JPH0662346B2 - Inorganic / organic composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a novel inorganic / organic composite comprising a porous resin and a spatial resin in the pores, a method for producing the same, and the composite. It relates to a method for separating metallic elements using a body.

[Prior Art] Functional resins such as ion exchange resins and chelate resins, and polymer gels such as cross-linked dextran and cross-linked polystyrene can be used for their partition chromatography and adsorption chromatography. It is widely used in separation processes such as ion exchange chromatography and gel chromatography, and adsorption processes. However, these resins and polymer gels are not satisfactory in terms of physical strength and dimensional stability of particles. For example, when used as a packing material for liquid chromatography or the like, there are problems of physical strength and dimensional change of particles, and the conditions for use are limited. That is, the height of the packed tower, the particle packing density, the developing pressure, the specifications of the pump and the centrifuge, etc. are severely restricted. These restrictions have a detrimental effect on the separation time, the amount of separation, and the separation efficiency in the separation operation, and also have an adverse effect on the adsorption operation time, the number of times, the required resin amount, etc. in the adsorption operation. Exert. In addition, the packing density of the filler changes during expansion due to dimensional changes due to the swelling of the resin in the developing solution, and when several kinds of developing solution are passed through, the packing density is always unstable. Occurs, and stable development is not possible.

These drawbacks are major problems in using the resin in various operations such as separation and adsorption. That is, because the usage conditions are restricted, the high performance such as the separation performance and the adsorption performance originally possessed by those resins cannot be sufficiently exhibited.

On the other hand, as already known, by utilizing the physical strength of the inorganic material, the outer surface of the non-porous or porous inorganic material or the surface of the inorganic material inside the pores is coated with a resin, or the inorganic material is reacted by the reaction. Composites have been provided which bind a stationary phase to the surface and solve the above mentioned problems. As such an example, Japanese Patent Publication No. 52-48,518 is published for the former, and Japanese Patent Publication No. 52-146,298 is published for the latter.

However, in these composites, the volume of the coated resin and the bonded stationary phase is significantly smaller than the volume of the composite, and the adsorption amount per unit weight of the composite,
Performance such as separation amount is extremely low. As in the case of the porous resin alone, in order to obtain a large adsorption amount and separation amount, a very large amount of these composites is required, and therefore, they have been put to practical use only for special applications in which a small amount is sufficient.

The amount of resin can be increased in the composite obtained by coating the surface of the porous inorganic material with a resin. However, when it is used for applications such as adsorption and separation, the diffusion of the involved chemical species into the resin is extremely slow, the place where the performance is exhibited is limited to the resin surface, and it takes a long time before the performance is exhibited. There is a drawback that.

Further, in the coating type composite, if the pores of the inorganic porous material are blocked with the resin, the function is remarkably deteriorated.

As described above, the conventional composites do not satisfy the goal of having high physical strength while utilizing the original resin performance.

[Problems to be Solved by the Invention] The present invention has been made in view of the above points, and not only satisfies the physical strength but also has an effect such as separation and adsorption that the resin has. The object is to provide a novel inorganic / organic composite that does not deteriorate.

[Means and Actions for Solving Problems] In order to overcome the above-mentioned drawbacks of the prior art, the present invention is to partially or completely occupy the pores of the inorganic porous material, and The present invention provides a composite having an internal space and having a surface area larger than that of the inorganic porous material alone.

Such a composite of the present invention is essentially different from the conventional coating composite in two points. That is, a small amount of resin is present in the form of being in direct contact with the inner and outer surfaces of the inorganic porous body, and in contrast to the coating type complex having no space inside the resin, the complex of the present invention is It is characterized in that a large amount of resin occupies the pores of the porous body and that the resin has a space.

Therefore, the composite of the present invention has a large amount of resin weight that can be contained per unit weight of the inorganic porous body, and the presence of the resin internal space allows the resin performance to be exerted not only on the resin surface but also in the entire resin interior. Has spread to.

Further, in the complex of the present invention, "space" referred to here
Is different from the porosity of mere ion exchange resin,
It has a special function and is essential. The reason is as follows. That is, in a simple ion exchange resin, when it is brought into contact with an ion-containing liquid, the penetration of the liquid into the pores in the resin causes the resin to swell, and the swelling secures a passage through which the liquid reaches the exchange group on the resin. . On the other hand, when the ion-exchange resin is contained in a highly rigid inorganic porous material like the composite of the present invention, the swelling of the resin is hindered by the wall of the inorganic material even when contacted with the ion-containing liquid. I will end up.

Therefore, the complex of the present invention can utilize its function only when a sufficient amount and size of the space are present in advance. Thus, this space provides a passageway for liquids to enter the complex and also provides a field for reaction.

The surface area of the composite of the present invention as described above is quantitatively defined because it is larger than the surface area of the inorganic porous material alone.

This is enough to create a large surface area in the resin,
This is because there is space.

The properties of the composite are not limited to the particle size, surface area, and pore characteristics (pore volume, average pore diameter, pore diameter distribution) of the inorganic porous material, and their properties, as well as the pore characteristics of the spatial resin and the type of resin. Etc. Further, the quantitative occupancy ratio of the spatial resin to the composite is also important.

