JPS63267447A - Cation exchange resin and its manufacture - Google Patents

Abstract

PURPOSE:To improve ion elution characteristics by preparing a cationic ion exchange resin which has a reactive functional group and an ion exchange capacity of at least 10-250mu equivalents per gram, and is stable in a reaction liquid at a specific pH value for 10hr or more. CONSTITUTION:A crosslinked copolymer resin which has a reactive functional group, and is stable in a suspension at pH 1-13 and in a reaction solution at pH 14 for 10hr or more, and insoluble in an organic solvent, is selected as a basic material. In addition, compounds which have a functional group permitting ether bonding with the basic material, and are not decomposed by acid or alkali after the bonding and allow introduction of a cationic exchange group into the unbonded end, are selected as spacer compounds. The basic material and the spacer compounds are allowed to react with each other in a solvent containing a catalyst and the basic material is washed after reaction to permit reaction with the objective cationic exchange group. As a result, a cationic exchange resin capable of ion exchange of 10-25mu equivalents per gram is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a cation exchange resin packed in a chromatography tube and used as a separation column for ion chromatography, and a method for producing the same.

<Prior art> Cation exchange resins packed in chromatography tubes and used as separation columns for ion chromatography include, for example, those made by adsorbing latex on the surface of polystyrene gel, and those made by directly sulfonating polystyrene gel. It is known that a very small amount of sulfone group (Fji ion exchange group) is introduced only on the surface. In such a packing material (cation exchange resin), ions with a weak retention force, such as Cu2+ ions, are eluted almost overlapping with the water dip (a large negative peak caused by water in the liquid to be measured), and the ions are The quantification was very inaccurate. For this reason, attempts are made to improve quantitative performance by changing the mobile phase (eluent, etc.), but changing the mobile phase (eluent, etc.) changes the entire ion elution pattern, resulting in ion analysis. The disadvantage was that it became complicated. Additionally, attempts have been made to improve the ion separation properties of the filler (cation exchange resin) itself by changing the type of base or latex; The drawback was that it required significant changes to the manufacturing process for ion exchange resins. On the other hand, in the field of immobilized enzymes, spacers are widely used to chemically immobilize enzymes on stationary phases and carriers, and this spacer avoids steric hindrance between enzymes and allows the enzyme to be immobilized on the stationary phase and carrier. The rate has improved significantly. Furthermore, it is known that since the enzyme immobilized via such a spacer is separated from the stationary phase and carrier, the enzymatic reaction proceeds quickly and exhibits high enzymatic activity.

<Problems to be solved by the invention> However, there are almost no examples of using spacers in ion exchange resins, and in polystyrene-based anion exchange resins in which linear alkyl groups are introduced as spacers, hydrophobicity occurs between the sample and the spacer. There has been only one academic conference presentation in which adsorption was observed.

Furthermore, there are no examples of using spacers in cation exchange resins or high performance liquid chromatography such as ion chromatography.

The present invention was made in view of the above situation, and its purpose is to provide a cation exchange resin (filler) and a cation exchange resin (filler) with improved ion elution characteristics by suppressing the interaction with the base material and the effects of the bore of the filler. The object of the present invention is to provide a manufacturing method thereof.

Means for Solving the Problems> The feature of the present invention for solving the above problems is that the cation exchange resin (filler) and the method for producing the same have a reactive functional group and have a pH of 1 to 13. in suspension and pH 14
Select a crosslinked copolymer resin that is stable in the reaction solution for at least 10 hours or more and is insoluble in organic solvents, and use it as a base;
It has a functional group that can form a chemical bond with the base material in the form of an ether bond or a covalent bond between carbons, does not decompose in acid or alkali after the chemical bond, and has an ion exchange group introduced at the unbonded end. The compound that can be produced is selected and used as a spacer compound, the base material and the spacer compound are reacted in a solvent containing a catalyst, the base material into which the spacer is introduced is washed, and the desired cation exchange group is introduced through the spacer. The purpose is to introduce the above-mentioned cation exchange resin (filler).

