JPH0764890B2 - Method for producing crosslinked polystyrene derivative having hydroxyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a hydrophilic crosslinked polystyrene derivative having a hydroxyl group, which is useful as a synthetic adsorbent or a chromatographic packing material.

[Prior Art] Conventionally, porous cross-linked polystyrene has been used as a synthetic adsorbent for adsorbing and recovering an organic compound from an aqueous solution. However, since polystyrene is not well compatible with water, the synthetic adsorbent will float unless the column is filled with an alcohol (water) solution and then the alcohol is replaced with water. There was a drawback that it could not be used as. As a device for making such a porous cross-linked polystyrene hydrophilic so as to improve water familiarity, there is introduction of a hydroxyl group into polystyrene.

Several methods are known as methods for synthesizing crosslinked polystyrene having a hydroxyl group. For example, after chlormethylating crosslinked polystyrene with chloromethyl methyl ether,
There is a method of hydrolyzing the chloromethyl group. However, the chloromethyl group of crosslinked chloromethylated polystyrene is not easily hydrolyzed, and a sufficient amount of hydroxyl groups cannot be introduced by hydrolysis using alkaline water such as sodium hydroxide.

There is also a method of obtaining a crosslinked polyvinylbenzyl alcohol by using vinylbenzyl ester as a monomer, copolymerizing with a crosslinking agent, and then hydrolyzing it, but in this method, only one hydroxyl group can be introduced into one benzene ring, As a cross-linking agent, porous highly cross-linked polyvinyl benzyl alcohol using a large amount of divinylbenzene was insufficient in hydrophilization. A resin obtained by reacting a polyvinyl benzyl alcohol with a sugar to improve hydrophilicity is also known, but the reaction process is long and complicated.

Examples of hydrophilic synthetic adsorbents and chromatographic fillers include cross-linked polysaccharides such as dextran and cellulose, cross-linked polyvinyl alcohol, cross-linked polyhydroxyethyl (meth) acrylate and other cross-linked synthetic polymers and hydrophilic resins thereof. A resin in which an alkyl group or a phenyl group is introduced is known. However, these resins have problems that they are soft and have problems in pressure resistance, and that they are unstable to acids and alkalis.

[Object of the Invention]

An object of the present invention is to provide a method for producing a resin having excellent hydrophilicity by an industrially advantageous method. That is, the present invention provides a method for producing a hydrophilic resin by introducing a hydroxyl group or a polyethylene glycol group into a crosslinked polystyrene excellent in physical stability and chemical stability.

[Structure of Invention]

The method for producing a hydrophilic resin of the present invention is a method in which a styrene derivative having a glycidyl group represented by the following general formula (I) is copolymerized with a crosslinking agent, and then the glycidyl group of the obtained copolymer is treated with water or alcohol. , Polyethylene glycol, or
It is a method of obtaining a crosslinked polystyrene derivative having a hydroxyl group by reacting with a compound having a hydroxyl group such as polypropylene glycol.

(M and n show the number of 0-6, R shows H or an alkyl group.) Hereinafter, the component of this invention is demonstrated in detail.

Examples of the styrene derivative having a glycidyl group represented by the general formula (I) used in the present invention include vinylbenzyl glycidyl ether, methylvinylbenzyl glycidyl ether, vinylphenyl butyl glycidyl ether,
Examples thereof include vinylbenzyloxyethyl glycidyl ether and the like.

As the cross-linking agent, a monomer having two or more vinyl groups capable of copolymerizing with styrene, such as divinylbenzene, divinyltoluene, divinylnaphthalene, ethylene glycol dimethacrylate, and trimethylolpropane tri (meth) acrylate is used.