For the analysis of the pore characteristics of the inorganic porous material, the composite is analyzed, for example, at 700 to 800
The amount of pores and the average pore diameter can be obtained by measuring the collected inorganic porous material with a mercury porosimeter after the resin is burned off by heating to a high temperature of ° C.

The surface area of the inorganic porous material is calculated by using the obtained amount of pores and the value of the average pore diameter and assuming a cylindrical model of pores as described later.

On the other hand, the pore characteristics of the composite can be determined by measuring the composite with a mercury porosimeter without pretreatment. The surface area is calculated in the same manner as in the case of the inorganic material. The pore characteristics of the spatial resin are determined by the method described below from the pore characteristics, weight and specific gravity of the composite and the inorganic porous material.

Porous ceramic particles containing a metal oxide are used as the inorganic porous particles in the present invention. Specific examples include porous particles of silica, alumina, silica-alumina, titania, and zirconia.

Further, porous glass, chamotte, porous ceramics and the like can also be used.

Among them, the silica porous particles are most preferable because they can be easily made into substantially spherical particles, the particle size distribution thereof is narrow, and the acid resistance of silica is high. That is, in terms of manufacturing method,
Silica particles can be easily molded into a spherical shape or a shape close to that of water glass or silica sol by an apparatus such as a spray dryer. Further, the pore formation in the particles, water glass or silica sol of the undiluted solution, or silica gel after molding, include an inorganic salt such as sodium chloride, the inorganic salt-containing silica gel as an intermediate product, for example 50
This can be achieved by heating to 0 ° C. or higher and baking and then desalting. At this time, a silica porous body having a desired pore size or a narrow pore size distribution can be obtained by selecting the conditions. Moreover, the silica porous particles are almost pure (at least
It is composed of silica with a purity of 98%) and can exhibit its essential chemical resistance. Particularly, in the case of an aqueous solution, it exhibits excellent chemical resistance to neutral or acidic liquids.

The shape of the inorganic porous material particles is not limited,
The shape is preferably spherical or close thereto. The average particle size varies depending on the use, but is preferably 10 μm to 1 mm. A more preferable range is 20 to 500 μm. The porosity can be in a wide range of 0.01 ≦ α ≦ 0.99 when the porosity (expressed by α) is the ratio of the volume of the pores to the total volume of the particle, but is preferably 0.3 ≦ α ≦ 0.9. is there.
A more preferable range is 0.40 ≦ α ≦ 0.85.

The porosity α is a non-invasive substance, and a volume measurement method using the invasive substance, that is, a mercury porosimeter (unpressurized mercury-pressurized mercury), or a pycnometer using mercury-helium, a bulk specific gravity, It can be easily calculated by obtaining the true specific gravity. That is, Is.

When α <0.3, the amount of the spatial resin included in the pores of the inorganic porous material particles is small, and the performances such as adsorption performance and decomposition performance of the included resin are relatively reduced. Further, when α> 0.9, the strength of the particles decreases, which may be difficult to handle.

The pore diameter of the inorganic porous material particles can be measured by a mercury porosimetry method using a porosimeter, and refers to a pore diameter of 3.7 nm or more which is a measurement limit here. The average pore size of the particles is not particularly limited, but is preferably 20 nm to 2000 nm. A more preferred range is 50 nm to 1500 nm. The surface area of the inorganic porous material particles is obtained from the values of the amount of pores and the average pore diameter according to the cylindrical model of pores as described above. That is, for cylindrical holes, (S: surface area, V: amount of pores, D: average diameter of pores, l: length of cylindrical pores) Is induced. If a unit weight of particles is taken, S represents a specific surface area. Preferably 0.1~1000m ² / g as specific surface area, more preferably 0.4~800m ² / g.

The surface area of the composite is also measured in exactly the same manner as described above.

It is essential that the surface area of the composite is larger than the surface area of the inorganic porous material that constitutes the composite.

That is, W _c s _c > W _i s _i where W and s represent respective weights (g) and specific surface areas (m ² / g), and subscripts c and i refer to respective composites and inorganic porous bodies.

A complex that does not satisfy such a condition of the surface area amount means that the amount of resin is too small or the surface area of the space in the resin is too small, which is different from the complex of the present invention.

The average pore diameter of the spatial resin depends on the application and the average pore diameter of the inorganic porous material, but in proportion to the average pore diameter of the inorganic porous material.
It is 0.9 or less, preferably 0.5 or less.

The absolute value is preferably 800 nm or less, more preferably 100 nm or less. Further, the lower limit of the average pore size is not particularly limited within the range of measurement limit. However, the average pore size is preferably 10 nm or more in order to obtain a sufficient reaction rate in ion exchange and chemical conversion of the resin.

The average pore diameter of the spatial resin is determined from the mercury porosimeter measurement of the composite and the porosity determined as described below.

