JPS59139941A - Surface functional type anion exchange resin and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare high-capacity surface functional type anion exchange resin withstanding longterm use, by a method wherein the glycidyl ester group in the surface layer part of a crosslinked polymer particle is subjected to ring opening reaction by using an aqueous hydrogen halide solution and the treated copolymer particle is aminated with a tertiary amine. CONSTITUTION:A crosslinked copolymer particle having a glycidyl ester group obtained by copolymerizing a glycidyl ester of an unsaturated carboxylic acid, such as glycidyl acrylate, and a polyvinyl monomer as a crosslinking agent, such as divinylbenzene, is reacted with an aqueous solution of hydrogen halide, such as HCl, in a water-insoluble solvent, such as benzene or n-hexane, to subject the glycidyl ester group in the surface layer part of the aforementioned crosslinked copolymer particle to ring opening reaction to introduce a halogen atom and the treated copolymer particle is aminated through the reaction with a tertiary amine, such as triethylamine, in a solvent, such as water or methanol. By this method, a surface functional type anion exchange resin wherein 5-200mueq./g of a group represented by the formula (wherein R<1>, R<2> and R<3> are each an alkyl or a hydroxyalkyl group) is contained in the surface layer part of the above-mentioned crosslinked copolymer particle is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface functional anion exchange resin and a method for producing the same. In particular, it relates to a surface functional anion exchange resin suitable as a packing material for ion exchange chromatography.

When performing ion exchange analysis of various ions, ion exchange resins with high performance are required as packing materials for ion exchange chromatography.
It is well known in madography. Here, "high performance" means separation of a high degree and speed, and resins having ion exchange groups only in the surface layer have high performance in ion chromatography, and are therefore highly preferred in ion exchange chromatography. Several production methods have been reported to date for such surface-functionalized ion exchange resins, but they have advantages and disadvantages. One method is to coat the surface of a crosslinked polystyrene carrier of several tens of microns with fine particles of a strongly basic anion exchange resin of 7 microns or less. However, the filler made in this way is
There are problems with durability, and there are limits to reducing the filler particle size.

A conventionally known method has been developed in which the surface of spherical silica or glass is made porous and ion exchange groups are introduced therein. However, these ion exchangers
Since the surface is easily attacked by strong acids, strong bases, etc., there is a drawback that the eluents that can be used are limited.

Recently, a method has been proposed to produce a surface-functionalized anion exchange resin by carrying out a chloromethylation reaction of porous cross-linked polystyrene in a short time followed by an amination reaction, but it is difficult to precisely control the amount of functional groups introduced. The problem is that it is difficult to control.

The anion exchange resin according to the present invention has the formula -COOOH2CHCH,NRIR2R" in the surface layer of the crosslinked copolymer particles having glycidyl ester groups.
or an alkyl group or a hydroxyalkyl group) on the left μgq/r~:lOOμeq/? A surface-functional anion exchange resin having a glycidyl ester group, which is prepared by reacting crosslinked copolymer particles having a glycidyl ester group with an aqueous solution of hydrogen chloride in a water-insoluble organic solvent to form a surface layer of the crosslinked copolymer particles. It can be obtained by ring-opening the glycidyl ester group of , introducing a halogen, and then reacting with a tertiary amine for amination.

When ring-opening the glycidyl ester group, if the reaction is performed with only an aqueous hydrogen halide solution without using an organic solvent, the aqueous hydrogen halide solution will penetrate not only the surface layer but also the inside, causing the reaction to occur inside. However, it is difficult to precisely control the amount of halogen introduced, and in ion exchange chromatography using an anion exchange resin obtained by reaction with a tertiary amine, there is a problem that the reproducibility of the chromatogram is poor.

Surface-functional anion exchange resins that have functional groups only on the surface layer of glycidyl ester groups have good chromatograms.
Furthermore, it can withstand long-term use. Furthermore, resins with arbitrary particle sizes can be produced.

Hereinafter, the surface functional anion exchange resin and the method for producing the same according to the present invention will be explained in detail.

The crosslinked copolymer is produced by copolymerizing a glycidyl ester of an unsaturated carboxylic acid and a polyvinyl monomer as a crosslinking agent in a conventional manner.

As the glycidyl ester of unsaturated carboxylic acid, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, diglycidyl itaconite, diglycidyl fumarate, diglycidyl maleate, etc. are used.

