JPS59193141A - Novel compound body and its preparation - Google Patents

Abstract

PURPOSE:To obtain a compound body having higher physical strength than the products made of conventional resin by including an ion exchange resin or a chelate resin in the pores of porous glass particles. CONSTITUTION:A compound body is formed by including an ion exchange resin or a chelate resin in the pores of porous glass particles. For the formation of this compound body, a monomer incorporated in the pores of glass particles is polymerized, further, if necessary, an introducing reaction of an exchange group is carried out. The compound body is a novel one having both the characteristics as an ion exchange resin or a chelate resin in combination with the strength as glass, having higher physical strength than conventional products. The compound body is useful for an ion exchange body or chelate forming body requiring high strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel composite comprising an ion exchange resin or a chelate resin contained within the pores of porous glass particles, and a method for producing the same.

Ion exchange resins and chelate resins that are currently commercially available are organic bodies that have a three-dimensionally crosslinked structure, and
It is usually a sphere having a diameter of about S microns to millimeters. Ion exchange resins are broadly classified into cation exchange resins and anion exchange resins, and cation exchange resins include those with sulfone groups and carboxyl groups.
As anion exchange resins, those having amino groups or ammonium groups are used. In addition, many types of chelate resins are used, such as polyol type, polycarbonyl type, and polycarboxylic acid type. However, these ion exchange resins or chelate resins are not satisfactory in terms of their physical strength. It wasn't something. For example, when used as a packing material in liquid chromatography, there are many disadvantages such as the flow rate being restricted due to its strength, and the length of the column being restricted in the case of industrial packed columns.

As a result of repeated studies from this perspective, the present inventors have
We have discovered a new composite consisting of glass containing an ion exchange resin or a chelate resin. That is, the present invention relates to a composite containing an ion exchange resin or a chelate resin in the pores of porous glass particles, and a method for producing the same.

The ion exchange resin in the present invention refers to a cation and anion exchange resin. There are no particular limitations on the chemical structure of these compounds, and any structure may be used as long as it has the property of exchanging cations and/or anions. It may be an amphoteric ion exchange resin that has the ability to exchange both anions and cations.

A preferred example of the cation exchange resin is a polymer having a sulfone group or a carboxyl group. More specific examples include three-dimensional polymers containing polyvinylbenzenesulfonic acid, polyvinylbenzoic acid, polyacrylic acid, polymethacrylic acid, etc. in polymerized units. Preferred examples of anion exchange resins include those having primary to tertiary amino groups or those having t-class ammonium groups. To give a more specific example, a functional group represented by -CH2-N RI R2 (R1, R2 represents hydrogen, a hydrocarbon group, an alkanol group, an aminoalkyl group, etc.) is added to the side chain of polystyrene or polyacrylamide. or -CH2-NRIR2R3X (R3 is R1, R
Same as 2, those containing a secondary ammonium group represented by Examples include compounds that have Examples of the heterocycle include not only pyridine and imidazole, but also pyrazole, thiazole, triazole, carbazole, benzimidazole, and indole.

A chelate resin is one that has the property of capturing metal ions, and its chemical structure is not particularly limited, but specific examples include polymers with hydroxyl groups such as polyvinyl alcohol, vinyl methyl ketone,
Polymers with a ketonic carbonyl group as typified by methacryl acetone, polymers with a hydroxycarbonyl group as typified by salicylic acid formaldehyde resin, polyacrylic acid, polymethacrylic acid, polyitaphonic acid, thiophene maleate, or iminodiacetic acid groups Polymers having carboxyl groups represented by polymers, polymers having amine groups, oxime groups, azo groups, etc., polymers having thioalcohols, thiophenol groups, thioketones, dithiolates, thioamides, polymers having thiourea groups, first, Examples include polymers having secondary and tertiary alkylarylphosphine groups.

These ion exchange resins or chelate resins exist in the pores of the glass particles in a three-dimensionally crosslinked form.

