KR101723681B1 - Synthesis method of Ion-exchange Resin based on Sulfonated phenyl functionalized polystyrene-conjugated diene copolymer and Ion-exchange Resin manufactured by using the same - Google Patents

Abstract

The present invention relates to a method for synthesizing a sulfonated phenyl-functionalized polystyrene-conjugated diene random copolymer ion exchange resin produced through non-hydrogenation thiol-ene reaction and sulfonation reaction of styrene and conjugated diene, and an ion exchange resin produced through the same to show high electrical conductivity and ion exchange capacity. Through the method for synthesizing a PSB-T-S ion exchange resin of the present invention, the contents of a phenyl group introduced as a branch to the main chain of a polystyrene-conjugated diene random copolymer which is a polymer and a sulfonated group are adjusted. Thus, water resistance, flexibility, electrical conductivity, and ion exchange capacity of the produced ion exchange resin are remarkably improved. Also, an ion exchange resin showing high regenerating efficiency and ion exchange capacity can be produced.

Description

Synthesis method of sulfonated polyfunctional polystyrene-conjugated diene copolymer ion-exchange resin and ion-exchange resin prepared therefrom (Ion-exchange resin based on sulfonated phenyl functionalized polystyrene-conjugated diene copolymer and ion-exchange resin manufactured by using the same}

The present invention relates to a process for synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene random copolymer ion exchange resin capable of exhibiting high electrical conductivity and ion exchange capacity and an ion exchange resin exhibiting high regeneration efficiency and ion exchange capacity prepared therefrom .

In recent years, environment-friendly energy resources and technologies have been actively developed in various fields due to environmental damage caused by excessive use of fossil fuels and depletion of energy sources. As the pollution problem of industrial water and river water becomes serious due to the industrial development of modern society, ion exchange resin is the most important in the field of environment friendly energy technology, and researches on the ion exchange resin are actively conducted. The process using ion exchange resin has attracted worldwide attention as a clean technology that can reduce the use of chemical raw materials and reduce environmental pollution at the same time. Recently, the application range of ion exchange resin has been expanding as a high performance ion exchange membrane has been developed.

The ion exchange is a method of bringing a solution containing ions into contact with an ion exchange resin to exchange the ions to be extracted in the ions present in the solution with functional groups of the resin to recover the ions, , An adsorption step of adsorbing the adsorbed ions from the resin into an acid or an alkali solution, and a regeneration step of reusing the resin.

The ion exchange resin can be classified according to the type of the ion exchange group and the type of the ion exchange resin introduced into the base resin. Classification according to functional groups is a cation exchange resin which removes cations in solution by replacing cations in solution with their own cations and an anion exchange resin which removes anions in solution by replacing anions in solution with their anions. The classification according to the form can be divided into a granular ion exchanger and a fibrous ion exchanger.

A styrene resin in which an ion-exchange group is introduced into a resin having a three-dimensional network structure prepared by using divinylbenzene as a crosslinking agent in styrene as a cation exchange resin has been conventionally used. It is chemically stable in strong acid and strong bases, and has sulfonic acid group as an exchanger. It has the advantage of ion exchange in the entire pH range. However, it has low ion exchange capacity, density and moisture adsorption, There is a downside to this. Also, in the regeneration of the cation exchange resin, a large amount of strong acid such as hydrochloric acid or sulfuric acid is inevitably used, and a large amount of regenerated waste liquid is generated. Accordingly, various devices and chemicals for treating environmental pollution and regenerated waste liquid are required, There is a required problem. In order to improve the limit of the conventional cation exchange resin having a low ion exchange capacity, studies have been actively conducted to introduce a hydrophilic ion group such as a sulfonic acid group into the cation exchange resin in order to impart a high hydrogen ion conductivity of the cation exchange resin.

Korean Patent Laid-Open Publication No. 1997-0006365 discloses a method for producing a strongly acidic cation-exchange resin by adding a swelling agent to a crosslinked styrenic copolymer, heating it to swell, and then sulfonating it . The cation exchange resins proposed by the prior art are prepared through a construction in which cross-linked styrenic spherical particles are heat-treated in the presence of a swelling agent and then sulfonated in an anhydrous sulfur phase to improve surface defects, mechanical strength and cycle strength Respectively. However, the cation exchange resin does not exhibit a remarkable improvement effect of the ion exchange capacity, and due to the introduction of the hydrophilic sulfonic acid group, the cation exchange resin excessively swells by moisture, resulting in deterioration of mechanical properties and stability, .

Korean Patent Publication No. 1997-0006365

Disclosure of the Invention The present invention has been made to overcome the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for producing a polystyrene polymer, which comprises reacting styrene and a conjugated diene through a non- -Sulfonation which can lead to remarkable improvement in water resistance, flexibility, electrical conductivity and ion exchange capacity of the produced ion-exchange resin by controlling the content of the phenyl group and the sulfonated phenyl group introduced into the main chain of the conjugated diene random copolymer A method for synthesizing a phenyl-functionalized polystyrene-conjugated diene random copolymer ion-exchange resin, and an ion exchange resin exhibiting high regeneration efficiency and ion exchange capacity,

The present invention relates to a method for producing a polystyrene-conjugated diene copolymer, comprising the steps of: 1) synthesizing a polystyrene-conjugated diene copolymer; 2) synthesizing a phenyl functionalized polystyrene-conjugated diene copolymer through a thiol-enclosure reaction of the polystyrene-conjugated diene copolymer; And 3) synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer through a sulfonation reaction of the copolymer synthesized through the step 2); To a method for synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin.

In the present invention, the polystyrene-conjugated diene copolymer in the step 1) may be a polystyrene-conjugated diene random copolymer synthesized through polymerization of anion living solution of styrene and a conjugated diene.

In the present invention, the conjugated diene is not particularly limited, but may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3- -1,3-butadiene. ≪ / RTI >

In the present invention, the molar ratio of the styrene and the conjugated diene added in the anion living solution polymerization of step 1) may be 10:90 to 25:75.

In the present invention, the polystyrene-conjugated diene copolymer in the step 1) comprises a styrene repeating unit and a conjugated diene repeating unit, wherein the repeating unit derived from the conjugated diene of the copolymer is a repeating unit May be 0.001 to 35 mol%.