<Example> Hereinafter, the present invention will be described in detail using the drawings. 1st
The figure is a process explanatory diagram for explaining the method for producing a cation exchange resin (filler) according to the present invention. In this figure, initially, a cross-linked copolymer resin (e.g. , hydroxyl group-containing methacrylate-based crosslinked spherical resin) are selected and used as the base material. Next, this base is dispersed in dimethyl sulfoxide (hereinafter abbreviated as DMSO) and sufficiently swollen. Thereafter, for example, glycerin polyglycidyl ether, which is a mixture of diglycidyl ether and triglycidyl ether, is selected and used as a spacer compound. That is, it has a functional group that can form a chemical bond with the base material that is stable against acids and alkalis (for example, an ether bond or a chemical bond formed by a covalent bond between two carbon atoms),
After the chemical bonding, a compound that does not decompose in acid or alkali and can introduce an ion exchange group to the unbonded end is selected and used as a spacer compound. Thereafter, a large excess amount of the spacer compound is added to the gel slurry made of DMSO or the like and sufficiently dissolved to form a uniform slurry reaction solution. A boron trifluoride etherate solution serving as a catalyst is added to this slurry reaction solution, and the mixture is reacted at 40° C. for 2 hours with stirring.

In this way, the base and spacer compound can be reacted in a solvent containing a catalyst. After the reaction is completed,
The reaction product is transferred onto a glass filter, and the reaction product is washed with DMSO, methanol, and pure water in this order to wash out reaction byproducts and excess DMSO. Next, 3 times the amount of pure water as the base is added and stirred to form a uniform slurry, and anhydrous sodium sulfite is added and reacted for 7 hours with stirring in a water bath at 80°C. After the reaction is completed, pure water is added to the reaction slurry and the slurry is cooled. Thereafter, the slurry is transferred onto a glass filter and thoroughly washed with pure water. Furthermore,
Hydrochloric acid, caustic soda, and sodium chloride were poured into the slurry on the glass filter in that order, with pure water washing in between, to change the counterion type of the base to hydrogen type and sodium type, and then store it in sodium chloride. do. In this way, a substance corresponding to the desired cation exchange group is reacted with the base material, and the desired cation exchange group is introduced into the base material via the spacer. By such a manufacturing method, a cation exchange resin into which a desired cation exchange group is introduced via a spacer is realized. This cation exchange resin is based on a crosslinked copolymer resin that has a reactive functional group, is stable in a suspension of P 1-11 to 13, and is insoluble in an organic solvent. It has a structure in which it has a functional group having an ether bond or a covalent bond between carbon atoms with the agent, and a spacer compound having a desired cation exchange group introduced at the unbonded end. In addition, this cation exchange resin
For example, a stainless steel chromatography tube with an inner diameter of 4.6 mm and a length of 150 mm is filled using a high-pressure slurry filling method and used as a column for ion chromatography. still,
The present invention is not limited to the above-described embodiments, and can be modified in various ways. For example, as a resin stable in the above solution,
Resins based on polystyrene, polymethacrylate, or polyvinyl alcohol may also be used.

In addition, the above compounds include diol compounds, triol compounds, polyol compounds, jepoxy compounds, triepoxy compounds, polyepoxy compounds, alcohols with primary chlorine, epoxy compounds with primary chlorine, and epoxy compounds with alcoholic hydroxyl groups. It is also possible to use any one of these substances.

FIG. 2 is an explanatory diagram of the configuration of a general ion chromatograph apparatus. When the liquid feed pump 2 is driven, the eluent in the eluent tank 1 is transferred from the liquid feed pump 2 to the injector 3 to the fluid preheating tube 4. →separation column 5→detector 6, and flows to waste liquid tank 7. Also, fluid preheating tube 41 separation column 5. The detector 6 is housed in a constant temperature bath 9 at a constant temperature (for example, 40
'C) and the liquid feeding pump 2. Injector 3, fluid preheating tube 40 separation column 5. and the detector 6 are often housed within the casing 10 of the analyzer. In the ion chromatography apparatus having such a configuration, a signal detected by the detector 6 is guided to a display device 8 (for example, a recorder) to draw a chromatogram. FIG. 3(A) shows a 2pp
m L i + ions, 10 ppm Na + ions, 1
0 pl) m of NHa+ ions, and 20 ppm of NHa+
This is a chromatogram showing the results of analyzing a test liquid containing ions (hereinafter referred to as "standard solution"). In addition, Figure 3 (b) shows that the above standard solution was analyzed using an ion chromatograph using Yokogawa Electric's cation separator 5CX3, which was prepared by filling a surface sulfonated column packing material, as a separation column. This is a chromatogram showing the results, and the third
Figure (c) shows the results of analyzing the above standard solution using an ion chromatograph using Yokogawa Electric's cation separator 5CX1, which was prepared by packing a surface sulfonated column packing material, as a separation column. This is a chromatogram shown.

