JPS59150544A - Strong acid type cation exchange substance having inclusion action and preparation thereof - Google Patents

Abstract

PURPOSE:To easily prepare a strong acid type cation exchange substance having inclusion action, by reacting monohalogenoalkylsulfonate with polycyclodextrin resin. CONSTITUTION:Usually, 0.5-5pts.wt. per 1pts.wt. of polycyclodextrin resin of monohalogenoalkylsulfonate is added to an aqueous alkaline solution in which the polycyclodextrin is dispersed under stirring and both reactive components are reacted under stirring while the temp. of the reaction liquid is held, for example, at about 40-60 deg.C to easily obtain polycyclodextrin into which a predetermined sulfoalkyl group is introduced. The obtained resin is an extremely specific new substance having not only the inclusion action of cyclodextrin but also strong acid type cation exchange capacity. Therefore, not only the respective characteristics of both components can be individually utilized but also both characteristics are utilized to be capable of performing separation of substances which are conventionally hardly separable and similar in molecular sizes or shaped.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel ion exchangers, more specifically,
The present invention relates to a strong acid type cation exchanger having an inclusion effect obtained by reacting a polycyclodextrin resin with a monologenoalkyl sulfonate, and a method for producing the same.

Cyclodextrin has six or more glucose α-1
, 4-linked cyclic oligosaccharides, which have a cylindrical cavity within the molecule and can envelop various substances in the cavity to form clathrate compounds. Substances that have the ability to form clathrates form clathrates by incorporating into them substances with molecular shapes and sizes that suit the cavity, and the affinity varies depending on the type of clathrate. Form different clathrates. Substances capable of forming clathrate compounds have such properties, and by utilizing these properties, it is possible to divide or isolate a specific compound or compound group from a mixture of various substances. When used for practical purposes such as substance separation, the clathrate-forming substance is usually made insoluble by, for example, crosslinking and polymerization, and then used to fill a chromatography column.

By the way, the formation of cyclodextrin inclusion compounds is
As mentioned above, it works effectively on substances of a shape and size that can be included in the cavity, but generally when separating substances using a resin that has inclusion forming properties, it is difficult to It is difficult to separate substances with similar shapes, and the same difficulty exists in the case of polycyclodextrin resin.

The present inventors utilized the clathration effect of Schiflobukis IJ to polymerize it to perform substance separation using a polycyclodextrin resin obtained by polymerizing it. In order to develop a method that can effectively separate similar compounds, we have conducted extensive research in particular on the modification of polycyclodextrin resins. When introducing sulfoalkyl groups into polycyclodextrin resins,
It was discovered that a desirable polycyclodextrin resin having both inclusion action and cation exchange ability can be obtained, and the present invention was completed.

That is, the present invention provides a method for producing a strong acid type cation exchanger having an inclusion effect, which is characterized by subjecting a polycyclodextrin resin to a total reaction with a monohalogenoalkyl sulfonate, and a method for producing a cation exchanger having an inclusion effect, which is characterized by subjecting a polycyclodextrin resin to a total reaction with a monohalogenoalkyl sulfonate, and cations obtained by such a method. It provides an exchange body.

The cyclodextrin used to form the polycyclodextrin resin in the present invention may be any of α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin, and two or three types of these may be used. Can also be used in combination. Polycyclodextrin resins are polymerized cyclodextrins, and any resin that can withstand the sulfoalkyl group introduction reaction can be used, but in particular, polycyclodextrin resins that have been crosslinked and polymerized using epichlorohydrin or jepoxy compounds can be used. Polycyclodextrin resins are preferred. Such a crosslinked polymerized resin is extremely suitable because it not only has high resistance to heat and alkali, but also has a large number of hydroxyl groups capable of reacting with the monohalogenoalkyl sulfonate.

In the method of the present invention, such a polycyclodextrin resin is reacted with a monohalogenoalkyl sulfonate, and examples of such a monohalogenoalkyl sulfonate include monochloroalkyl sulfonic acid containing a lower alkyl group, monobromo Alkali metal salts and alkaline earth metal salts of alkylsulfonic acids, monoiodoalkylsulfonic acids are used.

In this reaction, the polycyclodextrin resin is dispersed in an alkaline aqueous solution, such as a relatively high concentration aqueous solution of 20 to 50% by weight of sodium hydroxide or potassium hydroxide, and a monohalogenoalkyl sulfonate is added to this dispersion. It will be done. This reaction medium aqueous solution has strong alkalinity, and solid polycyclodextrin resin swells in an alkaline aqueous solution and the strength of the resin decreases, so it is preferable that the polycyclodextrin resin is subjected to the reaction in the form of beads. It can also be used as a ground powder. Further, for dispersing the polycyclodextrin resin, the above-mentioned alkaline aqueous solution is usually suitably used, for example, in an amount of 3 to 10 times the weight of the resin.

The amount of monochloroalkyl sulfonate added to the dispersion is selected depending on the desired introduction rate of sulfoalkyl groups, but it is usually 0.5 to 5 parts by weight per 1 part by weight of polycyclodextrin resin. A range of 50% is preferred. However, if a low introduction rate of sulfoalkyl group is desired, 0.5
It is also possible to add less than parts by weight.