In the present invention, the step 2) comprises: (a) preparing a copolymer solution by dissolving the polystyrene-conjugated diene copolymer in the step (1) in an aprotic polar solvent; And (b) synthesizing a phenyl functionalized polystyrene-conjugated diene copolymer through a thiol-enclination reaction by adding a thiol compound and a radical initiator to the copolymer solution prepared in the step (a) can do.

In the present invention, the polystyrene-conjugated diene copolymer used in the step (a) includes a styrene repeating unit and a conjugated diene repeating unit, and contains a double bond introduced side by side among the repeating units derived from the conjugated diene of the copolymer May be 0.001 to 35 mol%.

In the present invention, the thiol compounds include, but are not limited to, phenylmethanethiol, 2-phenylethanethiol, 3-phenylpropane-1- thiol, 4-phenylbutane-1-thiol, 5-phenylpentane-1-thiol, 6-phenylhexane- Phenylhexane-1-thiol, 7-phenylheptane-1-thiol, 8-phenyloctane-1-thiol, Phenylenecan-1-thiol, 11-phenylundecane-1-thiol, and 11-phenylundecane-1-thiol -1-thiol, and 12-phenyldodecane-1-thiol.

In the present invention, the radical initiator is not particularly limited, and examples thereof include 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis- 2-methylpropionamide, 2,2'-azobis-N-butyl-2-methylpropionamide, 2,2'-azobis- [N- (2- Dimethyl 2,2'-azobisisobutyrate, and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile.

In the present invention, the thiol compound in step (b) is preferably present in the repeating units of the polystyrene-conjugated diene copolymer in step (a) in an amount of 50 to 700 and the radical initiator is added in an amount of 10 to 50 mol% based on the total amount of the repeating units containing double bonds introduced side by side among the repeating units of the unit constituting the polystyrene-conjugated diene copolymer in the step (a) . ≪ / RTI >

In the present invention, the thiol-enclination reaction in the step (b) may be performed at 30 to 50 ° C for 10 to 40 hours.

In the present invention, the phenyl-functionalized polystyrene-conjugated diene copolymer synthesized from the step (b) contains 20 to 35 mol% of side chain phenyl groups relative to the total content of styrene and conjugated diene repeating units contained in the copolymer And may be a polystyrene-conjugated diene copolymer containing repeating units.

In the present invention, the step 3) comprises: (a) preparing a mixed solution by adding and mixing the phenyl functionalized polystyrene-conjugated diene copolymer synthesized in the step 2) to an organic solvent of C1 to C3; And (b) adding a C2 to C8 acylsulfonate to the mixed solution, followed by stirring to synthesize a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer through a sulfonation reaction.

In the present invention, the step (b) may further include bubbling the prepared mixed solution into an inert gas.

In the present invention, the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer synthesized from the step (b) can be obtained by copolymerizing 5 to 30 mol% of side chain sulfonated Lt; RTI ID = 0.0 > phenyl. ≪ / RTI >

The present invention also relates to a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin prepared from the method of synthesizing the polystyrene-conjugated diene copolymer ion exchange resin.

In addition, the present invention relates to a fuel cell comprising the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin.

The synthesis method of the sulfonated phenyl functionalized polystyrene-conjugated diene random copolymer ion exchange resin according to the present invention is characterized in that the non-hydrogenated thiol-ene reaction and the sulfonation reaction of the styrene and the conjugated diene produce a polystyrene-conjugated diene random copolymer The water resistance, flexibility, electrical conductivity and ion exchange capacity of the produced ion exchange resin can be remarkably improved by introducing a phenyl group and a sulfonated phenyl group having a specific content range as a side chain in the main chain of the polymer, There is an advantage that it is possible to provide an ion exchange resin having a maximized capacity.

1- (a) is a result of measuring the absorbance of a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer according to an embodiment of the present invention; 1- (b) is a graph showing the degree of sulfonation according to the absorbance of a peak appearing in the extinction wavelength region inherent to the sulfonic acid group.
2 shows the results of measurement of mechanical properties of an ion exchange resin according to an embodiment of the present invention.

Throughout the specification, when an element is referred to as " including " an element, it does not exclude other elements unless specifically stated to the contrary.

The term " sulfonated phenyl functionalized polystyrene-conjugated diene copolymer " as used in the present invention refers to sulfonated phenyl (sulfonated phenyl) synthesized in the final step of the synthesis method of the present invention Quot; polystyrene-conjugated diene copolymer partially containing a repeating unit containing a functional group ", and the term " double bond side chain " means a side chain including some repeating units of the conjugated diene repeating units of the present invention Double bond introduced into the word '.

In addition, in the entire specification, "2) - (a) step", "2) - (b) step", "3) - (A) or step (b) 'belonging to step 2) or step 3), respectively.

Hereinafter, the synthesis method of the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin of the present invention and the ion exchange resin prepared therefrom will be described in detail. The following embodiments and drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Further, it is to be understood that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

The present invention relates to a method of synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin, comprising the steps of: 1) synthesizing a polystyrene-conjugated diene copolymer; 2) synthesizing a phenyl functionalized polystyrene-conjugated diene copolymer through a thiol-ene-click reaction of the polystyrene-conjugated diene copolymer; And 3) synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer through a sulfonation reaction of the copolymer synthesized through the step 2).

In the present invention, the step 1) may include a step of preparing a polystyrene-conjugated diene copolymer through polymerization of anion living solution of styrene and a conjugated diene. More specifically, styrene and a conjugated diene monomer may be reacted with C5 to C20 And then mixing and stirring an anionic polymerization initiator and a polar additive in the mixed solution to prepare a polystyrene-conjugated diene copolymer. In this case, the polystyrene-conjugated diene copolymer The diene copolymer may be a polystyrene-conjugated diene random copolymer synthesized through polymerization of the anion living solution.

In the present invention, the polystyrene-conjugated diene copolymer includes the styrene and the conjugated diene monomer, but not limited thereto, and may further include other monomers provided that the properties of the copolymer are not impaired.

In the present invention, the conjugated diene may be at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3 -butyl-1,3-octadiene, isoprene, , But is not limited thereto.

In addition, the molar ratio of the styrene and the conjugated diene added in the anion living solution polymerization in the step 1) of the present invention may be 10:90 to 25:75. In this case, the content range of the styrene and the conjugated diene is not particularly limited. However, in the above range, the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer, which is the final product of the present invention, Strength and other mechanical properties.

