 105.69 g of methanol, and then washed eight times with 211.38 g of purified water.

Experimental Example

The residual amount of K ⁺ ions was analyzed using ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry) equipment to measure the residual amount of calcium carbonate remaining in the examples and comparative examples.

Number of washes Primary Secondary Third Fourth 5th 6th Seventh 8th car Comparative Example 21% 0.49% 0.15% 465ppm 130 ppm 39ppm 13 ppm 4 ppm Example 0.13% 233 ppm 33 ppm 4 ppm - - - -

However, when the branched sulfonated multifunctional copolymers prepared in the above Examples and Comparative Examples are made into an electrolyte membrane after the production, the mechanical strength of the thin membrane is lowered when the carbonate anhydride is remained, but when the branched anhydride is present in the copolymer at less than 10 ppm, And the measurement was performed only in the fourth example and the second example in the comparative example.

Measurement results As shown in Table 1, it can be seen that, in the case of the neutralized washing method, only four times of washing shows the same results as the conventional 8 times of washing.

Claims (17)

1) precipitating a sulfonated multiblock copolymer in a sulfonated multiblock copolymer solution;
2) diluting the solution in which the sulfonated multiblock copolymer is precipitated with water and adjusting the pH with acid;
3) filtering the sulfonated multiblock copolymer in the pH controlled solution; And
4) washing the filtered sulfonated multi-block copolymer. The method according to claim 1,
The sulfonated multiblock copolymer solution of step 1)
a) An aromatic dihalide monomer having a bisphenol-based monomer or aromatic dihalogen monomer, an acid substituent, or an acid substituent, a carbonate anhydride catalyst, a first organic solvent and a second organic solvent are charged in a reactor, Producing a block; And
b) In the reactor comprising the hydrophilic block, the first organic solvent, the bisphenol-based monomer, the aromatic dihalide-based monomer, the carbonate anhydride catalyst, Adding a first organic solvent and a second organic solvent, and polymerizing the resultant to prepare a minor block and preparing a multi-block copolymer. The method according to claim 1,
The sulfonated multiblock copolymer solution of step 1)
a) reacting a bisphenol-based monomer, an aromatic dihalogen-based monomer, a carbonate anhydride catalyst, Adding a first organic solvent and a second organic solvent to prepare a minor block; And
b) preparing the minor block, The first organic solvent An aromatic dihalogen monomer having a bisphenol-based monomer or an aromatic dihalide-based monomer, a bisphenol-based monomer having an acid substituent or an acid substituent, a carbonate anhydride catalyst, A step of adding a first organic solvent and a second organic solvent and polymerizing them to prepare a hydrophilic block and simultaneously preparing a multiblock copolymer. The method according to claim 1,
The sulfonated multiblock copolymer solution of step 1)
a) preparing bisphenol-based monomer, aromatic dihalide-based monomer, carbonate anhydride catalyst, first organic solvent and second organic solvent in a reactor and polymerizing to prepare a minor block;
b) An aromatic dihalide monomer having a bisphenol-based monomer or aromatic dihalogen monomer, an acid substituent, or an acid substituent, a carbonate anhydride catalyst, a first organic solvent and a second organic solvent are charged in a reactor and polymerized to prepare a hydrophilic Producing a block; And
c) dissolving the hydrophobic block prepared in the step a) and the hydrophilic block prepared in the step b) in a first organic solvent and a second organic solvent, and reacting the resultant with a carbonate anhydride catalyst to prepare a multiblock copolymer; ≪ / RTI > wherein the sulfonated multiblock copolymer is prepared by the process comprising: The method according to any one of claims 2 to 4,
The bisphenol-based monomer
At least one selected from the group consisting of 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-biphenol and 9,9-bis (4-hydroxyphenyl)
The aromatic dihalogen monomers include
4,4'-difluorobenzophenone, 4,4'-difluorobenzophenone, and 4,4'-dichlorobenzophenone. The method according to any one of claims 2 to 4,
The bisphenol-based monomer having an acid substituent
Dihydroxynaphthalene-3,6-disulfonic acid disodium salt, 1,7-dihydroxynaphthalene-3-sulfonic acid monosodium salt, bis (4-fluoro Sulfonylphenyl) sulfone, and 2,3-dihydroxynaphthalene-6-sulfonic acid monosodium salt,
The aromatic dihalogen monomers having an acid substituent include
(2-fluorobenzenesulfonate), 4,4'-difluorodiphenylsulfone and potassium 2,2 '- [9,9-bis (4-hydroxyphenyl) A sulfonate group, and a sulfonate group; and a sulfonate group. The method according to any one of claims 2 to 4,
Characterized in that a branching agent is added in the production of said hydrophilic block or minority block to produce a branched hydrophilic block or fractional block. The method of claim 7,
The branche was prepared by reacting [3,5-bis (4-fluorobenzoyl) phenyl] (4-fluorophenyl) methanone, [3,5- Phenyl) methanone, 3,5-difluoro-4'-fluorobenzophenone and (3,5-difluoro-4'-fluorophenyl) sulfone. Wherein the sulfonated multiblock copolymer is prepared by reacting a sulfonated polybutadiene with a sulfonated polyimide. The method according to any one of claims 2 to 4,
Wherein the carbonate anhydride catalyst is potassium carbonate. ≪ RTI ID = 0.0 > 8. < / RTI > The method according to any one of claims 2 to 4,
The first organic solvent
At least one selected from the group consisting of N, N'-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and N, N-dimethylformamide,
The second organic solvent
Benzene, toluene, and xylene. The method for producing a sulfonated multiblock copolymer according to claim 1, The method according to claim 1,
Wherein the step 1) is carried out by adding a non-solvent. The method of claim 11,
The non-solvent being acetone; At least one alcohol selected from methanol, ethanol, isopropyl alcohol and n-butanol; One or more alkanes selected from hexane, cyclohexane and heptane; And a mixture thereof. The method for producing a sulfonated multiblock copolymer according to claim 1, The method according to claim 1,
Wherein the water in the step 2) comprises 1 to 15 parts by weight based on 100 parts by weight of the solution in which the sulfonated multiblock copolymer is precipitated. The method according to claim 1,
In the step 2)
Wherein at least one selected from the group consisting of sulfuric acid, nitric acid, carboxylic acid and hydrochloric acid (HCl) is contained. The method according to claim 1,
Wherein the adjusted pH of step 3) is from 6 to 8. < RTI ID = 0.0 > 8. < / RTI > The method according to claim 1,
Wherein the step 4) is carried out one or more times. 18. The method of claim 16,
Wherein the step 4) is carried out from 1 to 7 times.