KR960012440B1 - Cation exchange resin and method for manufacturing the same - Google Patents

Abstract

The cation exchange resins of weak acid type are prepared by suspension polymerization of a pentaerythritol di(meta)acrylate shown in formula (I), 1,4-cyclohexanedimethyl di(meta)acrylate of formula (II) and glycidyl (meta)acrylate of formula (III), and then reacting with carboxylic acid derivative of formula (IV). In the formula, R is hydrogen or methyl, R1 is chloro or bromo, R2 is hydrogen, methyl or ethyl. The resin product by this process has an excellent mechanical property, good ion exchange capacity and small volume change.

Description

Weak acid cation exchange resin with excellent mechanical strength and preparation method thereof

The present invention relates to a weakly acidic cation exchange resin having excellent mechanical strength and a method for preparing the same. More specifically, the present invention relates to pentaerythritol di (meth) acrylate, 1,4-cyclohexanedimethyl di (meth) atrylate and grilling. The present invention relates to a weakly acidic cation exchange resin having a high mechanical strength, a large ion exchange capacity, and a low volume change by preparing ion copolymerized with a copolymer obtained by aqueous suspension polymerization of dill (meth) acrylate, and a method for producing the same.

In general, ion exchange chromatography is used as a method for separating and purifying water-soluble substances such as proteins, enzymes, amino acids, and antibiotics, wherein ion exchange resins include styrene-divinylbenzene copolymer, hydrophilic dextran gel, Ion exchange resins incorporating ion exchange functional groups into agarose gels, polyacrylamide gels, polymethacrylate gels and silica gels have been used. However, ion exchange resins incorporating ion exchange functional groups into styrene-divinylbenzene copolymers cause protein denaturation due to physical adsorption due to hydrophobic bonds to proteins, and ions produced by introducing dextran gels and polyacrylamide gels. Exchange resins have low mechanical strength, and silica gels are vulnerable to alkalis. Recently, ion exchange resins with ion exchange functional groups in polymethacrylate gels with excellent mechanical strength, high ion exchange capacity, low adsorption properties and high separation capabilities have been used for analysis and preparative ion exchange chromatography. have.

As a prior art for the preparation of the weakly acidic cation exchange resin, U.S. Patent No. 4,614,751 prepared by directly polymerizing unsaturated carboxylic acid, which is difficult to control the polymerization reaction due to the exothermic generated during the polymerization, and also the ion of the production resin Due to the low exchange capacity, copolymers polymerized using unsaturated alkyl methacrylates (alkyl groups having 1 to 3 carbon atoms) that can be hydrolyzed under alkaline conditions and using divinylbenzene or ethylene glycol dimethacrylate as crosslinking agents A method of preparing a weakly acidic cation exchange resin having excellent physical durability by decomposition is presented. However, since the ion exchange resin prepared by this method shows hydrophobicity, there is a problem of denaturation and adsorption due to hydrophobic bonding with the protein to be used as a hydrophilic weakly acidic cation exchange resin for separation of proteins and the like.

In addition, Japanese Patent Laid-Open No. 48-24512 and Japanese Patent Laid-Open No. 48-64187 allow a polyvinyl ester of a polyhydric alcohol to react with a hydrophilic monomer such as glycidyl methacrylate and 2-hydroxy ethyl methacrylate as a crosslinking agent. The ion exchange resin was prepared by hydrolyzing the polymerized copolymer or introducing a cationic functional group. This method has a problem of low ion exchange capacity and low mechanical strength due to a limited number of hydroxyl groups.

Accordingly, the present inventors focused on developing weakly acidic exchange resins having high ion exchange capacity, small volume change, and excellent mechanical strength, and as a result, pentaerythritol di (meth) acrylate, 1,4-cyclohexanedimethyl di (meth) acrylic The present invention was completed by copolymerizing rate and glycidyl (meth) acrylate and then introducing an ion exchange functional group to prepare a weakly acidic cation exchange resin.

Accordingly, an object of the present invention is to provide a weakly acidic cation exchange resin and a method for preparing the same, which have high ion exchange capacity, excellent mechanical strength, and small volume change according to ion type, which can be used for preparative and purification.