The anion polymerization initiator used in the step 1) of the present invention may be an organic lithium compound, and preferably an organic lithium compound such as methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, N-octyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyllithium, 3,5-di-n-octyl lithium, Heptylcyclohexyllithium, and 4-cyclopentyllithium. The content of the anion polymerization initiator may be 0.01 to 10 mmol, preferably 0.1 to 10 mmol based on 100 g of the styrene and the conjugated diene monomer, To 5 mmol, more preferably from 0.3 to 1 mmol, but is not limited thereto. The conjugated diene according to the present invention is a copolymer comprising a repeating unit having a double bond introduced into a side chain represented by the following formula (1) and a side chain represented by the following formula (2) by a radical generated through addition of the anion polymerization initiator It may be converted into a repeating unit and included in the polystyrene-conjugated diene copolymer in the step 1) together with the styrene repeating unit.

[Chemical Formula 1] < EMI ID =

R ₁ , R ₂ and R ₄ are each independently hydrogen or a C 1 to C ₃ aliphatic alkyl group, and R ₃ may be hydrogen, a phenyl group or a C 1 to C 3 aliphatic alkyl group, It is not.

In addition, the polar additive used in the step 1) of the present invention may be selected from the group consisting of trimethylamine, triethylamine, diethylether, di-n-propylether, diisopropylether, Diisopropyl ether, di-n-butylether, tetrahydrofuran (THF), dioxane, ethyleneglycol dimethylether, ethyleneglycol diethylether, But are not limited to, ethylene glycol dimethyl ether, N-methylmorpholine, N-ethylmorpholine, N-methrylmorpholin and ditetrahydrofurylpropane. DTHFP), and tetrahydrofuran (THF) may be preferably used. The content of the polar additive may be selected from the group consisting of styrene And 0.01 to 5 mmol, preferably 0.05 to 1 mmol, per 100 g of the conjugated diene monomer. In the present invention, by using a polar additive having a relatively high polarity, it is possible to increase the rate of reaction of a conjugated diene monomer having a slower polymerization reaction rate relative to the styrene monomer, thereby increasing the reaction rate of the styrene repeat unit and the conjugated diene, Conjugated diene repeat units) can be minimized to enable the synthesis of effective random polystyrene-conjugated diene copolymers. In addition, by adding a polar additive having a relatively high polarity as described above to minimize the formation of a block polymer of the same repeating unit, the effect of the uniformity of the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer, which is the final product of the present invention, The effect of controlling the content of the conjugated diene repeating unit including the double bond introduced into the side chain of Formula 1 can be obtained.

Synthesizing the 1) polystyrene-conjugated diene copolymer in the present invention; The polymerization terminator may include at least one selected from the group consisting of water, C1 to C3 alcohols, and the like. But is not limited to.

Accordingly, the polystyrene-conjugated diene copolymer prepared through the above step 1) of the present invention may be characterized in that it comprises a styrene repeating unit and a conjugated diene repeating unit as described above. , Preferably 0.1 to 15 mol%, more preferably 5 to 15 mol%, of the conjugated diene repeating unit containing the double bond introduced in the side chain represented by the above formula (1) 12 mol%. In this case, the content range of the repeating unit including the double bond introduced into the side branch is not particularly limited. However, in the above range, the final product of the present invention, the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin It is possible to form a uniform film.

In the present invention, the step 2) comprises the steps of: (a) preparing a copolymer solution by dissolving the polystyrene-conjugated diene copolymer in step 1) in an aprotic polar solvent; And (b) adding a thiol compound and a radical initiator to the copolymer solution prepared in the step (a) and adding a phenyl-functionalized polystyrene-conjugate through a thiol-ene-click reaction (2) - (b)) of synthesizing a diene copolymer.

The polystyrene-conjugated diene copolymer used in the step 2) - (a) of the present invention is the same substance as the polystyrene-conjugated diene copolymer prepared from the step 1), and as described above, the styrene repeat unit and the conjugated diene repeat Wherein the copolymer contains 0.001 to 35 mol% of a conjugated diene repeating unit containing a double bond introduced into the side chain represented by the general formula (1) in the total amount of the conjugated diene repeating units contained therein, .

Also, the aprotic polar solvent used in step 2) - (a) of the present invention may be at least one selected from the group consisting of dioxane, tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO) But are not limited to, one or more selected from the group consisting of dimethylformamide (DMF) and 1-methyl-2-pyrrolidone (NMP).

As the thiol compound in the step 2) - (b) of the present invention, an organic sulfur compound having a mercapto functional group in the aromatic ring may be used, and phenylmethanethiol, 2-phenyl 2-phenylethanethiol, 3-phenylpropane-1-thiol, 4-phenylbutane-1-thiol, Phenylheptane-1-thiol, 6-phenylhexane-1-thiol, 7-phenylheptane-1-thiol, -thiol, 8-phenyloctane-1-thiol, 9-phenylnonane-1-thiol, Phenyldecane-1-thiol, 11-phenylundecane-1-thiol and 12-phenyldodecane-1-thiol, And the like, but the present invention is not limited thereto.

The radical initiator may be 2,2'-Azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (2,4-dimethylvaleronitrile) Azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis Azobis [N- (2-propenyl) -2-methylpropionamide]), 2,2'-azobis 2'-azobis (N-butyl-2-methylpropionamide), dimethyl 2,2'-azobisisobutyrate (dimethyl 2,2'- Azobis (isobutyrate), and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) May be used, but the present invention is not limited thereto.

In the present invention, the above-mentioned thiol compound in the step 2) - (b) is preferably a repeating unit of the repeating units of all the monomers constituting the polystyrene-conjugated diene copolymer in the step 2) - (a) May be added in an amount of 50 to 700 mol% based on the total amount of the conjugated diene repeating unit containing the introduced double bond, and the radical initiator may be added to the repeating unit of the polystyrene-conjugated diene copolymer of the 2) - (a) May be added in an amount of 10 to 50 mol% based on the total amount of the conjugated diene repeating unit containing the double bond introduced into the side chain represented by the formula (1), but the present invention is not limited thereto. In the present invention, the content range of the thiol compound is not particularly limited. However, in the above content range, the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin as the final product of the present invention has properties such as elastic modulus and elongation And a phenyl functionalized polystyrene-conjugated diene copolymer containing a phenyl group side chain content sufficient to cause a specific range of sulfonation reaction to exhibit a remarkable improvement effect of ion exchange capacity.