Examples of the polyvinyl monomer as a crosslinking agent include divinylbenzene, divinylethylbenzene, divinyltoluene,
Polyvinyl aromatic monomers such as divinylxylene and polyvinyl aliphatic monomers such as ethylene glycol dimethacrylate and tetramethylolmethane trimethacrylate are used. These copolymers may be of gel type or porous type. Any particle size can be used, but as a packing material for ion exchange chromatography,
The thickness is preferably about 7 μm to 50 μm. Examples of water-insoluble organic solvents used to open the glycidyl ester groups on the surface layer of crosslinked copolymer particles include aromatic compounds such as benzene, toluene, and xylene, dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene. Halogen-containing organic solvent, n-hexane, cyclohexane,
Water-insoluble organic solvents such as aliphatic compounds such as n-hebutane can be used, but aliphatic organic solvents that do not swell the polymer are preferred.

As a reaction reagent for ring-opening the glycidyl ester group on the surface layer of the crosslinked copolymer particles and introducing a halogen, an aqueous solution of hydrogen halide such as hydrochloric acid, bromic acid, hydrochloric acid, hydroiodic acid, etc. can be used. The hydrogen halide concentration of the hydrogen halide aqueous solution is preferably o, i to 5% by weight.

For example, a porous cross-linked polyglycidyl methacrylate with a diameter of 10 μm is prepared using resin/f and an organic solvent such as n-hexane in a volume of 0 to 0. /~j Aqueous hydrochloric acid solution with a concentration of 0. After ring opening by adding a volume of /~/, Od and stirring at room temperature for O,S~/h.

01 (By introducing halogen, the general formula ■-000C!H,0HCH
,01t or ■-CO00)(,0H(1!H20H([F]
indicates a crosslinked copolymer having a glycidyl ester group)
A resin having a structure represented by the above in its surface layer is obtained.

The amount of halogen introduced into the crosslinked copolymer is sμmOl/?
~, 2θQpmO1/f' preferably 10~/θOμm
ol/? Preferably.

The amount of halogen introduced is controlled by controlling the concentration of one reaction reagent and the reaction temperature and time.

After the reaction is completed, the organic solvent used for ring-opening of the glycidyl ester group is washed off using a water-soluble or organic solvent such as methanol, and then washed with water to obtain a resin into which no-rogen has been introduced. become

As the tertiary amine used during amination, in addition to trialkylamines such as trimethylamine and triethylamine, idroxyalkylamines such as methyljetanolamine and dimethylethanolamine can also be used.

Amination reactions are carried out using these amine solutions. Solvents used during amination include water and methanol,
Alcohols such as ethanol are used.

The concentration of the amine solution is / mmo for complete amination.
It is preferable to use z/-~/Ommot/ynl.

The amination reaction is carried out at 20'Q to the boiling point of the solvent for 7 to 70 hours.

For example, a tertiary amine such as dimethylethanolamine/~10 mrnol
A volume of 3 to 1 θd per 1 g of resin is added to a methanol solution having a concentration of 3 to 1 θd, and dimethylethanolamine is introduced by performing amino acidification while stirring at 30 to 6 θC for 3 to 3 hours. After the reaction is completed, it is filtered and washed with water to obtain the formula 10000H2.
A resin having a structure of 0HOH, -OH 02H,OH on the surface layer is obtained.

The amount of functional groups is measured by measuring the neutral salt decomposition capacity.

Since the anion exchange resin obtained in this way has ion exchange groups only on the surface, the chromatogram will collapse to a high degree and at a high rate in ion exchange chromatography. Therefore, it is useful as the packing material 1 for ion exchange chromatography.

As the packing material 1 for ion exchange chromatography, a particle size of 50 μm to 50 μm is preferable.

The amount of functional groups introduced into the surface layer of the crosslinked copolymer is S
μeq/f-yu00μeq/f preferably 10~IOθ
μs, q/j' is preferred.

The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples as long as they do not go beyond the gist of the invention.

Method for measuring neutral salt decomposition capacity Manufactured surface functional anion exchange resin dry product Ay (!
; ff or less) into an Erlenmeyer flask, and add 0. /N-Na
Add OH50- and shake at room temperature for 7 hours. After filtering this, the solution is thoroughly washed with water until the pH of the washing solution reaches 7. After removing water by suction filtration for 70 minutes,
Pack it into a glass column with a 50cm filter and place it at the top of the column! A container containing the I% Na0t aqueous solution is set, and the P solution is collected by suction filtration at room temperature for 2 hours. This F
Titrate the solution with 0.0/N-hydrochloric acid using a mixed indicator of methyl red and methylene blue.