Hereinafter, the present invention will be described in detail.

In the present invention, in preparing a weakly acidic cation exchange resin, pentaerythritol di (meth) acrylate represented by the following structural formula (I), and 1,4-cyclohexanedimethyl di (meth) acrylic represented by the following structural formula (II) It is characterized by preparing by suspending polymerization of the rate and glycidyl (meth) acrylate represented by the following structural formula (III), and then reacting the carboxylic acid derivative represented by the following structural formula (IV).

Wherein R is a hydrogen atom or a methyl group, R ₁ is chloro or bromo and R ₂ is a hydrogen atom, a methyl group or an ethyl group. The present invention also includes a weakly acidic cation exchange resin prepared by the above method.

Referring to the present invention in more detail as follows.

The present invention is a suspension and suspension aid in the hydrophilic crosslinking agent panthaerythritol di (meth) acrylate and hydrophobic 1,4-cyclohexane dimethyl di (meth) acrylate and glycidyl (meth) acrylate monomer for improving mechanical strength , A weakly acidic cation exchange having excellent mechanical strength, wherein a copolymer is prepared by adding a radical initiator in an aqueous solution in which a hydrogen ion concentration regulator and an inorganic salt are properly mixed and dissolved, and introducing a carboxylic acid group using a base catalyst. It is related with the manufacturing method of resin.

10 to 35% by weight of pantaerythritol di (meth) acrylate of the above formula (I) and 1,4-cyclohexanedimethyl di ( 1-15% by weight of the meth) acrylate compound and 50-89% by weight of the glycidyl (meth) acrylate compound of the formula (III) were added thereto, an organic solvent for initiator and processing formation was added thereto, followed by general aqueous suspension polymerization. Manufacture.

If the participation amount of pentaerythritol di (meth) acrylate used as a crosslinking agent is less than 10% by weight, the ion exchange capacity is lowered due to the lack of hydroxy groups of the produced particles, and when the weight is 35% by weight, the water is excessive due to hydrophilicity. It is difficult to obtain spherical particles by aqueous suspension polymerization using as a solvent. Hydrophobic, 1,4-cyclohexanedimethyl di (meth) acrylate 1,4-cyclohexane dimethanol and glycidyl (meth) acrylate or (meth) acrylic acid represented by the above structural formula (II) under It is produced and used by esterification reaction, and the addition amount is less than 1% by weight, the mechanical strength is lowered, and when it exceeds 15% by weight, the ion exchange capacity is lowered due to excessive hydrophobicity. When the amount of glycidyl (meth) acrylate added is less than 50% by weight, hydrophobic adsorption occurs due to increased crosslinking, and when 89% by weight is initialized, the mechanical strength decreases.

The suspension polymerization used in the present invention used a general hydrophobic suspension polymerization method, in particular, in order to prevent the crosslinking agent and monomers used to dissolve well in water as a suspension solvent, in addition to the commonly used suspensions, traces of salts and suspension aids By putting in, spherical porous particles can be obtained.

As the suspending agent used in the present invention, polyvinyl alcohol, gelatin polyvinylpyrrolidone, cellulose-based materials may be used. Particularly, in the case of polyvinylpyrrolidone, the suspending efficiency is good, and the amount used is the molecular weight of polyvinylpyrrolidone. According to the difference, low molecular weight polyvinylpyrrolidone may be used in an amount of at least 5 times higher than that of high molecular weight to achieve a similar suspension efficiency. The polyvinylpyrrolidone is used in an amount of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the water of the suspension solvent. In addition, as a salting agent for reducing the solubility of the hydrophilic reactant in water and controlling the surface tension of the water, metal salts such as sodium, calcium, potassium, magnesium, and lithium, such as sodium chloride, calcium chloride, calcium carbonate, or magnesium sulfate, are used for water as a suspension solvent. When 1 to 20% by weight is used, when the amount is less than 1% by weight, spherical particles cannot be obtained, and when the amount exceeds 20% by weight, a large amount of cracking of particles occurs.