In the present invention, the thiol-enantiomerization reaction in steps 2) - (b) is performed by adding a mixed solution prepared by adding a thiol compound and a radical initiator to the copolymer solution prepared in step 2) - (a) At 30 to 50 ° C for 10 to 40 hours, and cooling the mixed solution to -10 to 5 ° C to terminate the thiol-enclination reaction.

In addition, the present invention provides a process for producing a polyurethane foam, which comprises, after the completion of the thiol-enclosure reaction in steps 2) - (b) above, And adding at least one non-solvent to the mixed solution to purify the synthesized phenyl-functionalized polystyrene-conjugated diene copolymer present in the mixed solution.

Through the above process, the phenyl-functionalized polystyrene-conjugated diene copolymer synthesized from the step 2) - (b) of the present invention can be obtained by reacting the styrene-conjugated diene- And 35 mol% of the conjugated diene repeating unit represented by the formula (1) (the conjugated diene repeating unit containing a phenyl group as a side chain).

In the present invention, the step 3) comprises: (a) preparing a mixed solution by adding and mixing the phenyl functionalized polystyrene-conjugated diene copolymer synthesized in the step 2) to an organic solvent of C1 to C3; And (b) adding a C2 to C8 acylsulfonate to the mixed solution, followed by stirring to synthesize a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer through a sulfonation reaction.

The organic solvent used in the step 3) - (a) of the present invention may be a C1 to C3 halogenated hydrocarbon, preferably an organic solvent selected from the group consisting of dichloromethane, chloroform, tetrachloromethane, trichloroethane Trichloroethane, and dichloroethane. Dichloroethane may be used, but the present invention is not limited thereto.

Further, in the present invention, after the step 3) - (a), the method may further include bubbling the prepared mixed solution into an inert gas. At least one selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Ze), radon (Rn) and nitrogen Nitrogen gas may be used, but is not limited thereto. In the present invention, it is preferable to further include a step of bubbling the mixed solution prepared from the step 3) - (a) into an inert gas, whereby the thiol group of the phenyl-functionalized polystyrene-conjugated diene copolymer dissolved in the mixed solution It is possible to prevent oxidation of the thiol group by preventing contact of oxygen.

The acyl sulfonate used in the step 3) - (b) of the present invention may be an acyl sulfonate of C2 to C8, preferably an acetyl sulfonate, a propionyl sulfonate, Butyryl sulfonate, and more preferably, acetyl sulfonate, but is not limited thereto.

The sulfonated phenyl functionalized polystyrene-conjugated diene copolymer synthesized from the above step 3) - (b) of the present invention may be used in an amount of 5 to 30 mols relative to the total content of styrene and conjugated diene repeating units contained in the copolymer %, Preferably from 10 to 15 mol%, of a sulfonation degree of from 5 to 30 mol%, preferably from 10 to 15 mol%, including repeating units containing side-chain sulfonated phenyl groups.

In the present invention, the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer is not limited thereto, but when the sulfonation degree of the polystyrene-conjugated diene copolymer is 10 to 15 mol%, the water resistance improving effect is excellent, Ion exchange resin which exhibits remarkably improved electrical conductivity due to its low surface resistivity and which is excellent in elasticity and ion exchange ability makes it possible to produce an ion exchange resin which is the end product of the present invention and the sulfonated phenyl functionalized polystyrene- It is best if the coalescence has the degree of sulfonation in the above range.

In addition, the present invention relates to a method for producing a sulfonated polyfunctional polystyrene-conjugated diene copolymer, which comprises, after step 3) - (b), adding water, a C1 to C3 alcohol Or more of the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer is added to terminate the sulfonation reaction and distill to obtain the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer in a swollen state, and the obtained sulfonated phenyl functionalized polystyrene -Conjugated diene copolymer into a porous support mold and drying the solution to prepare a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin in the form of a membrane. At this time, the porous support may be any one selected from porous polyolefins such as porous polyethylene, porous Teflon, and porous polyimide. The sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion-exchange resin contains a porous support, whereby the effect of improving the tensile strength of the ion-exchange resin can be obtained.

The present invention may include a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin prepared from the method of synthesizing the polystyrene-conjugated diene copolymer ion exchange resin. The ion exchange resin of the present invention can have thermal stability and chemical stability of a polystyrene type polymer generally including the above polystyrene-conjugated diene copolymer, and it is possible to obtain a high ion conductivity And the water absorption is extremely low. Therefore, even when exposed to water for a long time, the characteristics of the resin are not changed and high film stability can be exhibited. Therefore, the ion exchange resin is excellent in performance and can be used in various fields such as a fuel cell or a secondary battery. .

 In addition, the present invention can include a fuel cell comprising the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin. The fuel cell of the present invention comprises the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer ion exchange resin of the present invention located between a cathode, an anode and an anode and a cathode. The anode may include a catalyst having a catalyst particle and a cation exchanger for accelerating a reduction reaction where a reduction reaction of oxygen occurs. The cathode may include a catalyst having catalyst particles and a cation exchanger for promoting an oxidation reaction, where oxidation reaction of the fuel occurs. The catalyst used for the positive electrode and the negative electrode may include catalyst metal particles and a catalyst carrier, and may contact the ion exchange resin of the present invention. In addition, various components commonly known in the art can be selectively added to the fuel cell in which the ion exchange resin of the present invention can be used.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, it should be understood that the present invention is not limited to the described embodiments, but various modifications and alterations may be made therein without departing from the spirit and scope of the invention.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

In an embodiment of the present invention, the term " double bond side chain " is used to mean a double bond introduced side chain included in some of the repeating units of the conjugated diene repeat units of the present invention.

In the embodiment of the present invention, the term " low-molecular weight double bond side chain " means that the conjugated diene repeat unit included in the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer of the present invention is a conjugate Quot; means that the content range of the diene (butadiene in the embodiment) repeating unit is 0.001 to 35 mol% based on the total content of the conjugated diene repeating unit, and the term " double bond side chain with intermediate content " The content range of the conjugated diene (butadiene) repeating unit containing a double bond introduced as a side chain among the conjugated diene repeating units contained in the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer is in the range of the total content of the conjugated diene repeating units 36 to 75 mol% ".

Further, in the embodiment of the present invention, the term " PSB (L) " is a word abbreviated to a polystyrene-butadiene copolymer (PSB) containing a low- , And the term " PSB (M) " was used to abbreviate a polystyrene-butadiene copolymer (PSB) containing a double bond side chain having a middle content (M).