0,'0/N -If the factor of HOj is j and the amount used is M-, the neutral salt decomposition capacity of the resin can be determined by the following formula.

Neutral salt decomposition capacity (μθq/'Q=M×10xf Example/ (a) Production of crosslinked copolymer particles having glycidyl ester groups Ethylene glycol dimethacrylate 901, glycidyl methacrylate 210?, dimethel phthalate) 4//
f and λ, a'-azobis-2+kudimethylvaleronitrile 3? The mixture was added to a solution of polyvinyl alcohol/2 and sodium chloride g2 dissolved in 2/00 ml of demineralized water, and suspension polymerization was carried out at 70C for 3 hours while stirring at high speed. After cooling the reaction product, the produced copolymer particles were separated and washed with water. Next, this copolymer,
Toluene //2! rwf! and water 37! rml, stirred at room temperature for 3 hours, and then filtered. Furthermore,
This copolymer was poured into 8 St methanol and stirred repeatedly, and then dried at GO'6 for g hours.

The particles that have gone through the above operations are sieved to have a particle size of t~/, 2μm.
A copolymer of io.

? I got it.

(bl) Introduction of 4'-class ammonium groups (a) The copolymer particles 3? obtained in step (a) were placed in an n-tube at 720 mA!, 7N-hydrochloric acid 3d was added thereto with stirring, and then s
The reaction was carried out at o'r3 for 30 minutes. The reaction product was separated, washed with demineralized water and then methanol, and air-dried at room temperature for 7 hours. Next, convert this to trimethylamine concentration/mmot/m
into a methanol solution λ5d of 1IO without stirring.
C was maintained for a long time. After cooling, the reactant was separated and washed with water.

When the neutral salt decomposition capacity of the obtained resin was measured, the body μ
eq/f.

Application Example/Example/- Using the resin produced in (b), ion exchange chromatography of mixed anions of sulfate ion, nitrate ion, bromide ion, phosphate ion, chloride ion, and fluorine ion was performed.

The equipment for ion exchange chromatography is a dissolution tank, a liquid pump (Milton Roy 0396SF)
Ato-■ Co., Ltd.), line sample injector, glass separation column (inner diameter 3tcn, length 2.7o wo)
n), glass suppressor column (inner diameter 5wR1
length,? 3o wtr) and conductivity detector (LDO
-E3FO70/manufactured by Atto Corporation) recorder (Hitachi Q: pD
-sb) Yosi naru.

The resin produced in Example- was packed into a separation column. The suppressor column is MCI-GELOKOfIP (M
C! ■-GEL is a product name of Mitsubishi Chemical Industries ■) was filled. As the eluent, a mixed eluent of 0.003M sodium bicarbonate θ and 00/gM sodium carbonate was used. The flow rate was in the order of / resistance /.

As a mixed anion sample, sulfate ion so p
pm, nitrate ion 30ppm, bromide ion/θppm,
20 μt of a mixed solution of SO ppm phosphate ions, 10 ppm nitrite, 1 ppm chloride ions, and 3 PPIn fluorine ions was injected through a line sample injector using a microsyringe.

The chromatogram is shown in Figure 1.9. A chromatogram with good sensitivity and resolution was obtained.

Example Preparation of crosslinked copolymer particles having co-glycidyl ester groups Example t-Production was carried out by the same procedure using 300 g of toluene in the modified bb of the dimethyl 7-talate solvent in t-(a).

The resulting copolymer was treated with p by the procedure of Example t-(b).
A + class ammonium group was introduced.

The neutral salt decomposition capacity of the resulting resin was measured/10
μθq/7.

[Brief explanation of drawings]

FIG. 1 is a chromatogram obtained when mixed anions were subjected to ion exchange chromatography using the anion exchange resin of the present invention obtained in Example.

Claims (2)

[Claims] (1) A group represented by the formula (wherein R1, R2 and R11 represent an alkyl group or a hydroxyalkyl group) is added to the surface layer of a crosslinked copolymer particle having a glycidyl ester group! ;
Surface functional anion exchange resin with μsc1/f~200 peq/f (2) Crosslinked copolymer particles having glycidyl ester groups are reacted with an aqueous hydrogen halide solution in a water-insoluble organic solvent to open the glycidyl ester groups on the surface layer of the crosslinked copolymer particles and introduce halogen. A method for producing a surface-functionalized anion exchange resin, which comprises: