JPS61181960A - Composite structure - Google Patents

Abstract

PURPOSE:To enable the manufacture of a composite structure useful as separa tion agent, filler or the like, by supporting polysaccharide on a whole porous carrier with the specified particle diameter and average bore diameter. CONSTITUTION:Polysaccharide is supported on a whole porous carrier with the particle diameter 1mum-1cm, the average bore diameter 10Angstrom -100mum and the ratio of bore diameter and particle size of below 1/10. The polysaccharide shall be cellose, amyloe and the like and the number-average degree of the polysaccharides is set at 5 or more, preferably 10 or more while the holding amount at 1-100 wt.% with respect to the carrier. Chemical and physical methods are available for holding the polysaccharide on the carrier. One of the physical methods is that a saccharide is disolved into a solvent to be mixed with the carrier thoroughly and the solvent is fractioned away in an air current under a reduced pressure and a raised heat. The chemical supporting method is a reactive functional group is added to the carrier and polysaccharide to bond the saccharide to the carrier. This facilitates the manufacture of a composite structure while a wide range of use is expected as it s hard in the nature.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a composite structure, and more particularly to a composite structure in which a polysaccharide is supported on a carrier and is useful as a separating agent, a filler, etc.

[Conventional technology]

Conventional granular optically active polysaccharides such as cellulose have good biocompatibility and are composed of a skeleton with asymmetric hydrocarbons, so they are expected to be used in a wide range of fields such as cosmetics and separation agents. ing.

[Problem that the invention seeks to solve]

However, it is difficult to synthesize granules consisting only of polysaccharide, and even if it were possible, it would require a relatively long process. Furthermore, polysaccharide granules are relatively sensitive to pressure and are generally soft, which has significantly narrowed the range of their use.

The present inventors have arrived at the present invention as a result of intensive research in order to overcome the above-mentioned drawbacks and make it possible to utilize polysaccharide in granular form without impairing the useful properties of polysaccharide.

[Means for solving problems]

That is, the present invention has a particle size of 1ttm to 1c11, an average pore size of 10 to 1OOIBn, and a ratio of pore size to particle size of l/
The present invention provides a composite structure characterized in that a polysaccharide is supported on a carrier having a total porosity of 10 or less.

The composite structure of the present invention consists of a polysaccharide and a carrier, and first, the carrier used in the present invention will be explained.

The carrier may be a porous organic carrier or a porous inorganic carrier, preferably a porous inorganic carrier.

Suitable porous organic carriers include polymeric substances such as polystyrene, polyacrylamide, and polyacrylate. Suitable porous inorganic carriers include silica, alumina, magnesia, titanium oxide, glass,
Examples include synthetic or natural substances such as silicates and kaolin, which may be surface-treated to improve their affinity with polysaccharides. Examples of surface treatment methods include silanization using an organic silane compound and surface treatment using plasma polymerization.

The particle size of the carrier is 1 IBn~fell, preferably l
-~1000-, more preferably II! In~3
It is 0〇-. The average pore size is from 10 to 100, preferably from 50 to 50,000. Further, the ratio of pore size to particle size is 1/10 or less.

Next, the polysaccharide used in the present invention will be explained.

The polysaccharide in the present invention may be any optically active polysaccharide, regardless of whether it is a synthetic polysaccharide, a natural polysaccharide, or a modified natural polysaccharide, but preferably one with a highly regular bonding pattern. Examples include β-1,4-glucan (cellulose), α-1゜4-glucan (amylose, amylopectin), α-1,6-glucan (dextran), β-
1゜6-glucan (pusullan), β-1,3-glucan (e.g. curdlan, schizophyllan, etc.), α-1,3
-glucan, β-1,2-glucan (CrownGal
1, β-1,4-galactan, β-1,4-mannan, α-1,6-mannan, β-1,2-fructan (inulin), β-2,6-fructan (levan) ,
β-1,4-xylan, β-1,3-xylan, β-1
, 4-chitosan, β-1,4-N-acetylchitosan (
chitin), pullulan, agarose, alginic acid, etc., and more preferably cellulose, amylose, β-1,4-chitosan, chitin, β-1,4-mannan, β- from which highly purified polysaccharides can be easily obtained. 1,4-xylan,
These include inulin and curdlan.

The number average degree of polymerization (-average number of pyranose or furanose rings contained in the molecule) of these polysaccharides is 5 or more, preferably 10 or more, and although there is no upper limit, it is preferably 500 or less for ease of handling. preferable.

In order to produce the composite structure of the present invention, the polysaccharide is supported on the carrier, and the amount of polysaccharide retained is 1 to 100% by weight, preferably 5 to 50% by weight, based on the carrier.

The method for retaining the polysaccharide on the carrier may be either a chemical method or a physical method.

As a physical method, polysaccharide is dissolved in a soluble solvent,
A method of mixing well with a carrier and distilling off the solvent by air flow under reduced pressure or heating, or dissolving the polysaccharide in a soluble solvent, mixing well with the carrier, and then stirring and dispersing it in a liquid that is incompatible with the solvent. There is also a method of diffusing the solvent. Furthermore, if there is no suitable solvent for dissolving and supporting the polysaccharide, the hydroxyl groups of the polysaccharide may be protected and supported, and then the protecting groups may be removed.

For example, cellulose and trityl chloride are reacted in the presence of a base to obtain 6-o-) lytyl cellulose. This is dissolved in chloroform and coated on silane-treated silica gel, and then the trityl group is removed with an acid such as hydrochloric acid to obtain a filler made of cellulose-coated silica gel.

Next, as a chemical loading method, loading can be carried out by attaching a reactive functional group to the carrier or attaching a reactive functional group to the polysaccharide and chemically bonding the carrier and the polysaccharide.