In addition, in the embodiment of the present invention, the term " PSB " is used to refer to a general and common polystyrene-butadiene copolymer which may include both the PSB (L) and PSB (M) The term " PSB (L) -TS " or " PSB (M) -TS " refers to a sulfonylphenyl functionalized via a thiol-ene reaction and a sulfonation reaction Quot; polystyrene-butadiene copolymer (PSB) " containing a double bond side chain having a low content (L) or an intermediate content (M)

First, the experimental method performed in the present invention is presented.

Experiment 1) Measurement of sulfonation degree of polystyrene-conjugated diene copolymer

The absorbance was measured using an infrared spectrometer (Bruker Equinox 55 FT-IR spectrometer, Bruker, Germany), and the degree of sulfonation of the sulfonated phenyl functionalized polystyrene-conjugated diene copolymer synthesized through the following Examples was measured.

Experiment 2) Measurement of mechanical properties of ion exchange resin

The elasticity and hardness of the ion exchange resin prepared through the following examples were measured using a universal tensile tester (Instron 4484, Instron, USA).

Experiment 3) Measurement of electrical resistance, conductivity and water resistance of ion exchange resin

To measure the electrical resistance of the ion exchange resin, a conductive capacitance resistance meter (LCR, HIOKI 3522-50 LCR HiTESTER, Japan) was used at a frequency of 100 kHz and a voltage of 0.8V.

The ion exchange resin prepared through the following examples having a size of 2 cm x 2 cm was immersed in 1M sodium chloride solution at room temperature for 24 hours to reach equilibrium. After the equilibrium ion exchange resin was inserted into the electrochemical cell, the electrical resistance (R ₁ ) was measured using a 0.5 M sodium chloride solution using the conductivity resistance meter, and the ion exchange resin was removed. The resistance (R ₂ ) was measured and the electrical resistance and conductivity were measured by the following equation (1).

(Where R ₁ is the electrical resistance measured after inserting the ion exchange resin into the electrochemical cell, R ₂ is the electrical resistance of the electrolyte only after removing the ion exchange resin, and A is the effective area of the ion exchange resin Lt; / RTI >

[Equation 1]

In order to measure the water content of the ion exchange resin, the ion exchange resin prepared through the following examples was cut into a size of 4 cm x 4 cm, and the dry weight was measured. Then, the ion exchange resin was immersed in distilled water at room temperature for 24 hours, Swell. Thereafter, the free water on the surface of the fully swollen ion exchange resin was removed to measure the weight of the swollen ion exchange resin, and the water content of the ion exchange resin was calculated through the following equation (2).

(Where W _dry is the weight of the ion exchange resin in the dry state and W _wet is the weight of the ion exchange resin in the wet state).

&Quot; (2) "

Experiment 4) Measurement of ion exchange capacity of ion exchange resin

The ion exchange capacity of the ion exchange resin was measured by a titration method.

The dried ion-exchange resin prepared in the following examples was immersed in a 1 M sulfuric acid solution for 24 hours to replace with the H-form, and then washed several times with distilled water until the pH became neutral. The washed ion-exchange resin was dried in a vacuum oven at 50 ° C. for 24 hours, and the weight of the dried ion-exchange resin was measured. The dried ion-exchange resin was put into a 200 ml Erlenmeyer flask, and 1N sodium hydroxide 50 ml of the standard solution was added. The flask containing the ion exchange resin and sodium hydroxide standard solution was stirred at room temperature for 24 hours to reach equilibrium. A predetermined amount of the supernatant was collected from the flask, 2 to 3 drops of phenolphthalein indicator was added, Solution, and the ion exchange capacity was measured using the following equation (3).

(Where V _HCl and V _NaOH are the volumes of hydrochloric acid and sodium hydroxide used in the titration and N _HCl and N _NaOH are the normal concentrations of hydrochloric acid and sodium hydroxide)

&Quot; (3) "

[Example 1] Synthesis of sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer having a low content (8.8 mol%) double bond side chain and a sulfonation degree of 7.3 mol% Manufacturing

<Synthesis of basic polystyrene-butadiene (PSB (L)) random copolymer>

12 g (0.12 mol) of styrene and 28 g (0.52 mol) of butadiene in 400 ml of cyclohexane were added and mixed to prepare a styrene-butadiene mixed solution. 0.16 mmol of 2-butyllithium as an anion polymerization initiator and 0.067 mmol of tetrahydrofuran (THF) as a polar additive were added to the mixed solution prepared above and stirred for 8 hours at a temperature of 50 ° C to polymerize anion living solution , And the polymerization reaction was terminated by adding methanol as a reaction terminating agent to the mixed solution in which the polymerization reaction proceeded. An excessive amount of methanol was added to the mixed solution in which the polymerization reaction was terminated, and the resulting polystyrene-butadiene copolymer was purified by three times of precipitation and dried to obtain a purified polystyrene-butadiene (PSB (L)) random copolymer .

The number average molecular weight of the obtained random copolymer of PSB (L) was confirmed to be 240,000 g / mol through Gel Permeation Chromatography (GPC) measurement. Also, it was confirmed by 1H-NMR analysis that the molar ratio of styrene to butadiene in the PSB (L) copolymer was 18.8 / 81.2, and the content of the butadiene repeating unit including the double bonds introduced into the side chain was 8.8 mol%.

<Synthesis of Phenyl-functionalized Polystyrene-Butadiene (hereinafter PSB (L) -T) Copolymer>

 In a nitrogen atmosphere, 20 g of a PSB (L) copolymer containing butadiene repeating units containing a double bond introduced in the side chain of 8.8 mol% prepared above in 500 ml of tetrahydrofuran (THF) (0.022 mol of a double bond Side branch) was dissolved to prepare a mixed solution. 13.18 ml (0.11 mol) of phenylmethane thiol was obtained as a thiol compound and 2.08 g (0.0066 mol) of 2,2-azobis (4-methoxy-2,4- 2-azobis (4-methoxy-2,4-dimethylvaleronitrile) V-70, Wako Pure Chemical Industries, Japan) was added to the solution, and the solution was stored at 40 ° C for 24 hours to obtain thionol And the phenyl-functionalization proceeded through the click reaction. (Mol ratio of [thiol compound] / [double bond side chain containing repeating unit] / [radical initiator] = 5/1 / 0.3)

Thereafter, the mixed solution in which the thiol-enclit reaction proceeded was cooled to 0 ° C to terminate the thiol-enclination reaction, and then excess methanol was added as a non-solvent to prepare a phenyl-functionalized polystyrene-butadiene (PSB ) -T) copolymer was refined three times. The PSB (L) -T copolymer obtained through the above process was dried until the solvent completely evaporated to obtain a purified phenyl-functionalized polystyrene-butadiene (PSB (L) -T) copolymer.

