KR20110062845A - 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 to enable use as a cation exchange resin or cation exchange membrane due to improved ion exchange capability and metallic ion adsorption ability. CONSTITUTION: A method for preparing a poly(arylene ether)copolymer represented by chemical formula 1 comprises: synthesizing a copolymer represented by 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 both phenyl ring parts 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) a method of preparing a poly (arylene ether) copolymer represented by Formula 1 including introducing a cation exchange group to both phenyl ring moieties of the copolymer 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, the present invention provides a poly (arylene ether) copolymer having a cation exchange group in the side chain, which has a flowable polymer chain, which has excellent processability and physical properties as well as high ion exchange capacity.

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 to both phenyl ring moieties of the copolymer of Formula 5:

Scheme 1

(In Scheme 1,

X is Cl, Br, I, or F,

Ar ₁ , Ar ₂ , x, n and Z are as described above)

First, in step S1), a copolymer represented by Chemical Formula 5 is synthesized by performing a polycondensation reaction of the dihydroxy monomer of Chemical Formula 2, the dihalide 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.

At this time, the dihydroxy monomer of the formula (2) and the dihydroxy monomer of the formula (4) with respect to the dihydroxy monomer of the formula (3) is preferably reacted at the equivalent ratio of 0.1 to 0.9, and 0.1 to 0.9, respectively.

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 both phenyl ring moieties of the copolymer of formula (5).

A cation exchange group is introduced by impregnating or reacting a copolymer of Formula 5 with a sulfonic acid compound, a phosphoric acid compound, or a carboxylic acid compound. 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, Can be phoneized.

In this case, it is preferable that the fonization reaction described below is performed at 0 to 100 ° C., preferably 25 to 50 ° C., using a sulfonic acid compound in an amount of 1 to 2 equivalents based on the copolymer of Formula 5. If the amount of the sulfonic acid compound is less than the above range, the sulfonation rate is low, on the contrary, if the amount of the sulfonic acid compound exceeds the above range, the final product is crosslinked or decomposed. In addition, when the reaction temperature is less than the above range, it is not possible to obtain a sufficiently sulfonated polymer. On the contrary, even if the reaction temperature is exceeded, the sulfonation rate does not increase any more, and in some cases, the polymer backbone may be decomposed.

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).

 Since the film forming method using the poly (arylene ether) copolymer is well known in the art, 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 7 (x = 0.4)

 A poly (arylene ether) copolymer represented by Chemical Formula 7 was prepared by the following Reaction Scheme 2.

Scheme 2

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

Three monomers 2,2'-bis (2-hydroxy-5-biphenylyl) propane (2,2- in a two-neck round bottom flask in a nitrogen atmosphere on a device equipped with a condenser, Deanstock trap and magnetic stub. Bis (2-hydroxy-5-biphenylyl) propane: 8mmol) and 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-(hexafluoroiopropylidene) diphenol: 12mmol), 4,4'-dimple Rudiphenylsulfone (4,4'-difluorodiphenylsulfone: 20 mmol) was added thereto, and potassium carbonate (24 mmol) was added thereto. Dimethylacetamide (Dimethylacetamide: DMAc: 70 mL) and toluene (50 mL) were used as the reaction solvent.

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, 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 through the Phonenization Process

A solution of 2.0 mmol of the polymer synthesized in Example 1 in 20 mL of dichloromethane was placed in a reactor, and a solution of 20 mL of dichloromethane and 4.8 mmol of chlorosulfonic acid was slowly dropped over 1 hour. At this time, the reaction temperature was room temperature and the reaction time was 3 hours.

As the sulfonation progressed, the solubility in dichloromethane decreased, and thus a precipitate of sulfonated polymer was formed during the reaction. After the reaction was completed, the remaining chlorosulfonic acid was removed by washing several times with hexane and distilled water. After the reaction was completed, it was filtered and dried in vacuo.

 After dissolving the dried copolymer in dimethylacetamide solution, an aqueous solution of 3% by weight potassium hydroxide was added dropwise, and the pH was adjusted to neutral with hydrochloric acid solution. The copolymer was then filtered and dried in vacuo to give a sulfonated poly (arylene ether) copolymer of formula (7).

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 2: Synthesis of Poly (arylene Ether) Copolymer (x = 0.6)

2,2'-bis (2-hydroxy-5-biphenylyl) propane (12 mmol), 4,4 '-(hexafluoroisopropylidine) diphenol (8 mmol) and 4,4'-difludi A final product of white solid was obtained in the same manner as in Example 1, except that the phenyl sulfone (20 mmol) was added in a molar ratio.

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 is introduced, a peak near 7.40 ppm is generated, which indicates that the hydrogen at the alpha position of the sulfonic acid group is downfielded and accurately synthesized through an area ratio.

Example 3: Synthesis of Poly (arylene Ether) Copolymer (x = 0.8)

2,2'-bis (2-hydroxy-5-biphenylyl) propane (16 mmol), 4,4 '-(hexafluoroisopropylidine) diphenol (4 mmol) and 4,4'-difludiphenyl A final product of white solid was obtained in the same manner as in Example 1, except that the molar ratio of sulfone (20 mmol) was added.

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 is introduced, a peak around 7.50 ppm is generated, which shows that the hydrogen at the alpha position of the sulfonic acid group is downfielded and accurately synthesized through an 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 1 123 2.87 Example 2 115 2.46 Example 3 183 2.97

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 45 37 31

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 1.29 Example 2 1.78 Example 3 2.24

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 1 127 121 Example 2 457 430 Example 3 621 580 Metal Ion Solution 850 850

division Nickel ion concentration (ppm) pH 1.65 pH 8.55 Example 1 102 135 Example 2 411 451 Example 3 521 604 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 85 85 Integer average pH 6.09 6.12 6.1 6.19

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.

Figure 1 shows the ¹ H-NMR spectrum of the poly (arylene ether) copolymer of Examples 1 to 3 of the present invention.

Figure 2 shows the ¹ H-NMR spectrum of the sulfonated poly (arylene ether) copolymer of Examples 1 to 3 of the present invention.

Claims (12)

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 both phenyl ring portions of the copolymer 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. 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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