The copolymerization of the styrene derivative having a glycidyl group and the crosslinking agent can be carried out by a known suspension polymerization. That is, in an aqueous phase containing a dispersion stabilizer, an ethylene derivative having a glycidyl group as a monomer phase, a cross-linking agent, a polymerization initiator and an organic phase containing a porosifying agent as necessary are dispersed,
A bead-shaped copolymer can be obtained by heating and polymerizing. Here, as the dispersion stabilizer, gelatin,
Polymer compounds such as polyvinyl alcohol and carboxymethyl cellulose, and fine powder inorganic compounds such as magnesium silicate and calcium sulfate are used at a concentration of 0.05 to 5%. As the polymerization initiator, a peroxide represented by benzoyl peroxide, an azo compound represented by azobisisobutyronitrile, or the like is used in an amount of 0.01 to 10% by weight based on the monomer. In order to obtain a porous crosslinked copolymer, it is necessary to add a porosifying agent to the monomer phase. Examples of the porosifying agent include (cyclo) alkanes such as heptane, octane, decane, and cyclohexane, hexanol, pentanol, 2
-Ethanol such as alcohol such as ethylhexanol, which dissolves a monomer but does not dissolve a linear polymer (also referred to as a poor solvent), is used at 20 to 70% with respect to the monomer alone, or toluene,
With a solvent that also dissolves linear polymers such as sichloroethane (also called a good solvent), it is used at 40 to 200% with respect to the monomer, or linear polymer such as polystyrene is used at 2 to 40% with respect to the monomer alone. Or used together with a good solvent. The polymerization reaction is carried out mainly by heating at 50 to 90 ° C. for 5 to 24 hours under a nitrogen atmosphere.

Examples of the compound having a hydroxyl group that reacts with the glycidyl group of the obtained copolymer include aliphatic alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol and glycerin, and aromatic alcohols such as phenol, catechol and pyrogallol. , Polyethylene glycol such as diethylene glycol and triethylene glycol, polypropylene glycol such as dipropylene glycol and tripropylene glycol, and water.

The reaction of these compounds having a hydroxyl group can be carried out without using a solvent, but the reaction is facilitated by using a solvent which swells the copolymer such as dioxane, ethylene chloride and toluene. Further, this reaction requires an acid catalyst such as sulfuric acid, hydrochloric acid or boron trifluoride, or an alkali catalyst such as sodium hydroxide or potassium hydroxide or a tertiary amine such as triethylamine.

The degree of hydrophilization can be arbitrarily changed depending on the type of the compound having a hydroxyl group and the amount of the compound introduced. In order to maximize the reaction rate with the glycidyl group, a compound having 10 times or more hydroxyl groups as compared with the glycidyl group in the copolymer is used.
The reaction with the glycidyl group is carried out at 50 to 90 ° C. for about 2 to 24 hours.

If glycidyl groups remain after the reaction such as modification with polyethylene glycol, use 1 to 20% sulfuric acid to heat the ring at 50 to 80 ° C for 1 to 8 hours to perform the ring opening reaction. A cross-linked polystyrene derivative having a property of being obtained.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A: Synthesis of porous cross-linked polyvinyl benzyl glycidyl ether A stirring device, a nitrogen introducing tube, a condenser and a thermometer were attached.
A 500 ml four-necked flask was charged with 275 ml of water containing 2.5 g of polyvinylpyrrolidone as a dispersion medium, and as a monomer phase, 19 g of vinylbenzyl glycidyl ether, 15.4 g of divinylbenzene (purity 55%), 4-methyl-2-pen. 28g Tanol, 7g Octane, Azobisisobutyronitrile
0.7 g of the mixed solution was dispersed. After dispersing for 30 minutes in a nitrogen atmosphere, a polymerization reaction was carried out at 70 ° C for 24 hours.

The copolymer beads thus obtained were washed with excess methanol, hot methanol, washed with acetone, and dried under reduced pressure at 60 ° C. The yield was 31 g.

The epoxy ring content of the obtained copolymer beads was measured by the hydrochloric acid-dioxane method and found to be 2.5 mmol / g.