1H-NMR analysis confirmed that the phenyl content of the PSB (L) -T copolymer obtained was 28.4 mol% based on the total content of the styrene and butadiene repeating units.

<Synthesis of sulfonated phenyl functionalized polystyrene-butadiene (hereinafter referred to as PSB (L) -T-S) copolymer]

2 g of the phenyl functionalized polystyrene-butadiene (PSB (L) -T) copolymer synthesized above was dissolved in 150 ml of a 1,2-dichloroethane solvent to prepare a polymer solution. The polymer solution was bubbled with a nitrogen gas for 30 minutes, and then cooled and maintained at 0 캜.

In an ice batch, 0.12 ml of sulfuric acid was slowly added dropwise to a mixture of acetic anhydride (0.4 ml) and 1,2-dichloroethane (10 ml) to prepare 10.52 ml of acetyl sulfate. 10.52 ml of the acetyl sulfate solution was added to the above- The solution was added to the polymer solution and stirred for 3 hours to proceed the sulfonation reaction. Then, 10 ml of 2-isopropanol was added to the sulfonated reaction solution to terminate the sulfonation reaction. The solution having been subjected to the sulfonation reaction was purified by adding distilled water, and the 1,2- Dichloroethane was evaporated to obtain sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer.

<Preparation of sulfonated phenyl functionalized polystyrene-butadiene (hereinafter referred to as PSB (L) -T-S) copolymer ion exchange resin>

A solution prepared by dissolving the obtained sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer in N, N-dimethylformamide (DMF) was coated with Teflon And dried at room temperature for 12 hours and then further dried at room temperature under vacuum for 12 hours to prepare a PSB (L) -TS copolymer ion exchange resin in the form of a membrane.

[Example 2] Synthesis of PSB (L) -T-S copolymer having a degree of sulfonation of 9.0 mol% and preparation of ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 0.5 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed, and 0.15 ml (L) -TS copolymer was prepared and the ion exchange resin was prepared by the same procedure except that 10.65 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Example 3] Synthesis of PSB (L) -T-S copolymer having a sulfonation degree of 9.4 mol% and preparation of an ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 0.58 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed, and 0.17 ml PSB (L) -TS copolymer was synthesized and ion-exchange resin was prepared by the same procedure except that 10.75 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Example 4] Synthesis of PSB (L) -T-S copolymer having a degree of sulfonation of 10.9 mol% and preparation of ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 0.63 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed and 0.19 ml (L) -TS copolymer was prepared and the ion exchange resin was prepared by the same procedure except that 10.82 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Example 5] Synthesis of PSB (L) -T-S copolymer having a sulfonation degree of 11.1 mol% and preparation of an ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 0.68 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed and 0.20 ml (L) -TS copolymer was prepared and ion-exchange resin was prepared by the same procedure except that 10.88 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Example 6] Synthesis of PSB (L) -T-S copolymer having a sulfonation degree of 13.2 mol% and preparation of an ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 0.76 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed with 0.23 ml PSB (L) -TS copolymer was prepared by the same procedure as above except that 10.99 ml of the acetyl sulfate solution prepared by dropwise addition was added to prepare an ion exchange resin.

[Example 7] Synthesis of PSB (L) -T-S copolymer having a degree of sulfonation of 18.0 mol% and preparation of ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 1.0 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed, and 0.30 ml (L) -TS copolymer was prepared and ion-exchange resin was prepared by the same procedure except that 11.3 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Example 8] Synthesis of PSB (L) -T-S copolymer having a sulfonation degree of 21.5 mol% and preparation of an ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, a mixture of acetic anhydride (1.26 ml) and 1,2-dichloroethane (10 ml) (L) -TS copolymer was prepared and ion exchange resin was prepared by the same procedure except that 11.63 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Example 9] Synthesis of PSB (L) -T-S copolymer having a degree of sulfonation of 24.3 mol% and preparation of ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (L) -TS) copolymer of Example 1, 1.44 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed and 0.43 ml (L) -TS copolymer was prepared and ion-exchange resin was prepared by the same procedure except that 11.87 ml of the acetyl sulfate solution prepared by dropwise addition was added.

COMPARATIVE EXAMPLE 1 Synthesis of a sulfonated phenyl functionalized polystyrene-butadiene (PSB (M) -TS) copolymer having an average content (57.1 mol%) of double bond side branches and a sulfonation degree of 7.1 mol% Manufacture of resin

<Synthesis of basic polystyrene-butadiene (hereinafter referred to as PSB (M)) random copolymer>

Except that 0.16 mmol of tetramethylethylenediamine (TMEDA) was added as a polar additive in the synthesis of the basic polystyrene-butadiene random copolymer of Example 1, the rest being polystyrene-butadiene (PSB (M ) Random copolymer was synthesized.

The number average molecular weight of the obtained random copolymer of PSB (M) was confirmed to be 259,000 g / mol through Gel Permeation Chromatography (GPC) measurement. Also, it was confirmed through 1H-NMR analysis that the content of the butadiene repeating unit including the double bond introduced into the side chain of the PSB (M) copolymer was 57.1 mol% based on the total content of the butadiene repeating unit.

<Synthesis of Phenyl-functionalized Polystyrene-Butadiene (hereinafter PSB (M) -T) Copolymer>

 In the synthesis step of the phenyl-functionalized polystyrene-butadiene copolymer of Example 1, PSB ((meth) acrylate) containing butadiene repeating units containing double bonds introduced in a side chain of 57.1 mol% in 300 ml of tetrahydrofuran (0.38 mol) of Phenylmethane thiol as a thiol compound and 7.05 g (0.38 mol) of a radical initiator as a radical initiator were added to a mixed solution prepared by dissolving 10 g (containing 0.075 mol of a double bond side chain) 0.0225 mol) of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile); V-70, Wako Pure Chemical Industries (M) -T) copolymer was synthesized by the same procedure except that the silylation reaction was carried out for 6 hours. (Mol ratio of [thiol compound] / [double bond side chain containing repeating unit] / [radical initiator] = 5/1 / 0.3)

1H-NMR analysis confirmed that the phenyl content of the PSB (M) -T copolymer obtained was 35.7 mol% based on the total content of the styrene and butadiene repeating units.