Additionally, the carrier and polysaccharide can be chemically bonded by first physically coating the carrier with the polysaccharide and then reacting the reactive functional groups. For example, a composite structure in which silica gel and polysaccharide are chemically bonded by physically coating polysaccharide on aminopropylisilane-treated silica gel and then reacting it with a polyfunctional isocyanate derivative in a dry inert solvent. is obtained.

〔Effect of the invention〕

The composite structure in which the polysaccharide of the present invention is supported on a carrier is easy to manufacture, unlike conventional polysaccharide granules, and is hard, so it is expected to have a wide range of uses. For example, cosmetic powders, separating agents, fillers, sustained release carriers, etc.

〔Example〕

Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Cellulose 1.51 parts, LiCl 2.27 parts, N, N-
Mix 23 parts of dimethylacetamide, keep at 80°C for 10 hours, add 10 parts of pyridine, and 21.2 parts of trityl chloride.
1 part was added and reacted for 48 hours. This was precipitated into methanol, washed and dried in vacuo. Yield: 4.17 parts.

The obtained 6-o-)ditylcellulose 0. Five parts of the solution was dissolved in 10 parts of chloroform and supported on 3.00 parts of 3-aminopropyltriethoxysilane-treated silica gel in two portions.

tritylcellulose The elemental analysis values were as follows.

Cχ Hχ Nχ 15,40 1.23 0.09 30 parts of methanol and 0.3 part of concentrated hydrochloric acid were added to this silica gel, and the mixture was allowed to stand at room temperature. After 25 hours, it was collected using a No. 4 glass filter and washed with methanol.

When the solvent of this filtrate was distilled off, 0.545 parts of yellowish brown crystals were obtained. It was identified as triphenyl carbinol from the IR spectrum.

Transfer the silica gel collected with a glass filter to an eggplant flask, and add methanol-triethylamine (30m:0
．． 3 rnl) was added and the hydrochloride was removed.

The mixture is collected again using a No. 4 glass filter, washed with methanol, and then dried to obtain a filler in which cellulose is supported on silica gel.

The elemental analysis values of the filler after removing the trityl group were as follows.

Cχ H! N! 3,61 0.60 Application Example 1 The packing material prepared by supporting cellulose on the silica gel obtained in Example 1 was packed into a 25×0.46 (id) cm column with methanol. Using hexane-2-propertool as a solvent, flow rate 0.5 m7/minT:Co(acac)
When s was poured, the (-) body flowed out first and the (+) body flowed out later. However, the measurement wavelength of the optical rotation is 365nn+.

Example 2 The filler obtained in Example 1 is placed in an eggplant flask, dried, and replaced with nitrogen. Dry toluene and 0.062 parts of tolylene-2,4-diisocyanate are mixed together under a nitrogen stream, and this is added to the filler. Since the IR spectrum of the silica gel at this stage shows absorption of 1NCO, pyridine 2n7 was added and heated at 60 to 70°C. Then, in the IR spectrum of the silica gel, the absorption of one NGO disappears and the absorption of -N II C- appears, indicating that the silica gel and cellulose are chemically bonded.

Example 3 1.6 g of cellulose tris acetate was added to 1 part of methylene chloride.
After adding the solution dissolved in 0 ml to silica gel having a pore size of 1,000 and a particle size of 0-1 which had been surface-treated with diphenyldimethoxysilane, methylene chloride was distilled off to form a film on the surface. To this was further added a solution of 2d of bubble water hydrazine in 20% of isopropyl alcohol, and the mixture was heated to 60℃ for 7 hours.
The mixture was allowed to react for several hours and deacetylation was performed.

Application Example 2 The cellulose-coated silica gel packing material obtained in Example 3 was packed into a cylindrical stainless steel column with an inner diameter of 0.46 cm and a length of 25 ω. The number of theoretical plates for benzene and acetone in this packed column is 900 plates for benzene when 99.5% ethanol is flowed as a solvent at 0.2 m/min.
It was 1296 steps of acetone.

Example 4 2.0 g of cellulose acetate with a degree of substitution of 2.5 was dissolved in anhydrous pyridine and treated with trinotoxyglycidoxypropylsilane. Pore size: 1000, particle size: 10I! After adding In to 3.5 g of silica gel and reacting at room temperature for 4 days, the solvent was replaced with isopropyl alcohol, hydrazine hydrate 2+n7 was added, and the mixture was reacted at 60° C. for 9 hours to perform deacetylation.

Application Example 3 The silica gel packing material chemically bonded with cellulose obtained in Example 4 was packed into a cylindrical stainless steel column with an inner diameter of 0.46 cm and a length of 25 aa. The theoretical plate number of this packed column for benzene and acetone is 99.5 as a solvent.
When % ethanol was flowed at 0.2ff+7/minute, the flow rate was 2162 stages of benzene and 2824 stages of acetone. 9 of the solvent
When using 9.6% methanol, 2256 stages of benzene,
It was 2947 steps of acetone.

Comparative Example 1 Spherical cellulose gel with inner diameter of 0.46c+n and length of 25
The number of theoretical plates for benzene and acetone of the adsorbent for separation packed in a stainless steel cylindrical column of cm is when 0.2 m7/min of 99.5% ethanol is flowed as the solvent.
Benzene had 123 stages and acetone had 144 stages. Moreover, the peak wavenumber changed over time. However, the number of theoretical plates is given by the following formula.

When the solvent was allowed to flow for about 1 hour under the above conditions, a gap with a length of 2 cm was created at the column inlet.

Claims (1)

[Claims] Particle size is 1 μm ~ 1 cm, average pore size is 10 Å ~ 100 μ
A composite structure characterized in that a polysaccharide is supported on a fully porous carrier having a diameter of m and a ratio of pore size to particle size of 1/10 or less.