B: Modification of porous cross-linked polyvinyl benzyl glycidyl ether with water Into a three-necked flask equipped with a stirrer, a cooler and a thermometer, 5.0 g of the copolymer obtained in A and 100 ml of dioxane were put, and a resin was added using an aspirator. Degas from until no bubbles left. Then, 500 ml of a 5N H ₂ SO ₄ aqueous solution was added, and the mixture was reacted at 80 ° C. for 24 hours. After the reaction was completed, the resin was filtered, washed with water until the liquid became neutral, and then washed with acetone. After drying under reduced pressure at 60 ° C, 5.2 g of a resin having a 1,2-glycol group was obtained. In the IR spectrum of the resin produced, a peak at a characteristic absorption of hydroxyl groups of 3500 cm ^-1 was developed.

The ring-opening reaction rate of the glycidyl group was determined by quantifying the residual epoxy ring by the hydrochloric acid / dioxane method. The reaction rate was 92%.

Example 2 A: Synthesis of porous cross-linked polyvinyl benzyl glycidyl ether In a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a condenser and a thermometer, 300 ml of water containing 1.5 g of polyvinyl alcohol was placed as a dispersion medium, As a monomer phase, a mixed solution of 20 g of vinylbenzyl glycidyl ether, 20 g of divinylbenzene (purity 56%), 15 g of n-heptane and 0.2 g of 2,2'-azobis-2,4-dimethylvaleronitrile was dispersed. After dispersing for 30 minutes in a nitrogen atmosphere, a polymerization reaction was carried out at 70 ° C. for 8 hours. The obtained copolymer beads are
After washing with water, washing with acetone, and drying under reduced pressure at room temperature. The yield was 32 g. The abundance of the epoxy ring measured by the hydrochloric acid / dioxane method was 2.1 mmol / g.

B: Modification of porous cross-linked polyvinyl glycidyl ether with glycerin To a three-necked flask equipped with a stirrer, a cooler, and a thermometer, 5.0 g of the copolymer obtained in A, 35 ml of dioxane, and 14 ml of glycerin were added, and 3 as an acid catalyst 1 ml of boron fluoride ethyl ether complex was added and reacted at 80 ° C. for 6 hours. After the resin passed, it was washed successively with dioxane and water.

After the resin thus obtained was dried under reduced pressure at 60 ° C., the residual epoxy ring was quantified by the hydrochloric acid / dioxane method, and the reaction rate of the epoxy ring was determined. It was 89%. In addition, the generated resin
In the IR spectrum, a peak at a characteristic absorption of hydroxyl groups of 3500 cm ^-1 was developed.

Example 3 Modification of porous cross-linked polyvinyl benzyl glycidyl ether with polyethylene glycol 5.0 g of the copolymer beads obtained in Example 2A were added with a solution of 15 g of polyethylene glycol # 300 (Kishida Chemical Co., Ltd.) in 45 ml of dioxane, It was modified with polyethylene glycol. The reaction operation was performed in the same manner as in Example 2B.

A part of the obtained resin was dried under reduced pressure at 60 ° C., and the amount of residual epoxy groups was measured by the hydrochloric acid / dioxane method to obtain a reaction rate of epoxy ring, which was 63%. In the IR spectrum of the produced resin, a peak at a characteristic absorption of a hydroxyl group of 3500 cm ^-1 was confirmed.

35 ml of 10% sulfuric acid was added to the remaining resin, and the mixture was heated at 60 ° C. for 5 hours. A part of the treated resin was taken, dried under reduced pressure at 60 ° C., and the amount of residual epoxy ring was quantified by the hydrochloric acid / dioxane method.

[Advantages of the Invention] According to the present invention, a crosslinked polystyrene derivative having excellent chemical and physical stability can be easily obtained.

Claims (1)

[Claims] 1. A styrene derivative having a glycidyl group represented by the following general formula (I) is copolymerized with a monomer having two or more vinyl groups, and then the glycidyl group of the obtained copolymer is converted into A method for producing a crosslinked polystyrene derivative having a hydroxyl group, which comprises denaturing with a compound having a hydroxyl group. (M and n are numbers from 0 to 6, and R is H or an alkyl group)