<Synthesis of sulfonated phenyl functionalized polystyrene-butadiene (hereinafter referred to as PSB (M) -T-S) copolymer]

In the synthesis of the sulfonated phenyl functionalized polystyrene-butadiene copolymer of Example 1, a polymer solution prepared by dissolving 2 g of a PSB (M) -T copolymer in a 1,2-dichloroethane solvent was used, Except that 10.45 ml of an acetyl sulfate solution prepared by slowly adding dropwise 0.10 ml of sulfuric acid to a mixture of 0.35 ml of acetic anhydride and 10 ml of 1,2-dichloroethane in an ice batch was used. Butadiene (PSB (M) -TS) copolymer.

<Preparation of sulfonated phenyl functionalized polystyrene-butadiene (hereinafter referred to as PSB (M) -T-S) copolymer ion exchange resin>

Except that sulfonated phenyl functionalized polystyrene-butadiene (PSB (M) -TS) copolymer was used in the production step of the sulfonated phenyl functionalized polystyrene-butadiene copolymer ion exchange resin of Example 1 (M) -TS copolymer ion exchange resin in the form of a membrane was prepared by the same procedure.

[Comparative Example 2] Synthesis of PSB (M) -T-S copolymer having a degree of sulfonation of 8.8 mol% and preparation of ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (M) -TS) copolymer of Comparative Example 1, 0.44 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed, and 0.13 ml (M) -TS copolymer was prepared and the ion-exchange resin was prepared by the same procedure except that 10.57 ml of the acetyl sulfate solution prepared by dropwise addition was added.

[Comparative Example 3] Synthesis of PSB (M) -T-S copolymer having a sulfonation degree of 13.1 mol% and preparation of an ion exchange resin

In the synthesis step of the sulfonated phenyl functionalized polystyrene-butadiene (PSB (M) -TS) copolymer of Comparative Example 1, 0.66 ml of acetic anhydride and 10 ml of 1,2-dichloroethane were mixed and 0.20 ml (M) -TS copolymer was prepared and ion-exchange resin was prepared by the same procedure except that 10.86 ml of the acetyl sulfate solution prepared by dropwise addition was added.

1 shows the results of measurement of sulfonation degree of the sulfonated phenyl functionalized polystyrene-butadiene copolymer synthesized from Examples 1 to 9 through the method of Experiment 1, The results of measuring the mechanical properties of the ion exchange resins prepared in Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1 and FIG.

The results of measuring the electrical resistance, conductivity, water resistance and ion exchange capacity of the ion exchange resins prepared in Examples 1 to 9 through the methods of Experiments 3 and 4 are shown in Table 2 below Respectively.

As shown in FIG. 1- (a), sulfonated phenyl functionalized polystyrene-butadiene (hereinafter referred to as PSB (L) -TS) copolymer synthesized from Examples 1 to 9 of the present invention is a sulfonated It can be confirmed that it contains a functional group. The PSB (L) -TS copolymers prepared from Examples 1 to 9 of the present invention exhibited large absorbance peaks in the regions of 1030 cm ^-1 and 1160 cm ^-1 when sulfonic acid groups were present (PSB (L)) copolymer and a phenyl-functionalized polystyrene-butadiene (PSB (L) -T) copolymer that are not sulfonated do not exhibit an absorbance peak in this region. Further, it can be seen that the PSB (L) -TS copolymer of the example synthesized by increasing the content of sulfuric acid and acetic anhydride in the present invention shows a larger peak of absorbance in the above region. 1- (a), the PSB (L) -TS copolymers prepared from Examples 1 to 9 of the present invention were found to have, in turn, 7.3, 9.0 , 9.4, 10.9, 11.1, 13.2, 18.0, 21.5 and 24.3 mol%, respectively. As a result, the sulfonation degree of the PSB (L) -TS copolymer synthesized from the present invention increases together with the increase of the amount of acetyl sulfate produced by the reaction of sulfuric acid and acetic anhydride added during the synthesis And it can be confirmed through the present invention that a PSB (L) -TS copolymer having a wide range of sulfonation degree can be produced.

The results of measurement of the mechanical properties of the ion exchange resins of Table 1, Examples 1 to 6 and Comparative Examples 1 to 3 show that sulfonated phenyl functionalized polystyrene-butadiene (PSB-TS) It can be seen that the higher the content of the butadiene repeating unit including the double bond introduced into the side chain included in the copolymer is, the more difficult it is to produce an ion-exchange resin having uniform appearance characteristics and physical properties. ) -TS copolymers, the mechanical properties change depending on the degree of sulfonation. In the case of Examples 1, 2 and 6 and Comparative Examples 1 to 3 having similar degrees of sulfonation, the PSB (L) of the embodiment having a low content of butadiene repeating units containing a double bond introduced side chain, -TS copolymer can be prepared as a membrane-type ion-exchange resin having uniform physical properties, and exhibits a mechanical property to the extent that it can be used as an ion-exchange resin. However, the butadiene repeating unit The PSB (M) -TS copolymer of Comparative Example having a high content can be made of a resin in the form of a membrane, but in this case, the appearance and physical properties of the resin are not uniform and it is confirmed that the PSB (M) -TS copolymer is not suitable for use as an ion exchange resin. Further, according to the measurement results of the mechanical properties of the ion exchange resin according to the embodiment of the present invention, the PSB (L) -TS copolymer synthesized from Examples 1 to 6 of the present invention is a flexible resin suitable for use as an ion- As the sulfonation degree of the PSB (L) -TS copolymer increases, the Young's modulus and hardness of the produced ion exchange resin are increased, the elongation and elasticity are decreased, and the plastic characteristics are increased .

