KR20110062849A - Poly(arylene ether)copolymer, method of manufacturing the same, and use thereof - Google Patents

Abstract

PURPOSE: A poly(arylene ether)copolymer is provided to ensure excellent processability and physical properties, and improved ion exchange capability and metallic ion adsorption ability and to enable use as a cation exchange resin or cation exchange membrane. CONSTITUTION: A poly(arylene ether)copolymer is represented by chemical formula 1. A method for manufacturing the poly(arylene ether)copolymer comprises: synthesizing a copolymer of chemical formula 5 by polymerizing a dihydroxy monomer of chemical formula 2, a dihalide monomer of chemical formula 3, and a dihydroxy monomer of chemical formula 4; and introducing a cation exchange group to a copolymer phenyl ring of chemical formula 5.

Description

Poly (arylene ether) copolymer, method for preparing the same, and use thereof {Poly (Arylene Ether) copolymer, method of manufacturing the same, and use}

The present invention relates to poly (arylene ether) copolymers having excellent processability and physical properties, having improved ion exchange capacity and metal ion adsorption capacity, which can be used as cation exchange resins and cation exchange membranes, methods for preparing the same, and uses thereof.

In order to prevent the pollution of industrial water and river water according to the industrial development of the modern society, and to secure valuable metal resources, much attention has been focused. Physical and chemical methods are known as a method for this purpose, and ion exchange methods are most commonly used as a dual chemical method.

Ion exchange is a method of recovering ions in a solution by contacting a solution with an ion exchange resin to exchange ions to be extracted from the solution with a functional group of a resin. It can be described as an extraction step for recovering from the resin to the acid or alkaline solution and a regeneration step for reusing the resin.

Ion exchange resins can be classified according to the type of ion exchange groups introduced into the base resin and the type of ion exchange resin. The functional groups are classified into cation exchange resins for removing cations in a solution by replacing cations in the solution with their own cations, and anion exchange resins for removing anions in a solution by replacing anions in the solutions with their anions. In addition, the classification according to the form can be divided into granular ion exchanger and fibrous ion exchanger.

 Currently, styrene-based resins incorporating ion exchangers into resins having a three-dimensional network structure made by using divinylbenzene as a crosslinking agent in styrene as a cation exchange resin are commercially available. It is chemically stable to strong acids and strong bases and has the advantage of being capable of ion exchange in the entire pH range because of sulfonic acid groups as exchangers, but when heated to 150 ° C or higher, it decomposes to lower exchange capacity, density, and water adsorption, and 186 ° C. If it is heated for 24 hours at, the exchange capacity is reduced by 15 to 40%.

Such ion exchange resins are used for various purposes such as recovery of valuable metals, air purification, catalysts, water treatment, pharmaceuticals and protein separation.

However, currently used ion exchange resins have a limit in ion exchange capacity, and most of them are crosslinked, and thus have disadvantages of poor workability. Therefore, there is an urgent need for the development of new ion exchange resins that have alleviated these shortcomings.

It is an object of the present invention to provide a poly (arylene ether) copolymer having excellent processability and physical properties.

Another object of the present invention is to provide a method for preparing the poly (arylene ether) copolymer.

Another object of the present invention is to provide a cation exchange resin having improved ion exchange capacity and metal ion adsorption capacity, including the poly (arylene ether) copolymer.

Another object of the present invention is to provide a cation exchange membrane having an improved ion exchange capacity and metal ion adsorption capacity, including the poly (arylene ether) copolymer.