That is, a pore size-pore amount curve (also referred to as a pore size distribution chart) of the composite is obtained by measuring the porosimeter of the composite. This pore size distribution chart has one mountain shape when the spatial resin completely fills the pores of the inorganic porous body. On the other hand, when it is not completely filled, usually two mountain-shaped pore diameter distribution maps are shown. In the former case, the average pore size of the composite is directly given as the average pore size of the spatial resin. On the other hand, in the latter case, one of the two peaks is assigned to the resin space and the other is assigned to the remaining pores of the inorganic porous material. If the porosity is obtained in advance, which of the two peaks gives the pore amount that matches the porosity, that is, which peak gives the resin space is determined. Therefore, the average pore diameter of the resin space can be obtained from the peaks.

The porosity (γ) of the spatial resin is shown as the ratio of the space to the total volume of the spatial resin including the space. This porosity is shown as the porosity (α) of the inorganic porous material and the ratio of the apparent volume. This porosity is the porosity (α) of the inorganic porous material, the apparent volume, that is, the volume as particles.
(Vt) and a true specific gravity of the chromatic space resin ([rho _R), is determined according to the following equation from the weight (W _R).

This porosity is established when the porous resin completely fills the pores of the inorganic porous material. If this is not the case, the apparent volume coverage (f) of the resin with respect to the inorganic porous material is used, and it can be obtained from the equation in which Vt · α in the above equation is replaced by Vt · α · f. f is the hydrofluoric acid from the complex (relative to silica)
It is the ratio of the apparent volume (Vs) of the resin obtained after removing the inorganic material with hot sulfuric acid (relative to alumina) to the apparent volume Vt of the inorganic porous material.

The range of the void ratio γ of the spatial resin is 0.05 ≦ γ ≦ 0.95, preferably 0.20 ≦ γ ≦ 0.95, and more preferably 0.40 ≦ γ ≦ 0.95.

The inclusion amount (β) of the spatial resin is determined by the weight Wi of the inorganic porous material and the weight Wc of the composite. Given in.

A preferable range is 0.05 ≤ β ≤ 0.95, and more preferably 0.20 ≤ β ≤ 0.80 If β is smaller than the above range, the amount of resin contained is small, and the treatment of the substance to be treated in applications such as separation and adsorption of the complex is performed. The ability is significantly reduced. If β is too large,
The resin cannot be stored in the pores of the inorganic porous material particles,
There will be too little space in the resin,
Inadequate in terms of physical strength or separation / adsorption efficiency.

The method for measuring β is performed as follows. That is, two composite samples with the same weight are prepared, and one of them is treated by high temperature heating as described above to obtain an inorganic porous body, so that the weight is
Wi, and Wc is calculated from the other composite sample. In this way, β can be calculated.

In the composite, the resin may be present on the outer surface. The outer surface referred to here means the surface excluding the inner surface of the pores of the porous particles from the entire surface including the inner surfaces of the pores of the inorganic porous particles to be used. That is, the outer surface is a surface in contact with the outer space of the porous particles.

In the composite of the present invention, a value obtained by dividing the volume of the resin existing on the outer surface by the total volume including the original amount of the inorganic porous material, that is, the outer surface resin ratio, is represented by μ.

Preferably μ ≦ 0.1, more preferably μ ≦ 0.01.

When the amount of resin on the external surface increases, when the composite is used as a packing material for liquid chromatography, the resin on the external surface of the composite peels off due to friction between the composites, and the peeled resin clogs the filter etc. and causes pressure loss. In some cases, the separation performance and the adsorption performance of the filler may become unstable due to the increase of the temperature and mixing of the peeled resin with the filler. Further, when the composite is transported in the form of a slurry using a pump, a stirrer, or when mixing and stirring are performed, the external surface resin may be peeled off.

The external surface resin ratio μ is easily obtained from the difference between the apparent volume of the inorganic porous material particles used in the composite including the pores and the apparent volume of the composite particles.

That is, if the apparent volume of the inorganic porous material particles is x and the apparent volume of the composite particles is y, Is. The apparent volume of the inorganic porous material particles and the apparent volume of the composite particles can be measured by measuring with a mercury porosimeter in a non-pressurized state.

The resin referred to in the present invention is not limited to its chemical properties such as composition and molecular structure, and can be selected from various polymer compounds. For example, natural high molecular compounds such as polysaccharides (dextran, agarose, cellulose, etc.), polypeptides, and proteins can be used.

Examples of synthetic polymers include polystyrene, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polybutadiene, polyethylene terephthalate, 6,6-nylon, polyphenylene sulfide, poly (2,6-xylenol), polyether sulfone, polyethylene,
Polypropylene, polyacrylic acid, polyvinyl acetic acid, copolymer of acrylonitrile and styrene, copolymer of styrene and butadiene, copolymer of styrene and vinylbenzyl chloride, copolymer of acrylic acid and styrene, phenol resin, melamine resin, Examples thereof include epoxy resin and alkyd resin.

Further, not limited to the above-mentioned natural polymer or synthetic polymer,
A wide range of synthetic polymers using various monomers as described below are also preferable. Furthermore, a resin obtained by introducing a functional group as described below into the above-described polymer compound is also included in the scope of the present invention.

The included resin may be a linear-polymer or a cross-linked polymer. A crosslinked polymer is particularly preferable.
The reason is that by fixing the geometrical structure of the resin in the crosslinked polymer, it is possible to permanently retain the resin internal space and prevent the resin from escaping to the outside of the particles.