In addition, the electrical characteristics and ion exchange capacity of the ion exchange resin prepared from the examples of the present invention shown in Table 2 above show that the surface resistance is 100 Ω · cm ² or more, and when the ion exchange resin is immersed in water for 24 hours, %, And the ion exchange resin prepared from the PSB (L) -TS prepared from the example of the present invention had an ion exchange capacity of 75 Ω · m, when prepared for a conventional ion exchange resin having an ion exchange capacity of 1.1 meq / g on average Cm ² and exhibits a low water content of up to 2% and less than 13%, respectively, when immersed in water for 24 hours and 1 week, and a high ion exchange capacity of 2 meq / g or more . In addition, as the degree of sulfonation of the PSB (L) -TS copolymer of the present invention is increased, the surface resistance and water content of the produced ion-exchange resin are remarkably reduced and the ion exchange capacity is effectively improved. And an ion exchange resin having excellent resin stability and significantly improved ion exchange capacity can be produced. In the case of the ion exchange resins of Examples 4 to 6 of the present invention, the surface resistance was measured to be 5.72 to 22.49 Ω · cm ² and the surface resistance was very low. When the ion exchange resin was immersed in water for 1 week, the ion exchange resin showed 5.1 to 9.6% PSB (L) -TS having a sulfonation degree of 10 to 15 mol% when producing an ion exchange resin exhibiting a low water content and a high ion exchange capacity of 1.24 to 2.26 at the same time and having excellent conductivity, resin stability and ion exchange capacity. It is preferable to use a copolymer.

It can be seen from Tables 1 to 2 and FIGS. 1 and 2 which are the results of the Experiments 1 to 4 that, by the method of synthesizing the polystyrene-conjugated diene copolymer ion exchange resin of the present invention, A PSB (L) -TS copolymer having a sulfonation degree of 5 to 30 mol%, preferably 10 to 15 mol%, which can exhibit resin stability and mechanical properties at the same time and exhibits a high ion exchange capacity can be synthesized, (L) -TS copolymer, it is possible to produce an ion exchange resin having excellent mechanical properties, conductivity and resin stability and remarkably improved ion exchange capacity, thus completing the present invention.

Claims (17)

1) synthesizing a polystyrene-conjugated diene copolymer;
2) synthesizing a phenyl functionalized polystyrene-conjugated diene copolymer through a thiol-enclosure reaction of the polystyrene-conjugated diene copolymer; And
3) synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer through a sulfonation reaction of the copolymer synthesized through the step 2)
The step 2) comprises: (a) preparing a copolymer solution by dissolving the polystyrene-conjugated diene copolymer in the step (1) in an aprotic polar solvent; And
(B) synthesizing a phenyl functionalized polystyrene-conjugated diene copolymer through a thiol-enclination reaction by adding a thiol compound and a radical initiator to the copolymer solution prepared in the step (a) Synthesis method of sulfonated phenyl functionalized polystyrene - conjugated diene copolymer ion exchange resin.
The method according to claim 1,
Wherein the polystyrene-conjugated diene copolymer in the step 1) is a polystyrene-conjugated diene random copolymer synthesized through polymerization of anion living solution of styrene and a conjugated diene.
3. The method of claim 2,
The conjugated diene is preferably a group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl- Of the polystyrene-conjugated diene copolymer ion-exchange resin.
3. The method of claim 2,
Wherein the molar ratio of the styrene and the conjugated diene added in the anion living solution polymerization of step 1) is from 10:90 to 25:75.
The method according to claim 1,
The polystyrene-conjugated diene copolymer in the step 1) comprises a styrene repeating unit and a conjugated diene repeating unit, and the repeating unit containing a double bond introduced as a side chain among the repeating units derived from the conjugated diene of the copolymer has a repeating unit 35 mol%. &Lt; Desc / Clms Page number 23 &gt;
delete The method according to claim 1,
The polystyrene-conjugated diene copolymer used in the step (a) preferably includes a styrene repeating unit and a conjugated diene repeating unit, wherein the repeating unit derived from the conjugated diene of the copolymer has a repeating unit Is 0.001 to 35 mol%. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The thiol compound may be selected from the group consisting of phenylmethanethiol, 2-phenylethanethiol, 3-phenylpropan-1-thiol, 4-phenylbutan- Phenylheptane-1-thiol, 10-phenylheptane-1-thiol, 11-phenylheptane-1-thiol, 1-thiol and 12-phenyldodecane-1-thiol. 2. A method for synthesizing a polystyrene-conjugated diene copolymer ion-exchange resin according to claim 1,
The method according to claim 1,
The radical initiator may be selected from the group consisting of 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, Azobis- [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis-N-butyl-2-methylpropionamide, dimethyl 2,2'-azobisisobutyl Butyrate and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile. The method of synthesizing a polystyrene-conjugated diene copolymer ion-exchange resin according to claim 1,
The method according to claim 1,
The thiol compound in the step (b) may be added in an amount of 50 to 700 mol% relative to the total amount of the repeating units containing a double bond introduced side by side among the repeating units of the unit constituting the polystyrene-conjugated diene copolymer in the step (a) And the radical initiator is added in an amount of 10 to 50 mol% based on the total amount of the repeating units including double bonds introduced side by side among the repeating units of the unit constituting the polystyrene-conjugated diene copolymer in the step (a) Of a polystyrene-conjugated diene copolymer ion-exchange resin.
The method according to claim 1,
Wherein the step (b) is carried out at a temperature of 30 to 50 ° C for 10 to 40 hours. The method for synthesizing a polystyrene-conjugated diene copolymer ion-exchange resin according to claim 1,
The method according to claim 1,
The phenyl-functionalized polystyrene-conjugated diene copolymer synthesized from the step (b) has a repeating unit containing a phenyl group at 20 to 35 mol% relative to the total content of styrene and conjugated diene repeating units contained in the copolymer Wherein the polystyrene-conjugated diene copolymer is a polystyrene-conjugated diene copolymer.
The method according to claim 1,
The step 3) comprises: (a) preparing a mixed solution by adding and mixing the phenyl-functionalized polystyrene-conjugated diene copolymer synthesized in the step 2) to an organic solvent of C1 to C3; And
(B) synthesizing a sulfonated phenyl functionalized polystyrene-conjugated diene copolymer by adding a C2 to C8 acylsulfonate to the mixed solution and stirring the mixture by a sulfonation reaction;
Wherein the polystyrene-conjugated diene copolymer is a copolymer of ethylene and propylene.
14. The method of claim 13,
Further comprising a step of bubbling the prepared mixed solution into an inert gas after the step (a).
14. The method of claim 13,
The sulfonated phenyl functionalized polystyrene-conjugated diene copolymer synthesized from the step (b) can be produced by copolymerizing 5 to 30 mol% of a side-chain-sulfonated phenyl group with respect to the total content of styrene and conjugated diene repeating units contained in the copolymer Wherein the repeating unit contains a repeating unit containing at least one repeating unit.
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