In order to achieve the above object, the present invention provides a poly (arylene ether) copolymer represented by the following general formula (1):

[Formula 1]

(In the formula 1,

이고,Ar ₁ is

ego,

이고,Ar ₂ is

ego,

Where E ₁ , E ₂ , E ₃ , E ₄ , E ₅ and E ₆ is the same as or different from each other, a single bond, O, S, C (= O), S (= O), S (= O) ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , Si (CH ₃ ) ₂ , P (= 0) CH ₃ or C (= 0) NH,

Z represents one type of cation exchange group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carbonic acid group, a sulfonimide group, and a C ₁ to C ₁₀ alkylsulfonic acid group or a metal base thereof,

x is 0.01 to 1,

n is an integer from 10 to 800)

In addition, the present invention as shown in Scheme 1,

S1) synthesizing a copolymer represented by Formula 5 by polymerizing a dihydroxy monomer of Formula 2, a dihalide monomer of Formula 3 and a dihydroxy monomer of Formula 4; And

S2) provides a method of preparing a poly (arylene ether) copolymer represented by Formula 1, including introducing a cation exchange group to a copolymer phenyl ring portion of Formula 5:

Scheme 1

(In Scheme 1,

X is Cl, Br, I, or F,

Ar ₁ , Ar ₂ , x, n and Z follow the definition above)

The present invention also provides a cation exchange resin comprising the poly (arylene ether) copolymer.

In addition, the present invention provides a cation exchange membrane comprising the poly (arylene ether) copolymer.

The poly (arylene ether) copolymer of the present invention is not only excellent in physical properties, ion exchange capacity and metal ion adsorption capacity, but also easily processed and molded into various forms and thus can be widely applied.

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

Generally, most polymers are crosslinked with ion exchange resin. As a result, workability is inferior, and its application is limited. In addition, there is a disadvantage in that a catalyst for the crosslinking reaction is required and the crosslinking reaction is complicated.

In order to solve this problem, in the present invention, a cation exchange group is introduced into the side chain to have a flowable polymer chain, thereby providing excellent processability and physical properties, as well as a high cation exchange group introduction ratio, thereby providing excellent ion exchange ability (poly (arylene ether)). To provide a copolymer.

Specifically, the poly (arylene ether) copolymer of the present invention is represented by the following general formula (1):

[Formula 1]

(In the formula 1,

이고,Ar ₁ is

ego,

이고,Ar ₂ is

ego,

Where E ₁ , E ₂ , E ₃ , E ₄ , E ₅ and E ₆ is the same as or different from each other, a single bond, O, S, C (= O), S (= O), S (= O) ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , Si (CH ₃ ) ₂ , P (= 0) CH ₃ or C (= 0) NH,

Z represents one type of cation exchange group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carbonic acid group, a sulfonimide group, and a C ₁ to C ₁₀ alkylsulfonic acid group or a metal base thereof,

x is 0.01 to 1,

n is an integer from 10 to 800)

The poly (arylene ether) copolymers according to the present invention may be random or block copolymers.

In Formula 1, Z represents a cation exchange group that may independently have a proton, preferably Z is a sulfonic acid group or a metal base thereof. As the metal salt, sodium salt or potassium salt is preferable.

The poly (arylene ether) copolymer is designed to have an appropriate molecular weight in the manufacturing step, preferably to have a weight average molecular weight of 10,000 to 1,000,000. If it is less than the above range, the mechanical properties and chemical stability are insufficient, on the contrary, if the above range is exceeded, the viscosity becomes too high, which makes handling difficult.

Specific examples of the poly (arylene ether) copolymer according to Formula 1 above include, but are not limited to:

Poly (arylene ether) 1:

Poly (arylene ether) 2:

Such a poly (arylene ether) copolymer of the present invention, as shown in Scheme 1, S1) by dimerizing the dihydroxy monomer of formula (2), dihalide monomer of formula (3) and dihydroxy monomer of formula (4) Synthesizing a copolymer represented by; And S2) introducing a cation exchange group into the copolymer phenyl ring portion of Formula 5:

Scheme 1

(In Scheme 1,

X is Cl, Br, I, or F,

Ar ₁ , Ar ₂ , x, n and Z follow the definition above)

First, in step S1), the copolymer represented by Chemical Formula 5 is synthesized by performing a condensation polymerization reaction of the dihydroxy monomer of Chemical Formula 2, the dihydride monomer of Chemical Formula 3 and the dihydroxy monomer of Chemical Formula 4.