The cross-linking degree of such a cross-linking resin can take a wide range of values depending on the purpose, but the cross-linking agent unit is usually 90% or less by weight of the resin. It is preferably 0.1% to 80%, more preferably 1% to 50%.

It is often preferable that a functional group is present in the resin included in the composite in order to exert a specific function.

The functional group of the resin in the present invention refers to a functional functional group and a reactive group that is an atom or atomic group having a high chemical reactivity. Specific examples of the functionality of the functional group include, for example, ion exchange ability, chelate forming ability, redox ability, catalyst coordination ability, and the like, and the functional group having these functions includes a sulfonic acid group, There are carboxylic acid groups, phosphonic acid groups, primary to tertiary amines, hydroquinone groups, thiol groups and the like. Examples of the reactive group having high chemical reactivity include isocyanate group, diazonium group, chloromethyl group, aldehyde group, epoxy group, halogen group, carboxyl group and amino group.

For example, it is a complex including an ion exchange resin, a chelate resin containing a chelate ligand, a redox resin having hydroquinone, thiol and the like.

The ion exchange resin included in the composite may be a resin having an exchange group for cations or anions, or a resin having the ability to exchange both cations and anions.

Preferred cation exchange resins include those having a sulfonic acid group, a carboxyl group or a phosphoric acid group. Specifically, vinylbenzene sulfonic acid as a polymerized unit,
Examples include three-dimensional polymers having vinyl benzoic acid, acrylic acid, methacrylic acid, and the like. The anion exchange resin has a primary, secondary, or tertiary amino group, for example, -CH ₂ -NR ₁ R ₂ (R ₁ and R ₂ have 1 carbon atoms in the side chain of polystyrene or polyacrylamide). To a straight-chain alkyl group of 5 to 5), or -CH ₂ -N ⁺ R
₁ linear alkyl group _{R 2 R 3 X- (R 1} , R 2, R 3 from 1 carbons Any 5; X ^- is ^{Cl -, Br -, I -} , ClO 4 -, 1/2 SO ₄ ^2- or 1/3 PO
Some of them have a quaternary ammonium group represented by ₄ ^3- ) and some have a basic nitrogen-containing heterocycle represented by vinyl pyridine and vinyl imidazole as a functional group. The heterocycle is not limited to pyridine and imidazole, pyrazole, thiazole,
Triazole, carbazole, benzimidazole, indole and the like are also preferable.

In addition, resins that introduce various ion exchange groups into polysaccharides,
It is an example of a resin included in the composite of the present invention. For example, a cellulose containing a diethylamino group can be mentioned.

Examples of chelating groups preferred for the complex of the present invention include alcohol, phenol, carboxylic acid, ketone,
It is an atomic group composed of a plurality of functional groups such as aldehyde, amide, ester, oxide, primary amine, secondary amine, tertiary amine, thioether, thiophenol, arylphosphine and arylarsene. The functional groups constituting the chelate-forming group may be the same or different. More specifically,
Polymers having a hydroxyl group represented by polyvinyl alcohol, vinyl methyl ketone, polymers having a ketonic carbonyl group represented by methacryloylacetone, polymers having a hydroxy group and a carboxyl group represented by salicylic acid formaldehyde resin, polyacrylic acid, Polymethacrylic acid, polyitaconic acid, thiophene maleate, or a polymer having a carboxyl group represented by an iminodiacetic acid group, a polymer having an amino group, an oxime group, an azo group, a thioalcohol, a polymer having a thiophenol group, a thioketone, There are dithiolate, thioamide, polymers having thiourea groups, polymers having first, second, and third alkylarylphosphine groups, polymers having catechol groups, and the like.
More preferably, it contains a structure of polyaminocarboxylic acid, various oximes and oxines, and catechol in its molecule.

Examples of the polyaminocarboxylic acid are generally compounds represented by the following structural formula (I) and compounds in which any hydrogen atom in the formula (I) is substituted with a hydrocarbon group.

These polyaminocarboxylic acids include iminodiacetic acid, N
-Methyliminodiacetic acid, N-cyclohexyliminodiacetic acid, N-phenyliminodiacetic acid having a substituent such as N-phenyliminodiacetic acid, and polyaminocarboxylic acid having one nitrogen atom such as nitrilotriacetic acid, ethylenediamine-N, N, N ′, N ′
-4 acetic acid, 1,2-propylenediamine-N, N, N ', N'-4
Acetic acid, 1-phenylethylenediamine-N, N, N ', N'-4
Polyaminocarboxylic acid having two nitrogen atoms such as acetic acid, cyclohexylamine-N, N, N ', N'-4acetic acid, diethylenetriamine-N, N, N ", N" -5-acetic acid, diethylenetriamine represented by the following formula- N, N, N ′, N ″, N ″ -4 acetic acid Also, diethylenetriamine-N, N, represented by the following formula
N ', N "-4 acetic acid Etc. and substituted products thereof with various substituents introduced, and nitrogen atom 3 of triethylenetetramine-N, N, N ′, N ″, N, N-6acetic acid, or polyethyleneimine with acetic acid group introduced
There are polyaminocarboxylic acid groups having more than one group. Furthermore, N-hydroxyethylenediamine-N, N, N ', N'-3acetic acid, 1,3-diaminopropane-N, N, N', N'-4acetic acid, 1,4
Polyaminocarboxylic acids such as -diaminobutane-N, N, N ', N'-4acetic acid can also be used in the present invention. Of these, particularly preferred polyaminocarboxylic acid groups are iminodiacetic acid, ethylenediaminetetraacetic acid, and diethylenetriamine-N, N, N ", N".
-4 acetic acid, diethylenetriamine-N, N ', N ", N" -4 acetic acid and substituted products thereof.