In the chromatograms of FIGS. 3(a) to 3(c), peaks w, a, and b.

C1 and d represent water dip (a large negative peak caused by water in the liquid to be measured), Li+ ion,
Na+ ions, NHa+ ions, and Ni+ ions are shown. Furthermore, in the chromatogram shown in FIG. 3(a), Li+ ions (a) are eluted much later than the water dip (W). As is clear from a comparison of the chromatograms in Figure 3 (a) to (c), if the cation exchange resin according to the present invention is used as a column packing material, it is possible to The ions are strongly retained by the column packing material and elute much later than water dip (W), making it easier to obtain desired ions in cation analysis, which often uses large-volume or concentrated injection methods. It becomes possible to separate into In addition, in the chromatogram of FIG. 3 (in) to (c), peaks a, b, and c in the chromatogram of FIG. 3 (a) prepared using the cation exchange resin of the present invention as a column packing material , and d are not necessarily sharp peaks compared to the peaks in the chromatograms in Figure 3 (b) and (c), but they can be seen by making the column packing particles smaller or changing the elution conditions. This is something that can be easily improved to make the peak sharper.

By the way, when introducing a carboxyl group as the above-mentioned desired cation exchange group, it is carried out as follows. That is, the base material into which the spacer compound was introduced was mixed with 1
．． The mixture is washed with 4-dioxane to obtain, for example, 100 ml of dioxane-gel slurry, and then, for example, 5 g of sodium gelcholate is added and sufficiently dissolved to obtain a uniform slurry reaction solution. A boron trifluoride etherate solution serving as a catalyst is added to this slurry reaction solution, stirred at air temperature for, for example, 30 minutes, and then heated to 80'C and reacted for about 2 hours. After the reaction is completed, the reaction product is transferred onto a glass filter, and the reaction product is washed in the order of dioxane, methanol, and pure water. The resin thus obtained is placed in, for example, 0.05 normal (N) 82SOd and reacted at, for example, 600C for 3 hours, and then thoroughly washed with water. In this way, a substance corresponding to the desired cation exchange group is reacted with the base, and a carboxyl group, which is the desired cation exchange group, is introduced into the base via the spacer. FIG. 4 is an explanatory diagram for explaining the chemical reaction when a jepoxy compound is used as the spacer compound and a divine cation exchange group is introduced as the desired cation exchange group, and in the figure, B is The above base, R
, R- represents an alkyl group. In Figure 4, (
In 1), Lt is used as the desired cation exchange group.
(CH2CH2803-) is introduced, in (2) a carboxyalkyl group (-CH(R-')COO-> is introduced as the desired cation exchange group, and in (3) the above-mentioned desired cation exchange group is introduced. Cases in which a carboxyalkyl group (CH2(R'>Coo-) is introduced as a cation exchange group are shown in each case. In addition, in (4), a thiol group (-8H) is introduced as the desired cation exchange group.
) is introduced, and in the upper reaction of <5), a low a degree acid, for example 0. The epoxy ring of the spacer compound is opened by IN H2SO4), and in the lower reaction of (5), a carboxymethyl group (CH2COO
″″) are introduced.

<Effects of the Invention> According to the embodiments of the present invention as described in detail above, a spacer is introduced between the base material and the ion exchange group, and ultimately the selectivity of the separation column is significantly improved. This makes it possible to create a cation exchange resin (filler) with improved ion elution characteristics by suppressing interactions with the base material and the effects of filler bores.