This polycondensation reaction proceeds through a nucleophilic substitution reaction through an activation step and a polymerization step. This reaction may be carried out under reaction conditions generally known in the art to which the present invention pertains, and therefore, the present invention is not particularly limited.

In this case, it is preferable that the dihalide monomer of the formula (2) and the dihydroxy monomer of the formula (4) react with each mole ratio of 0.1 to 0.9 and 0.1 to 0.9 with respect to 1 mole of the dihydroxy monomer of the formula (3).

Such polymerization is carried out in an organic solvent, and is not particularly limited in the present invention as long as it can dissolve the reactants and the product well. In one example, toluene, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide or mixtures thereof are possible.

In this case, the reaction may proceed under an alkali metal base to facilitate the nucleophilic substitution reaction. The alkali metal base is preferably potassium carbonate, sodium carbonate, sodium hydroxide, or calcium hydroxide.

Next, in step S2), a cation exchange group is introduced into the copolymer phenyl ring portion of the formula (5).

The copolymer of formula 5 is impregnated or reacted with a sulfonic acid compound, a phosphoric acid compound, or a carboxylic acid compound to introduce a cation exchange group. For example, to obtain a sulfonated poly (arylene ether) by reacting with a copolymer of formula (5) and one sulfonic acid compound selected from the group consisting of chlorosulfonic acid, fuming sulfuric acid, triethylphosphate salt, and concentrated sulfuric acid It can be phoned later.

In this case, it is preferable that the fonning reaction described later is performed at 0 to 100 ° C, preferably at 25 to 50 ° C. If the reaction temperature is less than the above range, it is not possible to obtain a sufficiently sulfonated polymer. On the contrary, the sulfonation rate is not increased any more even if the reaction temperature is exceeded, and the polymer backbone may be decomposed in some cases.

At this time, if necessary, an additional oxidation reaction may be further performed between the steps S1) and S2).

For example, when Ar ₂ includes a sulfane functional group, it may be oxidized to a sulfone functional group through an additional oxidation reaction as in Scheme 2 below.

Scheme 2

The acid reaction is not particularly limited in the present invention, a method commonly used in this field is possible.

For example, in the presence of a solvent, the compound of Formula 5 and the oxidizing agent are mixed in a predetermined equivalent ratio to perform the oxidation reaction. As the oxidizing agent, metachloroperoxybenzoic acid, hydrogen peroxide, oxone or magnesium monoperphthalic acid may be used.

The solvent may be dichloromethane, toluene, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, styrene, benzene, n-butyl acetate, methylcyclohexane, dimethylcyclohexane or a mixed solvent thereof.

The reaction is carried out at 25 to 50 ° C. for 30 minutes to 10 hours.

The poly (arylene ether) copolymer of the present invention prepared as described above may be applied as a cation exchange resin or a cation exchange membrane because of excellent physical properties, ion exchange ability, and metal ion adsorption capacity.

Accordingly, the present invention provides a cation exchange resin comprising the poly (arylene ether) copolymer of Chemical Formula 1.

The poly (arylene ether) copolymer of the present invention can be molded in various forms because of its excellent solubility in various solvents at room temperature. For example, it may be prepared in the form of gel, porous spherical beads, granules, etc. to be applied as a cation exchange resin. The cation exchange resin of the present invention thus formed may be applied to a chromatography column including a cation exchange resin, a composite material including a cation exchange resin, a filtration member including a cation exchange resin, and the like.

In addition, the present invention provides a cation exchange membrane comprising the poly (arylene ether) copolymer of the formula (1).

 The method of forming a film using the poly (arylene ether) copolymer is well known in the art, and thus a detailed description thereof will be omitted. For example, the poly (arylene ether) copolymer may be dissolved in an organic solvent, cast on a glass substrate, and then the solvent may be removed to prepare a film. In particular, since the poly (arylene ether) copolymer of the present invention is excellent in workability, it is convenient to form a film.