These chelate compounds are contained in the chelate resin as radical groups obtained by removing one or more hydrogen atoms at arbitrary positions from the compound.

There is no particular limitation on the resin of the complex for introducing the chelate group. Examples thereof include those having a structure in which various substituents are introduced into a copolymer of a complex including a styrene-divinylbenzene copolymer.

The most preferable typical structure of the chelate resin used in the present invention is one containing the repeating units represented by the structural formulas (II) to (III). An example of the method for producing these chelate resin complexes is a method by the reaction of chloromethylstyrene-divinylbenzene copolymer complex with iminodiacetic acid ethyl ester (structural formula (II)), (1,2-dibromoethyl). ) Method by reaction of iminodiacetic acid on styrene-divinylbenzene copolymer composite (structural formula (III)), reaction of diethylenetriamine on chloromethylstyrene-divinylbenzene copolymer composite, and subsequent reaction with chloroacetic acid (Structural Formula (II)), and the para- (di (aminoethyl) aminoethyl) styrene-divinylbenzene copolymer complex by the reaction of chloroacetic acid (Structural Formula (II)).

Structural formula (II) Structural formula (III) An example of the oxime is obtained by reacting a polymer having a carbonyl group with hydroxylamine. This reaction may be carried out in the pores of the inorganic porous material.

Further, as a resin containing oxine, a resin obtained by an addition condensation reaction of oxine and formalin is typical. It can also be obtained by reacting a polymer having a formyl group or a hydroxyl group with oxine. This reaction can also be carried out in the pores of the inorganic porous material.

Those having a catechol group are represented by the following structural formula (IV). Of the four bonds in formula (IV), Up to three may be hydrogen atoms or other substituents, but at least one forms the main chain of the polymer,
Alternatively, it is attached to the main chain.

There are no particular restrictions on the type and bonding mode of the polymer, but if some preferred specific examples are given, firstly, the following formula (V)
It has a polymerized unit represented by.

R ₉ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.

Such a polymer can be produced by a polyaddition condensation reaction between catechols and formaldehyde. In addition,
If desired, phenol, resorcinol, hydroxybenzenes such as p-chlorophenol, aniline,
Aminobenzenes such as p-phenylenediamine and o-phenylenediamine, phenylales such as anisole and diphenyl ether can be used with catechols.

The second one has a polymerized unit represented by the following formula (VI).

R ₉ and R ₁₀ are each hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ₁₁ is hydrogen, a hydroxyl group, and 1 to 8 carbon atoms
Represents a hydrocarbon group and a catechol group.

A method for producing such a resin can be obtained, for example, by adding or dehydrating condensation of catechols to a three-dimensional cross-linked copolymer of a styrene derivative having a formyl group or a hydroxyl group.

In the case of having a polymerized unit represented by (V), a polymerized unit having three bonds as represented by (VII) is formed by reacting one molecule of catechol with two or more molecules of formaldehyde, and The coalesced is three-dimensionally crosslinked.

The polymer having the polymerized units represented by (VI) is three-dimensionally crosslinked by the crosslinking agent which is a bifunctional or polyfunctional monomer. Examples of those cross-linking agents having a vinyl group are divinylbenzene, divinyltoluene, divinylxylene, divinylethylenebenzene, trivinylbenzene, divinyldiphenyl, divinyldiphenylmethane, divinyldibenzyl, divinylphenyl ether,
Divinyl diphenyl sulfide, divinyl diphenyl amine, divinyl sulfone, divinyl ketone, divinyl pyridine, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl oxalate,
Diallyl adipate, diallyl sebacate, diallylamine, triallylamine, N, N'-ethylenediacrylamide, N, N'-methylenediacrylamide, N, N'-methylenedimethacrylamide, ethylene glycol dimethacrylate, ethylene glycol diacrylate , 1,3
-Butylene glycol diacrylate, triallyl isocyanurate, triallyl citrate, triallyl trimellitate, triallyl cyanurate and the like.

The method for producing the composite of the present invention comprises a homogeneous mixture of a polymerizable monomer or polymerizable oligomer, a cross-linking agent and a diluent in the pores of the inorganic porous material, or a polymer compound, a cross-linking agent and a diluent. After the addition of a homogeneous mixture consisting of and, the resin is formed by heating or electromagnetic radiation, and then the diluent is removed from the inside of the formed resin. The present production method is started by introducing the mixed liquid into the pores by contacting the inorganic porous material with the above-mentioned homogeneous mixed liquid. As the polymerizable monomer used in the homogeneous mixed liquid, those having a vinyl group are preferable.

