JPS5926142A - Cation exchange element having inclusive action and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a cation exchange element having inclusive action, by introducing a carboxymethyl group into polycryclodextrine resin. CONSTITUTION:In order to introduce a carboxymethyl group into polycyclodextrine, monohalogenoacetate is added to polycyclodextrine dispersed in an alkaline aqueous solution and the resulting mixture is held at 40-60 deg.C under stirring to carry out reaction. The obtained product is washed by distilled water until the pH of washing water becomes neutral and dehydrated by acetone to be dried to be converted to an alkali metal salt or an alkaline earth metal salt. The obtained one is wahed by dilute hydrochloric acid to substitute a cation with a hydrogen ion and the treated one is used as a cation exchange element. By this method, the cation exchange element having inclusive action is obtained. The obtained resin can be used as an ion exchange element, a separating agent and an adsorbent.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to its production method, and more specifically relates to an ion exchanger of polycyclodextrin resin having a carboxymethyl group and its production method by reacting a polycyclodextrin resin with a monohalogenoacetate. be.

Cyclodextrin has six or more glucose molecules α-3,
, 4-bonded cyclic oligosaccharide, which has a cylindrical cavity within its molecule, and forms clathrate compounds by incorporating various substances into it. 0 This clathrate compound is formed. In order to achieve this, the shape and size of the molecule of the clathrate must be compatible with the cavity of the cyclodextrin, and depending on the degree of compatibility, there may be a gap between the clathrate and the cyclodextrin. Since there is a difference in the Attempts are being made to use it as a packing material for column chromatography.

However, since the clathrate compound-forming action of cyclodextrin mainly depends on the size and shape of the substance to be included, when separating substances using polycyclodextrin resin obtained from Kotoni, which polymerizes cyclodextrin, The more similar the sizes and shapes, the more difficult it is to separate them. Therefore, in such a case, the mere effect of inclusion is insufficient for separation, and it is necessary to introduce some effect that is effective for separation.

In view of these circumstances, the present inventors have conducted extensive research into improving polycyclodextrin (salmon), and as a result,
By introducing carboxymethyl threads into polycyclodextrin resin, polycyclodextrin (polycyclodextrin) resin not only has an inclusion effect but also has an ion exchanger effect, so it can be
, f'/i'? The present inventors have discovered that the effect of the interaction is added, and therefore the ability to separate substances due to the difference in charge distribution can be provided, and the present invention has been accomplished based on this knowledge.

The polycyclodextrin used in the present invention is α-
Cyclodextrin, β-cyclodextrin, r-cyclodextrin, and mixtures thereof are crosslinked into 26 molecules or bonded to a polymer,
Any material that can withstand the reaction conditions for introducing a carboxymethyl group can be used. In particular, polycyclodextrin resin crosslinked with ribic chlorohydrin or jepoxy compound not only has high resistance to heat and alkali, but also has a large number of hydroxyl groups that can react with mono- and D-genoacetates. This is suitable because there are many

In order to introduce carboxymethyl groups into polycyclodextrin resin, monohalogenoacetate is added to polycyclodextrin dispersed in an alkaline aqueous solution. The shape of the resin used is a mixture of solid polycyclodextrin resin! There are resins in the form of shells and beads, but
When the resin swells in an alkaline aqueous solution, the strength of the resin becomes weaker, so a bead-like shape is preferred. As an alkaline aqueous solution, sodium hydroxide or hydroxide IJ
Ram v) 2. A concentration of O-50, ffl river per cent is suitable, and is added in an amount of 3 to 10 parts by weight per part by weight of the polycyclodextrin resin. As monohalogenoacetic acid salts, alkali metal salts and alkaline earth metal salts of monochloroacetic acid, motu 1 comoacetic acid, and monoiodoacetic acid are used, and the amount is 0.5 to 51 parts by weight per 1 it r'flI of polycyclodextrin resin. The range is preferably O85 or less, but if the introduction rate of carboxymethyl groups is to be reduced, it may be O85 or less.