Specifically, the cation exchange membrane of the present invention is applied as a desalting membrane, a concentrated membrane, a specially selected permeable membrane, and an electrolyte membrane according to the use, and thus can be widely used in the fields of electrodialysis, diffusion dialysis, reverse osmosis, electrodialysis, fuel cells, and the like. have. It can also be used to remove metal ion contaminants in positive and negative photoresist fabrication.

Hereinafter, preferred examples and experimental examples of the present invention are described. The following examples and experimental examples are described for the purpose of more clearly expressing the present invention, but the contents of the present invention are not limited to the following examples and experimental examples.

Example 1 Synthesis of Poly (arylene Ether) Copolymer of Formula 8 (x = 0.25)

 A poly (arylene ether) copolymer represented by Chemical Formula 8 was prepared by the following Scheme 3.

Scheme 3

1-1. Preparation of Poly (arylene Ether) Copolymer of Formula 6

Three monomers 1,2-bis (4-hydroxyphenyl) -1,2-diphenylethylene (1,2) in a two-necked round-bottom flask in a nitrogen atmosphere on a device equipped with a condenser, Deanstock trap and magnetic stub. -bis (4-hydroxyphenyl) -1,2-diphenylethylene: 5 mmol), 4,4'-difluorodiphenylsulfone (20 mmol), and 4,4'-thiodiphenol ( 4,4'-Thiodiphenol: 15 mmol) was added, and potassium carbonate (24 mmol) was added thereto, using dimethylacetamide (Dimethylacetamide: DMAc: 70 mL) and toluene (50 mL) as reaction solvents.

The activation step was carried out for 4 hours at the reaction temperature of 140 ℃, water produced as a by-product during the reaction was removed with one of the reaction solvent toluene. The reaction temperature was gradually raised to 165 ° C. for polymerization for 24 hours. After the reaction, the mixture was washed several times with methanol / water (volume ratio = 1: 1) and vacuum dried at 60 ° C. for 24 hours.

The final product was obtained as a white solid (yield: 97%), ¹ H-NMR was performed for structural analysis of the final product, the results are shown in FIG.

1-2. Preparation of Poly (arylene Ether) Copolymer of Chemical Formula 7 by Oxidation

After dissolving 5 g of the copolymer of Chemical Formula 6 synthesized in 1-1 in 100 mL of dichloromethane, 5 g of metachloroperoxybenzoic acid (MCPBA) was mixed. After reacting for 6 hours at room temperature, the reaction solution was poured into methanol to precipitate. Then washed three times with methanol and dried in vacuo at 120 ℃ to give the final product (yield: 95%).

¹ H-NMR was performed on the final product to analyze the structure, and the results are shown in FIG. 1. Referring to FIG. 1, it was confirmed that the peak of the benzene hydrogen of Ar-S-Ar around 6.9 ppm was changed to sulfone (SO ₂ ) and disappeared, and the synthesis was confirmed by comparing the area ratio thereof.

1-3. Preparation of Poly (arylene Ether) Copolymer of Formula 8 through Subsequent Phonenization Process

In a 100 mL flask equipped with a condenser and a magnetic stirrer bar, in a nitrogen atmosphere, 5 g of the copolymer of formula 7 obtained in 1-2 were dissolved in 60 mL of concentrated sulfuric acid, followed by 12 hours at 45 ° C. Reacted for a while. Subsequently, the reaction solution was poured into distilled water to precipitate the polymer. The precipitated polymer was then washed several times with distilled water to remove residual sulfuric acid. The purified polymer was dried in vacuo at 120 ℃ to obtain a sulfonated poly (arylene ether) copolymer of formula (8) (yield: 94%).

¹ H-NMR was performed for structural analysis of the final product, and the results are shown in FIG. 1. Referring to FIG. 1, when the sulfonic acid group was introduced, a peak around 7.50 ppm was generated, which was shown to be downfield of hydrogen at an alpha position of the sulfonic acid group, and was accurately synthesized through an area ratio.