There is no particular restriction on the shape of the porous glass particles in the present invention, and they may be spherical or irregularly shaped, typified by crushed particles. Although there is no limit to the size of the particles, it is preferred that the particles have a maximum length of 7 microns to 5 millimeters.

“Glass particles have pores that open to the outside.The ratio of the volume of the pores to the total volume of the glass particles (porosity (α)) is O〈α〈/, but preferably OθS or 0.9&.The average pore diameter (r) of the open pores is not particularly limited, but is preferably less than go, oooh.

α and r can be measured by a porosimeter using mercury, a gas adsorption method, or the like.

Porous glass particles may preferably have silylated surfaces.

Next, a method for producing a composite according to the present invention will be described.

A typical method for synthesizing porous glass particles is to melt a mixture of oxides such as B2O3 and Na2O and silicon oxide, and then phase-separate the mixture. Commercially available porous glass particles having open pores may also be used.

It may be preferable to silylate the surface of the raw material glass particles. As a silylation method, Y 83 R4R5Rs (R4R5
Rs is a hydrocarbon group, Y is a halogen), Y2 Si R
It can be obtained by reacting 4R5, Y3 Si R4, etc.

In order to incorporate an ion exchange resin or a chelate resin into the pores of the glass particles, a monomer is introduced into the pores of the glass particles, and then a polymerization reaction is performed, and if necessary, a reaction to introduce an exchange group is performed. Just do it.

The monomer may be contained in the pores by mixing the glass particles and the monomer. The monomer may be a mixture with a diluent or solubilizer, if necessary. At this time, it is more preferable to adopt a method of introducing the monomer into glass particles under vacuum.

Furthermore, it is also preferable to apply ultrasonic vibration for a period of several seconds to several minutes.

It is preferable that the monomers contain a polymerization initiator. The monomer-containing glass particles obtained in this manner may be subjected to a polymerization reaction after the liquid is removed from the outside by p-filtration or the like.

The polymerization may be carried out directly by heating, but it is preferable to disperse it in an appropriate solid or liquid. Preferably, the solid is a particle approximately equal to or smaller in size than the glass particle. Specific examples include common salt, metal halides such as potassium bromide and sodium iodide, sulfates such as sodium sulfate and calcium sulfate, nitrates such as potassium nitrate, calcium oxide, aluminum oxide, and These include metal oxides such as silicon and phosphates such as calcium phosphate. Organic powders that are solid at room temperature may also be used. Since these solids are to be separated in the after-treatment, they must be dissolved in a suitable solvent. Among these, water-soluble ones are preferred.

When dispersing in a liquid, it is preferable to select a liquid in which the monomer contained in the pores will not be eluted into the dispersion liquid. When a hydrophobic monomer is contained in the pores of glass particles and polymerization is carried out in a dispersion, it is preferable to use porous glass particles whose surfaces are silylated.

Although there are no particular restrictions on the temperature and time of polymerization, a temperature of 10°C to 700°C and a time of about 30 hours is usually employed.

After the polymerization is completed, a reaction may be carried out to introduce a functional group, if necessary. For example, in order to obtain a structure made of a mukaion-exchanged resin containing polyvinylbenzenesulfonic acid as a polymerization unit, styrene is copolymerized with a crosslinking agent, etc., and then copolymerized with chlorosulfonic acid, sulfuric acid, sulfuric anhydride, etc. All you have to do is react. In addition, instead of a sulfonation reagent, chloromethylation is performed using chloromethyl ether, etc.
Further, by reacting with an amine represented by NRI R2 or NRI Rz R3, an anion exchange resin can be obtained. After chloromethylation, a dicarboxylic acid type chelate resin can be obtained by reacting with iminodiacetic acid. It is also possible to use commercially available chloromethylstyrene instead of styrene. These are not necessary when using a monomer that already has a functional group exhibiting ion exchange or chelation properties, such as vinylpyridine, acrylic acid, meccrylic acid, or vinylimidazole.