According to the present invention, it is difficult to obtain particles having a uniform particle surface and uniform pore distribution using only the salting agent. Therefore, in the present invention, a cellulose-based substance such as carboxymethyl cellulose sodium salt, hydroxy ethyl cellulose, methyl cellulose or hydroxy butyl methyl cellulose is extremely used as a suspension aid for uniform particle surface and uniform pore distribution. It is used in a small amount, and the suspension aid is used within the range of 0.0005 to 0.1% by weight with respect to the water of the suspension solvent.When the amount is less than 0.0005% by weight, the surface of the particles appears unevenly. It becomes larger and shows the phenomenon of aggregation between particles. As a polymerization initiator, a common radical polymerization initiator is used, in particular, azobisisobutylnatrile, benzoyl peroxide, t-butylperoxide, di-t-butylperoxide, t-butylperoxybenzoate and the like are effective. , The addition amount is used 0.05 to 10% by weight based on the total content of the mixture of the formula (I), (II), (III).

In addition, an organic solvent is added to the mixture of a crosslinking agent and a monomer to form pores. The organic solvent is an organic solvent such as an aliphatic alcohol, an aliphatic ether, or an aliphatic ketone having some solubility in water. Aliphatic primary or secondary alcohols such as propyl alcohol, isopropyl alcohol, normal butyl alcohol, amyl alcohol, isoamyl alcohol, butanediol, normal hexyl alcohol, hexanediol, noylheptyl alcohol, normal octyl alcohol, benzaldehyde, normal butyl acetate, cyclo Hexonone, monochlorobenzene, or metal ethyl carton is used.

Suspension polymerization of the present invention is carried out over a second step, the first suspension polymerization at a temperature of 40 ~ 50 ℃ and rise in the degree of odo again to prepare a copolymer by the second suspension polymerization at a temperature of 60 ~ 80 ℃.

When the temperature of the first polymerization is less than 40 ℃ the reaction is very slow, when proceeding at a temperature higher than 50 ℃ because the aggregation of particles appears remarkably the first polymerization temperature does not exceed 50 ℃. In addition, when the secondary polymerization temperature is higher than 80 ° C., there is a problem in that the particle strength is lowered due to rapid radical polymerization, in which cracks are generated in the generated particles.

A cation exchange group is introduced into the copolymer prepared by the polymerization process, which is introduced under an alkali catalyst such as sodium hydroxide, potassium hydroxide or lithium hydroxide, and the carboxylic acid derivative having a cation exchange group is chloroacetyl acid and bromoacetyl. Acid, 2-chloropropionic acid, 3-chloropropanoic acid, 2-bromopropionic acid, 3-bromopropionic acid, 2-chlorobutanoic acid, 4-chlorobutanoic acid, 2-bromobutanoic acid, 4-bromobutanoic acid Or effective in fumaric acid and the like, wherein the introduction of the cation exchange group is carried out by addition reaction of a hydroxy group to a double bond in the case of fumaric acid, and the weakly acidic functional group except for furaric acid proceeds by substitution reaction between hydrogen and halogen of the hydroxy group. At this time, the content of the weakly acidic functional group to be used is 5 to 70% by weight based on the weight of the copolymer particles to obtain an ion exchange resin having a high exchange capacity. If the content of the cation exchanger is less than 5% by weight, the exchange capacity is lowered, and when the content of the cation exchanger is more than 70% by weight, the manufacturing cost is increased due to the disposal of excessive unreacted weakly acidic functional groups. At this time, the reaction temperature is preferably in the range of 20 to 70 ° C. When the reaction temperature is less than 20 ° C, the reaction occurs very slowly, and when it exceeds 70 ° C, decomposition of the copolymer by an alkali catalyst occurs.

In addition, the reaction time is suitably in the range of 2 to 10 hours. When the reaction time is less than 2 hours, a resin having a low ion exchange capacity is obtained. When the reaction time exceeds 10 hours, decomposition of the copolymer occurs. In addition, the particle size and the formation of pores can be solved by adjusting the size and size of the particle size and the degree of pore formation depending on the purpose of the suspension system stirring speed.