Example 2: Synthesis of Poly (arylene Ether) Copolymer (x = 0.3)

2-1. Preparation of Poly (arylene Ether) Copolymer of Formula 6

1,2-bis (4-hydroxyphenyl) -1,2-diphenylethylene (6 mmol), 4,4'-difluorodiphenylsulphone (20 mmol), and 4,4'-thiodiphenol (14 mmol) was added in the same manner as in Example 1, except that the final product was obtained in a white solid (yield: 95%).

¹ H-NMR was performed for structural analysis of the final product, and the results are shown in FIG. 2.

2-2. Preparation of Poly (arylene Ether) Copolymer of Chemical Formula 7 by Oxidation

Using the copolymer of Formula 6 obtained in 2-1 in the same manner as in Example 1-2, the oxidation reaction was carried out to obtain a copolymer of Formula 7 (yield: 93%).

¹ H-NMR was performed on the final product to analyze the structure, and the results are shown in FIG. 2. Referring to FIG. 2, it was confirmed that the peak of the benzene hydrogen of Ar-S-Ar around 6.9 ppm was changed to sulfone (SO ₂ ) and disappeared, and the synthesis was confirmed by comparing the area ratio thereof.

2-3. Preparation of Poly (arylene Ether) Copolymer of Formula 8 through Subsequent Phonenization Process

Using the copolymer of Chemical Formula 7 obtained in the above 2-2 was carried out in the same manner as in Example 1 to 1-3 to the phonation reaction described below, to obtain a copolymer of Chemical formula 8 (yield: 93%).

¹ H-NMR was performed for structural analysis of the final product, and the results are shown in FIG. 2. Referring to FIG. 2, when the sulfonic acid group was introduced, a peak around 7.50 ppm was generated, which was shown to be downfield of hydrogen at an alpha position of the sulfonic acid group, and was accurately synthesized through an area ratio.

Example 3: Synthesis of Poly (arylene Ether) Copolymer (x = 0.3)

A poly (arylene ether) copolymer represented by Chemical Formula 10 was prepared as shown in Scheme 4 below.

Scheme 4

3-1. Preparation of Poly (arylene Ether) Copolymer of Formula 9

1,2-bis (4-hydroxyphenyl) -1,2-diphenylethylene (5 mmol), 4,4'-difluorodiphenylsulfone (20 mmol), and bis (4-hydroxy-3, A copolymer was prepared under the same conditions and methods as in Example 1-1 except that 5-dimethylphenyl) sulfone (15 mmol) was used as the monomer.

The final product was obtained as a white solid (yield: 95%), and the structure was analyzed by ¹ H-NMR, and the results are shown in FIG. 3.

3-2. Preparation of Poly (arylene Ether) Copolymer of Chemical Formula 10 through Subsequent Phonetion Process

A sulfonated poly (arylene ether) copolymer of Chemical Formula 10 was prepared under the same conditions and methods as in Example 1 1-3 except that the copolymer of Chemical Formula 9 synthesized in 3-1 was used (yield: 94%).

¹ H-NMR was performed on the final product to analyze the structure, and the results are shown in FIG. 3. Referring to FIG. 3, when the sulfonic acid group was introduced into the copolymer, a peak near 7.50 ppm was generated, which is indicated by down-field hydrogen in the alpha position of the sulfonic acid group, and it was confirmed that the synthesis was accurately performed through the area ratio.

Experimental Example 1 Measurement of Molecular Weight and Dispersion

The weight average molecular weight and polydispersity index (PDI) of the poly (arylene ether) copolymers prepared in Examples 1 to 3 were measured using chromatography, and the results are shown in Table 1 below. The instruments and conditions used for the measurements are as follows:

GPC unit: Waters, model 2424

Column: Waters, model HR3,4,5 Column temperature: 80 ℃

Elution solvent: dimethylformamide

Elution rate: 1 ml / min.

Reference Material: Polymethylmethacrylate (PMMA)

division Weight average molecular weight (X10 ³ ) Polydispersity Index (PDI) Example 1 164 1.77 Example 2 173 1.89 Example 3 123 1.81

Experimental Example 2: Solubility in Organic Solvents

N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethyl sulfonide (DMSO) at room temperature of the poly (arylene ether) prepared in Examples 1 to 3, Solubility in methanol (MeOH) and water is summarized in Table 2 below.

division NMP DMAc DMF DMSO MeOH water Example 1 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 2 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 3 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble

As shown in Table 2, the poly (arylene ether) copolymer according to the present invention is excellent in solubility at room temperature in various kinds of solvents has a great advantage when processing for various uses.