The composite in the present invention is a novel composite that has both the properties of an ion exchange resin or chelate resin and the strength of glass, and has physical strength superior to conventional resins. It is useful as an ion exchanger or chelate former.

Examples are shown below.

Example: A porous powdered glass with an average pore diameter of 00θ, a longest particle diameter of 37 to 37μ, a specific pore volume of o, and a g of 12 is placed in an eggplant-shaped flask with a magnetic stirrer and pumped with a vacuum pump. The pressure was reduced at Next, 2.0% of chloromethylstyrene (purity q2%, m/p-Otsu/41.) was added to this eggplant flask. Off,
m-Divinylbenzene2. :12? , azobisisoduthyronitrile 0.2:i? A mixed solution of toluene 301 was introduced, and the mixture was stirred at room temperature under reduced pressure for 2 hours.

Next, pass this through a glass filter, and combine it with 309.
of sodium chloride were thoroughly mixed, and the mixture was reacted at 90° C. for 6 hours under a nitrogen atmosphere.

The reaction product was thoroughly washed with water to dissolve the common salt, and then thoroughly washed with acetone.

Add to this acetone 10O1n1. , dimethylamine were added thereto, and the mixture was allowed to react at room temperature for S hours. The product was thoroughly washed again with acetone and water.

The exchange capacity of the resulting complex was /k meq/f.

The composite obtained here and commercially available DOWEX ■MSA-
/ is packed into a cylindrical column of l0cnφ to a height of 70 ports, and from the top! ; When applying a pressure of kg/cril and looking at the change in height, it was observed that the height of DOWEX ■MSA-/ decreased to t,9 crn, but the height of this composite decreased. was not recognized.

Example average pore diameter 3000A, longest diameter of particles SOO~300A
Porous crushed powder glass with a specific pore volume of 10 mVt in the μ range A, Of? After washing thoroughly with concentrated nitric acid,
The mixture was poured into 2 parts of dichloromethylsilane and reacted for 7 hours at room temperature under a nitrogen atmosphere. After the product was separated, it was thoroughly washed with anhydrous methanol and dried under reduced pressure. On the other hand, styrene 20.0? , divinylbenzene (purity 5A%
, m/p=q/3. lI3% ethylstyrene, 7%
A solution was prepared by mixing and dissolving diethylbenzene)S, Ot, azobisisobutyronitrile θ2co2, and methyl benzoate 109, and the monomer was contained in the pores by the same method as in Example. The glass particles were dispersed in 500° C. of water, heated to 90° C., and reacted with stirring for hours. The obtained product was washed successively with acetone and water, and then dried under reduced pressure. Next, the glass particles and 100% of methylene chloride were mixed, and 301% of chlorosulfonic acid was added dropwise to the mixture while stirring at 10°C. At the same temperature 2
After continuing the reaction for a certain period of time, the reaction mixture was poured into ice-water, and the mixture was washed with water and then combined overnight. The exchange capacity of the complex is 12
/meq/t (cation).

Example 3 Glass particles containing a styrene-divinylbenzene copolymer obtained by the same method as in Example 3 were chloromethylated by a conventionally known method, and then iminodiacetic acid ethyl ester 22.0? was reacted in 100 ml of water at 90° C. for 1/S hour. After thoroughly washing the product with water, it was then washed with O5N sodium hydroxide solution.
The reaction was carried out at 0°C for 5 hours. The exchange capacity of the resulting composite was ygmeq/f.

Claims (2)

[Claims] (1) A composite comprising an ion exchange resin or a chelate resin contained in the pores of porous glass particles. (2) The composite according to claim 1, wherein a monomer is contained in the pores of the porous glass particles, and then a polymerization reaction is performed to introduce a functional group as necessary. How the body is manufactured.