The monohalogenoacetate is used in powder form or as an aqueous solution. In the case of an aqueous solution, if the IA degree is low, the introduction rate of carboxymethyl groups decreases, so it is preferably 20% by weight or more.

While stirring the polycyclodextrin resin dispersed in the alkaline aqueous solution, the monohalogenoacetate is added, and then the reaction is carried out while maintaining the temperature at 40 to 60°C. The stirring speed is preferably 100 to 500 rpm, and vigorous stirring is not preferred since it may crush the resin. Even if the humidity is outside the range of 40 to 60 degrees Celsius, however, above 60 degrees Celsius, the fat will become discolored. At 40°C or higher, the introduction rate of carboxymethyl groups becomes 77μ. Reaction time is 5 hours ~
1 [ko is appropriate. The obtained product is obtained as an alkali metal salt or an alkaline earth metal salt by dehydrating it with distilled water until the pH of the washing water becomes neutral and avoiding drying. It will be done. By washing this with dilute hydrochloric acid, it can be converted to 1r1 with a cation (:L hydrogen) and used as a cation (1'<J1).

The feature of the present invention is that a cation exchanger having an inclusion effect can be obtained by introducing 3 tons of carboxymethyl groups into a polycyclodextrin resin. Next, the present invention will be further explained using a reference example and a tip 1Δ1.

Reference example 25P of powdered β-cyclodextrin and 12.5M of water
37.5 ni of IJium aqueous solution and 10 ml of sodium borohydride (30% hydroxide)
Add to make a homogeneous m solution, keep it at 50℃ and turn it to 20Orpm.
Add 1.5 ml of epichlorohydrin dropwise while stirring at a speed of
The temperature was kept at 50°C for 0 minutes. Add 3"15vnl of liquid paraffin to the resulting syrupy liquid and stir at LOOORPM for 5 minutes while maintaining the temperature at 50°C to uniformly change the mixture.
Then, 2'5 m, 1 of epichlorohydrin was added, and the mixture was stirred at 50°C for an additional 2 hours. The obtained beads were filtered, strained, and washed with 100 ml of Hekilin three times.
Then 3 times with acetone 1oofn7? After the first nI, b
It was washed with distilled water until the ER solution became neutral, and then immersed in distilled water Je to remove 1 J of water and 147 components.

After washing this with 50% acetone water, 30Off+/
Dehydrated by soaking in acetone of
Let it dry in the sun. The thus obtained poly-β-cyclodextrin beads 29? 5 by pulling the power bow into the sieve.
26 beads of 0-200 mesh? I was attacked.

Holly β-cyclodextrin Heath 10 obtained according to Examples and Reference Examples was dispersed in 30 ml of 30% sodium hydroxide aqueous solution, and while stirring at 200 rpm, 30 ml of 30% sodium monothallacetate aqueous solution was added dropwise, stirred at room temperature for 30 minutes, and then continued stirring at 60°C for 10 hours. . Generation 14. BL +: 61g with distilled water until the pH of the purified water becomes neutral; After purification, soak in distilled water 500°C for 1 day to remove water-soluble components, wash with 50% acetone water, (After cleaning twice with 100 m7 of acetone, dehydrated by soaking in 20 Q ffl1 of acetone, and diluted with 5111 phosphorus in a vacuum desiccator.
l:Re-dried-Uta. Thus, the poly-β-cyclodextrin beads 11 having carboxymethyl groups? was obtained as sodium 1111. This is IN 11
4 m]-thorium r ion with hydrogen imen
After diluting with 4 mols of water and thoroughly removing M and H, titration with 4 ml of sodium hydroxide solution revealed that IOP contained 7.6 x 1 mole of carboxyl groups. Therefore this poly β
- SixtJ Dextrin Beads 109 are sodium chloride, 7.6
It can be used as a positive energy exchanger.

Claims (1)

[Scope of Claims] l A cation exchanger having an inclusion effect, which is made of a polycyclodextrin resin having a carboxymethyl group. 2. A method for producing a cation exchanger having an inclusion effect, which comprises reacting a polycyclodextrin resin with a monohalogenoacetate.