Specific examples of such a polymerizable monomer are as follows.

Styrene, methylstyrene, diphenylethylene, ethylstyrene, dimethylstyrene, vinylnaphthalene, vinylphenanthrene, vinylmesitylene, 3,4,6-trimethylstyrene, 1-vinyl-2-ethylacetylene,
Hydrocarbon compounds such as butadiene and isoprene; chlorostyrene, methoxystyrene, bromstyrene, cyanostyrene, formylstyrene, fluorostyrene, dichlorostyrene, N, N-dimethylaminostyrene, nitrostyrene, chloromethylstyrene, trifluoromethyl Styrene derivatives such as styrene and aminostyrene; vinyl sulfide derivatives such as methyl vinyl sulfide and phenyl vinyl sulfide; acrylonitrile derivatives such as acrylonitrile, methacrylonitrile, α-acetoxyacrylonitrile; acrylic acid, metacrylic acid; methyl acrylate, lauryl acrylate , Chlormethyl acrylate,
Acrylic esters such as ethyl acetoxyacrylate;
Methacrylic acid esters such as cyclohexyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate; diethyl maleate, diethyl fumarate; vinyl ketone chloride such as methyl vinyl ketone, ethyl isopropenyl ketone Vinylidene compounds such as vinylidene, vinylidene bromide, vinylidene cyanide, etc .;
Acrylamide derivatives such as acrylamide, methacrylamide, N-butoxymethyl acrylamide, N-phenyl acrylamide, diacetone acrylamide, N, N-dimethylaminoethyl acrylamide; fatty acid vinyl derivatives such as vinyl acetate, vinyl butyrate, vinyl caprate, etc .;
Thio fatty acid derivatives such as phenyl thiomethacrylate, methyl thioacrylate, vinyl thioacetate; and 2-vinylpyrrole, N-vinylpyrrole, N-vinylpyrrolidone, N-vinylsuccinimide, N-vinylphthalimide, N-vinylcarbazole, N-vinyl indole,
2-vinylimidazole, 5-vinylimidazole, 1
-Vinyl-2-methylimidazole, 1-vinyl-2-
Hydroxymethylimidazole, 5-vinylpyrazole, 3-methyl-5-vinylpyrazole, 3-vinylpyrazoline, vinylbenzoxazole, 3-phenyl-
5-vinyl-2-isoxazoline, N-vinyloxazolidone, 2-vinylthiazole, 2-vinyl-4-methyl-thiazole, 2-vinyl-4-phenylthiazole, 2-vinyl-4,5-dimethylthiazole, 2 -Vinylbenzothiazole, 1-vinyltetrazole, 2-vinyltetrazole, 2-vinylpyridine, 4-vinylpyridine, 2-N, N-dimethylamino-4-vinylpyridine,
2-vinyl-4,6-dimethyltriazine, 2-vinyl-
Nitrogen-containing heterocyclic compounds such as 4,6-diphenyltriazine, isopropenyltriazine and vinylquinoline; heterocyclic vinyl compounds such as vinylfuran, 2-vinylbenzofuran and vinylthiophene. It goes without saying that two or more kinds of these polymerizable monomers can be used at the same time.

Instead of a monomer, an oligomer or a polymer compound may be used as a raw material for producing a composite. Here, the oligomer refers to a compound having a number average molecular weight of 10,000 or less, and the polymer compound refers to a compound having a number average molecular weight of 10,000 or more, both of which are composed of monomer units.

Any of the monomer, oligomer, or polymer compound is dissolved or dispersed in a diluent to form a uniform mixed solution, but the monomer is more advantageous because it easily forms a uniform mixed solution. .

Various compounds can be used as the cross-linking agent, and specific examples thereof are as follows.

Divinylbenzene, dividyltoluene, divinylxylene, divinylnaphthalene, divinylethylbenzene, divinylphenanthrene, trivinylbenzene, divinyldiphenyl, divinyldiphenylmethane, divinyldibenzyl, divinylphenylether, divinyldiphenylsulfide, divinyldiphenylamine, divinylsulfone, divinylketone, Divinylfura, divinylpyridine, divinylquinoline, di (vinylpyridinoethyl)
Ethylenediamine, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallyl tartrate, diallylamine, triallylamine, triallyl phosphate, triallyl tricarballylate, Triallyl aconitate, triallyl citrate, N, N'-ethylene diacrylamide, N, N'-methylene diacrylamide, N, N'-methylene dimethacrylamide, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol di Methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, 1,3-butylene glycol diacrylate, 1,6-
Hexanediol diacrylate, trimethylpropane triacrylate, pentaerythritol tetraacrylate, triallyl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, diarylmelamine, formaldehyde, acetaldehyde,
1,3-divinylpropane, polyalcohol, α, ω-dihalogenoalkane, polyamine, polyepoxide, diisocyanate, sulfur, alkyl peroxide, polyaziridine, dicarboxylic acid and the like.