The weakly acidic cation exchange resin prepared by the production method of the present invention has high mechanical strength and high hydrophilicity, and is applied to ion exchange chromatography used for analysis, separation and purification of biological materials such as water-soluble proteins, enzymes, polysaccharides, and antibiotics. It is very effective when used, and the average particle diameter of the importer manufactured in the present invention can be used for analytical ion exchange chromatography, and the average particle diameter of 20 to 150 μm is used for preparative and industrial preparative ion exchange. It can be used for chromatography.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

Example 1

A 2- liter round bottom flask was equipped with a thermometer, a nitrogen inlet tube and a paddle-shaped stirrer, under a stream of nitrogen, 10 g of 1,4-cyclohexanedimethyl dimethacrylate, 60 g pentaerythritol dimethacrylate, and glycy Add 130 g of dimethyl methacrylate and 2 g of benzoyl peroxide, stir and add 300 g of normal butyl alcohol to dissolve. Then, 10 g of polyvinylpyrrolidone, 1 g of carboxymethylcellulose sodium salt, and 20 g of sodium chloride are slowly added to 1 l of distilled water. Stir at a rate of 450 rpm at a temperature of 50 ℃.

After the reaction at that temperature for 6 hours, the reaction temperature was raised to 70 ° C. for 10 minutes to further react and terminated to obtain 10 to 60 μm of copolymer particles. The produced particles were washed with distilled water and acetone to obtain 20-40 μm particles. 50 g of the hydrophilic particles thus obtained were put into a 1 l round bottom flask, and 150 ml of distilled water was poured and dispersed. Then, 20 g of chloroacetyl acid and 250 ml of 0.5 N sodium hydroxide solution as an alkali catalyst were reacted at 50 ° C. for 5 hours, and the reaction product was filtered and distilled water was used. Was washed to obtain a weakly acidic cation exchange resin having a carboxyl group as a functional group.

Example 2

A weakly acidic cation exchange resin was obtained in the same manner as in Example 1 except that 25 g of 2-chloropropionic acid was used instead of chloroacetyl acid in the cation exchange group introduction reaction.

Example 3

A weakly acidic cation exchange resin was obtained in the same manner as in Example 1 except that 30 g of 2-chlorobutanoic acid was used instead of chloroacetyl acid in the reaction of introducing the cation exchange resin.

Example 4

A 2-liter round bottom flask was equipped with a thermometer, a nitrogen inlet tube and a paddle-shaped stirrer, under a stream of nitrogen, 6 g of 1,4-cyclohexanedimethyl dimethacrylate, 64 g of pentaerythritol dimethacrylate, and glycidyl Add 130 g of methacrylate and 2.5 g of benzyl peroxide, stir and add 350 g of normal butyl alcohol to dissolve it. Then, 10 g of polyvinylpyrrolidone, 1 g of carboxymethylcellulose sodium salt, and 25 g of sodium chloride are dissolved in 1 l of middle water and slowly While stirring at a temperature of 450rpm at 50 ℃ temperature.

After the reaction at that temperature for 6 hours, the reaction temperature was raised to 70 ° C. for 10 minutes to further react and terminated to obtain 15 to 55 μm of copolymer particles. The produced particles were washed with distilled water and acetone to obtain 20-40 μm particles. 50 g of the hydrophilic particles thus obtained were put into a 1 l round bottom flask, and 150 ml of distilled water was poured to disperse. Then, 20 g of chloroacetyl acid and 250 ml of an alkali catalyst 0.5N sodium hydroxide solution were added and reacted at 50 ° C. for 5 hours. It picked up and obtained the weakly acidic cation exchange resin which has a carboxyl group as a functional group.

Example 5

A weakly acidic cation exchange resin was obtained in the same manner as in Example 4 except that 25 g of 2-chloropropionic acid was used during the cation exchange group introduction reaction.

Example 6

A weakly acidic cation exchange resin was obtained in the same manner as in Example 4 except that 30 g of 4-chlorobutanoic acid was used for the cation exchange group introduction reaction.

Comparative Example 1

Separation particles were obtained in the same manner as in Example 1, except that 70 g of petaerythritol dimethacrylate was added as a crosslinking agent and 1,4-cyclohexanedimethyl dimethane acrylate was not added.