After adding the monohalogenoalkyl sulfonate to the alkaline aqueous solution in which the polycyclodextrin resin is dispersed while stirring, the temperature of the reaction solution is adjusted to 40 to 60℃, for example.
When the reaction is carried out under gentle heating conditions of about 0.degree. C. and stirred, a polycysphrobutyl resin into which a predetermined sulfoalkyl group has been introduced can be easily obtained. The reaction temperature can also be carried out at a temperature higher than 60°C,
The desired resin may be colored, and the temperature at 40°C
Below, the above temperature range is preferable since there is a risk that the introduction rate of the sulfoalkyl group will decrease and it will take a long time to achieve a predetermined introduction rate. The stirring conditions for the reaction system are not preferable if the stirring conditions are too harsh since the resin will be pulverized, and the stirring conditions are generally preferably about 100 to 500 rpm.

When the reaction is carried out under such conditions, the reaction is usually completed in 5 to 24 hours, and a polycyclodextrin resin having a sulfoalkyl group is obtained. The reaction product is then separated, washed with distilled water until the washings become neutral, and then dehydrated with acetone or lower alcohol and dried. In the thus obtained polycyclodextrin resin having a sulfoalkyl group, the sulfonic acid group is in the form of an alkali metal salt of the alkali hydroxide used.
This can be easily converted into the H type by treatment with a dilute acid such as dilute hydrochloric acid in the water washing step, and can be used as a strong acid type cation exchanger.

The polycyclodextrin-based resin into which a sulfoalkyl group has been introduced according to the present invention is an extremely unique new substance that not only has a cyclodextrin inclusion effect but also has a strong acid type cation exchange ability.

Therefore, not only can each characteristic be used individually, but also
Utilizing both properties, it is possible to separate substances with similar molecular sizes and shapes, which were difficult to separate in the past. Therefore, it is advantageous over a wider range of areas as an ion exchanger, separation agent, and adsorbent. It can be used for.

Next, the present invention will be explained in more detail with reference to Examples.

Reference example Powdered β-cyclodextrin 252 to water 12.51
Add nlV and knead and 30% hydroxide) IJium aqueous solution 37.5- and sodium borohydride 100F'
Add 1g to make a homogeneous solution, keep it at 50℃ and boil it at 20Or
7.5m7 while stirring at a speed of pm! of epichlorohydrin was added dropwise, stirred for 30 minutes, and kept at 50° C. for 30 minutes to eliminate bubbles. 375 fnl of liquid paraffin was added to the resulting syrupy liquid and stirred at 1000 rpm for 5 minutes while keeping it at 50°C to uniformly disperse it, then epichlorohydrin 25- was added and stirred at 50°C for an additional 2 hours. .

The obtained beads were separated by filtration, washed 3 times with 100-hexane and then 3 times with 100-acetone, washed with distilled water until the pH of the washing solution became neutral, and further washed with 1 t of distilled water at 1 t of distilled water. The water-soluble components were eluted and removed by oral infusion. This is 5
After washing with 0% acetone water, it was dehydrated by being immersed in acetone at 300 mA, dried at a temperature of 70° C. for 1 day, and further dried with phosphorus pentoxide in a vacuum desiccator for 1 day. By sieving 29v of the poly-β-cyclodextrin beads thus obtained, 262 beads of 50 to 200 mesh were obtained.

Example 1 The poly-β-cyclodextrin beads 57 obtained in the reference example were dispersed in 30 rnl of a 33% aqueous sodium hydroxide solution, and while stirring at a speed of 200 rpm, 5 g of sodium 2-chloroethanesulfonate was added and the temperature was raised to 60°C. After heating and stirring for 5 hours, the mixture was kept at 50°C for 15 hours.

The reaction product was separated, washed with distilled water until the pH of the washing water became neutral, and then poured into 200ml of distilled water to remove water-soluble components. Then washed with 50% acetone water,
Further, it was dehydrated by adding one mouthful of acetone to 100 g of acetone, and dried with phosphorus pentoxide in a vacuum desiccator. Thus, 5.62 poly-β-cyclodextrin beads with sulfoethyl groups were obtained as the sodium salt. This 52 was immersed in IN hydrochloric acid to replace sodium ions with hydrogen ions, thoroughly washed with water, and then 0. As a result of titration using an aqueous sodium hydroxide solution of IN, 1.8
xlO" moles of sulfoethyl groups. Therefore, the poly-β-cyclodextrin beads 52 can adsorb cations equivalent to 1.8 x 10-8 moles of sodium ions, and can be used as a cation exchanger. can.

Claims (1)

[Scope of Claims] 1. A strong acid-type cation exchanger having an inclusion effect and comprising a polycyclodextrin resin having a sulfoalkyl group. 2. A method for producing a strong acid type cation exchanger having an inclusion effect, which comprises reacting a polycyclodextrin resin with a monologenoalkyl sulfonate. 3. The manufacturing method according to claim 2, wherein the monohalogenoalkylsulfonic acid is monochlorolower alkylsulfonic acid.