Any diluent may be used as long as it can form a uniform mixed liquid with the monomer, oligomer or polymer compound and the crosslinking agent. Generally, when the monomer, oligomer or polymer compound is lipophilic, an organic liquid is preferable, and conversely, when these raw materials are hydrophilic, water or an aqueous solution is preferable. The diluents may be used not only alone but also as a mixture. However, the type of the preferred diluent depends on various other conditions for producing the composite, such as the configuration of the reaction system, temperature and pressure, and the spatial characteristics to be imparted to the resin in the produced composite. To be done. For example, the method of forming the resin by polymerization or crosslinking reaction after containing the homogeneous mixed solution in the pores of the inorganic porous material is a method of directly heating or applying electromagnetic radiation, or a method of containing the homogeneous mixed solution in the dispersion liquid. The method is roughly divided into a method in which the inorganic porous material is dispersed and then heated or an electromagnetic radiation is applied. In the latter method, compatibility between the dispersion and the diluent must be considered. That is, when the dispersion is hydrophilic, a lipophilic organic liquid is preferable as the diluent, while when the dispersion is lipophilic,
Hydrophilic liquids are preferred.

The spatial properties of the spatial resin included in the composite depend on the type and amount of diluent. For example, the diameter of the space depends on the affinity of the diluent for the crosslinked resin. That is, the smaller the affinity, the larger the diameter of the space.

Further, the space amount of the resin changes according to the amount of the diluent, and the larger the amount of the diluent, the larger the space amount. As described below,
There is a case where the resin in the complex once formed is subjected to a post-reaction to introduce a functional group. For example, a sulfonic acid group can be introduced into a complex containing a copolymer of styrene and divinylbenzene by a post reaction to obtain a complex having an ion exchange ability. In such a case, not only the amount of space sufficient for the post-reaction to proceed, but also the amount of space sufficient for the new complex obtained after the reaction to exert its function (for example, ion exchange capacity) can be secured. It is preferable to preset the amount of the diluent.

Specific examples of the diluent include water and chlorobenzene, toluene, xylene, octane, decane, butanol, octanol, diethyl phthalate, dioctyl phthalate, ethyl benzoate, methyl isobutyl ketone, ethyl acetate,
Organic liquids such as diethyl oxalate, ethyl carbonate, nitroethane, cyclohexanone and the like can be mentioned.

A homogeneous mixture of a monomer, an oligomer or a polymeric compound, a cross-linking agent and a diluent is brought into contact with the inorganic porous particles for introduction into the pores. As the introduction method,
Various methods can be used. For example, a method of bringing the particles and the homogeneous mixed solution into contact with each other under atmospheric pressure, preferably while stirring at a low speed, a method of bringing the particles and the homogeneous mixed solution into contact with each other under vacuum, and treating the particles with a silyl reaction etc. and then uniformly mixing them. Examples include a method of contacting with a liquid.

When treating the particle surface by silylation, it is necessary to select the silylating agent in consideration of the properties of the homogeneous mixed solution to be introduced. For example, when the mixed solution is fat-soluble, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrichlorosilane and the like are preferable. If the mixture is water-soluble, γ-glycidoxypropyltrimethoxysilane, γ- (2-aminoethyl)
Aminopropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane and the like are preferable.

The silylation method is not particularly limited, but the silylating agent may be brought into contact as a liquid or in a gas state. When the silylating agent is a solid, it is preferably dissolved or dispersed in an organic liquid or water before use.

The amount of silylating agent used is 0.1, based on the weight of the particles.
-20%, preferably 0.5-10%. The silylation reaction is carried out at a temperature of 10 to 300 ° C., preferably 15 to 200 ° C. for 0.5 to 48 hours, preferably 1 to 24 hours.

Preferred silylating agents include, for example, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexamethyldisilazane, N-trimethylsilylacetamide, γ-mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gammamethacryloxypropyltrimethoxysilane, gammamethacryloxypropyltris (beta-methoxyethoxy)
Silane, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, gamma-aminopropyltriethoxysilane, N-beta ( Aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-chloropropyltrimethoxysilane, silyl peroxide and the like.

In the inorganic porous material particles containing the homogeneous mixed solution thus obtained, the mixed solution adheres to the outer surface to some extent and remains. The smaller this residual liquid, the better. In order to do so, for example, the amount of the mixed liquid to be brought into contact with the particles may be equal to or less than the amount of pores inside the particles in advance, and then the contact may be made under low speed stirring. In this way, the liquid mixture remaining on the outer surface of the particles can be made extremely small.

On the other hand, a method may be adopted in which the mixed liquid remaining on the outer surface of the particles is reduced as much as possible before the polymerization reaction or the crosslinking reaction is started. The first of these methods is illegal. That is, by passing the particles containing the mixed solution, the mixed solution remaining on the outer surface of the particles can be reduced. In this case, it is preferable to use an excessive method such as overpressurization, centrifugal overpass or the like because the overtime is shortened.

The second method is to include the mixed solution in the particles and then forcibly disperse the particles in a liquid that neither reacts with nor dissolves in the mixed solution while forcibly stirring. In this case, it is preferable to use a dispersion liquid containing a dispersant. The dispersion liquid has the effect of stably holding the mixed liquid, which is shaken off from the outer surface of the particles by forced agitation, in the dispersion liquid and preventing re-adhesion of the particles.