Comparative Example 2

Example 1 and the above except that 70 g of petaerythritol dimethacrylate was added as a crosslinking agent and 1,4-cyclohexanedimethyl dimethane acrylate was used, and 2-chloropropionic acid was used during the cation exchange group introduction reaction. Separation particles were obtained by the same method.

Experimental Example

The exchange capacity, the optimum ratio (Na / H) and the chemical stability for the cation exchange resin prepared from Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 1 below.

[Measurement method of exchange capacity]

Approximately 25 ml of the prepared cation exchange resin wet product was taken and filled in the resin tower, 200 ml of 1N sodium hydroxide solution was flowed at a space velocity of 5 m ³ / hr, then rinsed with demineralized water, and 200 ml of 1N hydrochloric acid solution was flowed at a space velocity of 5 m ³ / hr. Adjust the reference type resin by making H-type resin and washing with demineralized water at a space velocity of 50m ² / hr until no chlorine ions are identified in the solution. 20 ml of the adjusted standard resin is removed, centrifuged to remove adhered moisture, weighed exactly 5 g, dried at 10 ± 2 mmHg for 8 hours in a vacuum dryer adjusted to 50 ± 1.5 ° C., weighed, and the moisture is measured by weight loss. . Next, fill a 250 ml measuring cylinder with 0.2 N sodium hydroxide solution to the mark and accurately add 3 g of the dehydrated resin. After standing for 24 hours, 25 ml of supernatant was taken and titrated with 0.1 N hydrochloric acid solution (concentration coefficient f) using methyl orange as an indicator (A ml).

At the same time, titrate with 0.1 N hydrochloric acid solution (B ml) for the first 25 ml of 0.2 N sodium hydroxide solution. Neutralization titration was performed by automatic titration (Metron, Model-682).

[Volume change according to resin type]

The resin adjusted to the reference type was treated with 1N sodium hydroxide solution in excess to make Na-type, washed thoroughly with demineralized water, and the resin was accurately collected in a 10 ml measuring cylinder. 1N hydrochloric acid solution was flowed into the collected 10 ml of resin, transformed into H type, thoroughly washed with demineralized water, and the volume (γ ml) of the resin was measured in a 10 ml measuring cylinder.

[Chemical Stability Test]

The chemical stability test is an oxidation test method that is part of the mechanical strength test. After the particles were treated with 3% hydrogen peroxide solution at 72 ° C. for 72 hours, the moisture content was measured. Here, the lower the moisture content, the better the chemical stability, so the present invention can be seen that the chemical stability is superior to the comparative example.

TABLE 1

Claims (5)

In preparing the weakly acidic cation exchange resin, pentaerythritol di (meth) acrylate represented by the following structural formula (I), 1,4-cyclohexanedimethyl di (meth) acrylate represented by the following structural formula (II), and A method for producing a weakly acidic exchange resin, characterized in that it is prepared by suspending and polymerizing glycidyl (meth) acrylate represented by the structural formula (III) and then reacting the carboxylic acid derivative represented by the following structural formula (IV). Wherein R is a hydrogen atom or a methyl group, R ₁ is chloro or bromo and R ₂ is a hydrogen atom, a methyl group or an ethyl group. The method for producing a weakly acidic cation exchange resin according to claim 1, wherein the carboxylic acid derivative represented by Structural Formula (IV) is used in an amount of 5 to 70% by weight based on the weight of the copolymer particles. According to claim 1, wherein the carboxylic acid derivative represented by the formula (IV) is chloroacetyl acid, bromoacetyl acid, 2-chloropropionic acid, 3-chloropropanoic acid, 2-bromopropionic acid, 3-bro A method for producing a weakly acidic cation exchange resin, characterized by using morphopionic acid, 2-chlorobutanoic acid, 4-chlorobutanoic acid, 2-bromobutanoic acid, 4-bromobutanoic acid, or fumaric acid. The method of claim 1, wherein the alkali catalyst is sodium hydroxide, potassium hydroxide or lithium hydroxide. A weakly acidic cation exchange resin prepared by the method of claim 1.