Furthermore, if the cation exchange resin according to the present invention is used as a column packing material, ions with a relatively weak retention force such as L1+ ions will be retained considerably strongly in the column packing material, resulting in better retention than water dip (W). Since ions also elute with a considerable delay, it has the advantage that cations can be separated and analyzed well even when using large-volume injection methods or concentrated injection methods. Furthermore, even ions that are generally considered to have a weak retention force, such as Cu 2 + ions, are strongly retained by the column packing material and elute later than the water dip, so the effects of the water dip can be reduced. There is also the advantage that divalent transition metal ions can be separated and analyzed well without being affected. Furthermore, by changing the length of the spacer, by replacing it with a spacer compound having a hydroxyl group, amino group, carboxyl group, nitro group, etc. in the skeleton, or by changing the type of substance that corresponds to the desired ion exchange group. By changing the ion exchange group, it is possible to produce diversified cation exchange resins with different ion elution characteristics, and there is also the advantage that various cation exchange resins can be produced without significantly changing the production process.

[Brief explanation of the drawing]

Fig. 1 is a process diagram for explaining the method for producing a cation exchange resin (filler) according to the present invention, Fig. 2 is an explanatory diagram of the configuration of a general ion chromatography device, and Fig. 3 is a cation exchange resin (filling agent) manufacturing method. Chromatogram showing the results of analysis using an ion chromatograph with an exchange resin packed in a separation column,
FIG. 4 is an explanatory diagram for explaining chemical reactions when a jepoxy compound is used as a spacer compound and various cation exchange groups are introduced as the intended cation exchange group. 1...Eluent tank, 2...Liquid pump,
3... Injector, 4... Fluid preheating tube, 5... Separation column, 6... Detector, 7... Waste liquid tank, 8...Display device, 9
・・・・・・Thermostatic chamber, 10 ・・・・Analyzer housing Figure 1 Figure 4

Claims (6)

[Claims] (1) The base is a cross-linked copolymer resin that has a reactive functional group, is stable for at least 10 hours in a suspension with a pH of 1 to 13, and a reaction solution with a pH of 14, and is insoluble in organic solvents. , having a spacer compound having a functional group having an ether bond or a covalent bond between carbon atoms with the base material, and a cation exchange group introduced at the unbonded end;
A cation exchange resin having an ion exchange capacity of at least 10 to 250 μequivalents per gram. (2) The crosslinked copolymer resin is a resin based on polystyrene, chloromethylated polystyrene, methylolated polystyrene, polymethacrylate, or polyvinyl alcohol.
) Cation exchange resin described in section 2. (3) Packed into a chromatography tube and used as a separation column for ion chromatography, at least 1 gram per gram.
A method for producing a cation exchange resin, which comprises producing a cation exchange resin having an ion exchange capacity of 0 to 250 micro equivalents through the following steps (a) to (d). b) Select a crosslinked copolymer resin that has a reactive functional group, is stable for at least 10 hours in a suspension with a pH of 1 to 13, and a reaction solution with a pH of 14, and is insoluble in organic solvents and used as a base. Process. b) It has a functional group that can form a chemical bond with the base material in the form of an ether bond or a covalent bond between carbons, does not decompose in acid or alkali after the chemical bond, and has an unbonded end. A process of selecting compounds that can introduce cation exchange groups into spacer compounds. c) A step of reacting the base and the spacer compound in a solvent containing a catalyst. d) After washing the base that has reacted with the spacer compound, a step of reacting a substance corresponding to the desired cation exchange group with the base into which the spacer has been introduced to introduce the cation exchange group. (4) The method for producing a cation exchange resin according to claim (3), wherein the crosslinked copolymer resin is a resin based on polystyrene, chloromethylated polystyrene, methylolated polystyrene, polymethacrylate, or polyvinyl alcohol. . (5) The spacer compound includes a diol compound, a triol compound, a polyol compound, a diepoxy compound, a triepoxy compound, a polyepoxy compound, an alcohol compound having a primary chlorine, an epoxy compound having a primary chlorine, and an alcoholic hydroxyl group. Claim No. (3) consisting of any one of the epoxy compounds having
The method for producing a cation exchange resin described in Section 1. (6) The substance corresponding to the desired cation exchange group is a compound having a sulfone group, a compound having a carboxyl group, a compound having a phosphoric acid group, or a compound having a sulfone group by reacting with the terminal group of the spacer compound. A cation exchanger according to claim (3), which is a compound, a compound that reacts with the terminal group of the spacer compound and has a carboxyl group, or a compound that reacts with the terminal group of the spacer compound and has a phosphate group. Resin manufacturing method.