Experimental Example 3: Measurement of Mechanical Strength

The poly (arylene ether) copolymers obtained in Examples 1 to 3 above were dissolved in N-methylpyrrolidone (NMP), cast on a glass plate, and dried at 120 ° C. to prepare a cation exchange membrane. Tensile strength was measured using an Instron mechanical testing machine (model name 5540) according to ASTM D882, and the results are shown in Table 3 below.

The tensile strength
(Mpa) Nafion211 Example 1 Example 2 Example 3 20 39 31 48

As shown in Table 3, the poly (arylene ether) copolymer of the present invention is expected to be easily used as a cation exchange resin or a cation exchange membrane because of excellent physical and mechanical properties due to high molecular weight and excellent solubility in organic solvents. do.

Experimental Example 4: Ion Exchange Capacity Measurement

The poly (arylene ether) copolymer membranes obtained in Experimental Example 3 were each immersed in 0.1 M NaCl solution for at least 48 hours to replace hydrogen ions (H ⁺ ) with sodium ions (Na ⁺ ). The substituted hydrogen ion (H ⁺ ) is titrated with 0.01 N NaOH standard solution, and the ion exchange capacity (Ion Exchange Capacity, IEC) value of the polymer membrane is calculated according to Equation 1 as the amount of NaOH used in the titration, The results are shown in Table 4 below.

[Equation 1]

IEC (meq / g) = (V _NaOH C _NaOH ) / W _dry

(Equation 1, W _dry : weight of dried thin film (g), V _NaOH : consumed NaOH standard solution (mL), C _NaOH : NaOH standard solution (M))

division Ion exchange capacity (meq / g) Example 1 1.75 Example 2 2.02 Example 3 1.89

Experimental Example 5 Measurement of Adsorption Ability on Metal Ions

In order to determine the adsorption capacity of the poly (arylene ether) copolymer according to the present invention to metal ions, adsorption experiments on copper and nickel ions were carried out as follows.

The metal ion solutions prepared at 50 mg / L, respectively, were adjusted to pH 1.65 and 8.55 with hydrochloric acid and sodium hydroxide, 0.3 g of the poly (arylene ether) copolymers of Examples 1 to 3 were added thereto, and 25 The treatment was carried out at 占 폚 for 24 hours. After the adsorption experiment, the metal ion concentration in the metal ion solution was measured by Inductively Coupled Plama-Atomic Emission Spectrometer (ICP-AES), and the results are shown in Tables 5 to 6 below.

division Copper ion concentration (ppm) pH 1.65 pH 8.55 Example 1 110 105 Example 2 421 401 Example 3 598 578 Metal Ion Solution 850 850

division Nickel ion concentration (ppm) pH 1.65 pH 8.55 Example 1 98 138 Example 2 354 472 Example 3 520 592 Metal Ion Solution 850 850

According to Table 5 and Table 6, the cation exchange membrane containing the poly (arylene ether) copolymer according to the present invention in both the acidic solution of low pH and the basic solution of high pH was excellent in adsorption capacity for copper and nickel ions. .

Experimental Example 6: Investigation of cation exchange characteristics

The poly (arylene ether) copolymer membrane obtained in Experimental Example 3 was a raw water (100 ppm NaCl solution, pH 5.78) in a water treatment module equipped with a membrane as shown in Table 7 under a flow rate of 30 ml / min and a pressure of 0.3 to 0.5 kgf / The cation exchange characteristics were investigated by setting cm ² , an integer of 180 seconds, a short of 60 seconds, a withdrawal of 50 seconds, and a separation of 10 seconds, and the results are shown in Table 8 below.

cathode CMX Example 1 Example 2 Example 3 anode AMX AMX AMX AMX CMX (Astom cation exchange membrane) AMX (Astom anion exchange membrane)

CMX / AMX Example 1 Example 2 Example 3 Throughput (%) 84 84 86 86 Integer average pH 6.09 6.12 6.09 6.10

Referring to Table 8, the cation exchange membrane of the present invention is excellent in cation exchange capacity can be usefully used as a purification device for water treatment.

The poly (arylene ether) copolymer according to the present invention may be molded into various forms and applied to a cation exchange resin or a cation exchange membrane.

1 shows the ¹ H-NMR spectrum of the copolymer of Chemical Formulas 6 to 8 in Example 1 of the present invention.

Figure 2 shows the ¹ H-NMR spectrum of the copolymer of Chemical Formulas 6 to 8 in Example 2 of the present invention.

Figure 3 shows the ¹ H-NMR spectrum of the copolymers of formulas 9 and 10 in Example 3 of the present invention.

Claims (15)

Poly (arylene ether) copolymer represented by the formula [Formula 1]

(In the formula 1, Ar ₁ is

ego, Ar ₂ is

ego, Where E ₁ , E ₂ , E ₃ , E ₄ , E ₅ and E ₆ is the same as or different from each other, a single bond, O, S, C (= O), S (= O), S (= O) ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , Si (CH ₃ ) ₂ , P (= 0) CH ₃ or C (= 0) NH, Z represents one type of cation exchange group or metal salts thereof selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carbonic acid group, a sulfonimide group, and a C ₁ to C ₁₀ alkylsulfonic acid group, x is 0.01 to 1, n is an integer from 10 to 800) The poly (arylene ether) copolymer of claim 1, wherein Z is sulfonic acid or sulfonic acid salt. The poly (arylene ether) copolymer of claim 1, wherein the metal salt is a sodium salt or a potassium salt. The poly (arylene ether) copolymer of claim 1, wherein the copolymer is a random copolymer or a block copolymer. The poly (arylene ether) copolymer of claim 1, wherein the copolymer has a weight average molecular weight of 10,000 to 1,000,000. The poly (arylene ether) copolymer according to claim 1, wherein the copolymer is selected from those represented by the following formula: One)

; And 2)

As shown in Scheme 1 below, S1) synthesizing a copolymer represented by Formula 5 by polymerizing a dihydroxy monomer of Formula 2, a dihalide monomer of Formula 3 and a dihydroxy monomer of Formula 4; And S2) A method for preparing a poly (arylene ether) copolymer represented by Formula 1 comprising introducing a cation exchange group to a copolymer phenyl ring portion of Formula 5: Scheme 1

(In Scheme 1, X is Cl, Br, I, or F, Ar ₁ , Ar ₂ , x, n and Z follow the definition above) 8. The method of claim 7, wherein step S1) is performed under one alkali metal base selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydroxide, and calcium hydroxide. The method of claim 7, wherein the step S1) is performed under one organic solvent selected from the group consisting of toluene, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and mixtures thereof. 8. The method of claim 7, wherein step S2) is reacted with a copolymer of Formula 5 and one sulfonic acid compound selected from the group consisting of chlorosulfonic acid, fuming sulfuric acid, triethylphosphate salt, and concentrated sulfuric acid. The method of claim 7, wherein if Ar ₂ comprises a sulfane functional group after step S1), an oxidation reaction is further performed by oxidizing to a sulfone functional group through an additional oxidation reaction as in Scheme 2 below. : Scheme 2

The method of claim 11, wherein the oxidation reaction is performed using one oxidizing agent selected from the group consisting of metachloroperoxybenzoic acid, hydrogen peroxide, oxone, and magnesium monoperphthalic acid. The method of claim 12, wherein the oxidation reaction is performed at 25 to 50 ° C. for 30 minutes to 10 hours. Cation exchange resin comprising the poly (arylene ether) copolymer according to any one of claims 1 to 6. Cation exchange membrane comprising the poly (arylene ether) copolymer according to any one of claims 1 to 6.

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