For example, when water is used as a dispersion liquid, as a dispersant, arabic gum, rosin, pectin, alginate, tragacanth gum, agar, methylcellulose, starch, carboxymethylcellulose, karaya gum, viscous substances such as gelatin, sodium polyacrylate, polyvinyl alcohol. , Polyvinylpyrrolidone, carbopol, synthetic polymers such as diacetoolein, magnesium,
Inorganic substances such as aluminum silicate, velmagel, magnesium silicate hydrated, titanium oxide, zinc oxide, calcium carbonate, talc, barium sulfate, calcium phosphate, aluminum hydroxide, and anhydrous silicic acid anhydride are preferable, and if necessary, salts such as salt. It is also preferable to add a pH adjuster, a surfactant and the like.

Regarding the forced stirring for removing the mixed liquid from the outer surface of the inorganic porous particles, the lower limit of the stirring speed is the minimum speed required to shake off the mixed liquid from the outer surface, and the upper limit is not destroyed by the inorganic porous particles. It is the maximum speed. A preferable stirring speed is 1500 rpm or more. When the stirring is carried out at a suitable stirring speed, preferably at a speed close to the upper limit, the peeled mixed solution is reduced to particles having a diameter smaller than that of the inorganic porous material particles. The smaller the particle size of the peeled mixed solution, the more easily it can be removed by treatment such as excessive treatment. Further, by appropriately setting the kind and amount of the dispersant added to the dispersion liquid, the particle size of the dispersed mixed liquid can be made smaller than the diameter of the inorganic porous material particles. The excess of the dispersed uniform mixed solution is removed by excess or the like, but the removing operation may be performed immediately after the forced stirring, or may be performed after heating or electromagnetic radiation as described below.

The third method of removing the uniform mixed liquid adhering to the outer surface of the inorganic porous material particles is to place the inorganic porous material particles on a glass filter or the like, and then wash the particles with an inert liquid insoluble in the mixed liquid. Is. The type of inert liquid used will depend on the type of homogeneous mixture. For example, water is used as the inert liquid when the mixture is lipophilic.

In the production method of the present invention, the inorganic porous material particles including the homogeneous mixture are heated or subjected to electromagnetic radiation. When the homogeneous mixed solution comprises a monomer or an oligomer, a crosslinking agent and a diluent, heating or electromagnetic radiation causes a polymerization or a crosslinking reaction. The polymerization reaction when a monomer containing a vinyl group is used proceeds according to the mechanism of radical polymerization or ionic polymerization depending on the chemicals added and the constitution of the reaction system. Although any polymerization can be used, radical polymerization is preferred because the characteristics of the resin produced can be easily controlled. When radical polymerization is carried out, it is preferable to use a polymerization initiator in order to accelerate the reaction to lower the polymerization temperature and shorten the reaction time.

Suitable initiators for radical polymerization include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylmaleronitrile) and the like. There are azonitriles, ditertiary butyl peroxide, digmyl peroxide, peroxides such as methyl ethyl ketone peroxide, and hydroperoxides such as cumene hydroperoxide and tertiary hydroperoxide.

The amount of initiator required depends on the reaction temperature and the amount and type of monomer, but the usual range is 0.01 to 12 relative to the weight of monomer.
%.

The heating applied to cause the polymerization and the crosslinking reaction in the homogeneous mixed liquid is performed at a temperature of 40 to 150 ° C. and a range of 2 to 100 hours.
At this time, the particles containing the mixed liquid may be heated as they are, or may be heated in a state of being dispersed in the dispersion liquid. When the particles are heated as they are, it is preferable to perform low-speed stirring in order to prevent the particles from adhering to each other due to the resin generated on the outer surface. When heating in a state of being dispersed in the dispersion liquid, it is necessary to select a diluent that does not elute the mixed liquid contained in the pores of the particles into the dispersion liquid. Further, it is also preferable to use particles which have been surface-treated with a silylating agent as described above.

The inorganic-organic composite produced under the above conditions contains a diluent inside. Therefore, by dipping the complexes in a solvent that dissolves them, leaving them for a while and then separating them, or by putting the complexes into a column and allowing the washing solvent to flow down, the diluent can be effectively removed from the inside of the complex. Can be removed. For example, when an organic liquid is used as the diluent, a water-soluble one such as methanol or acetone is used as the washing solvent, and the washing solvent can be easily removed by further washing with water.

The thus-obtained composite is used as it is as a filler for ion-exchange resin chromatography, an adsorbent, or the like, or is subjected to a post-reaction, and a functional group is added to the resin in the composite. Will be introduced.

Speaking of an ion exchange resin as an example of the latter, if a monomer such as vinyl pyridine or vinyl imidazole that already has the property of ion exchange is used, it is possible to obtain a complex containing the ion exchange resin without the need for post reaction. Become. on the other hand,
Using a monomer such as styrene, polymerization is carried out in the pores of the inorganic porous material to obtain a composite having no ion exchange ability, and then as a post-reaction, chlorosulfonic acid, sulfuric acid, and sulfuric anhydride are added. By carrying out a reaction with either, a complex containing a cation exchange resin is obtained.

Further, instead of the above-mentioned sulfonating agent, chloromethylation is carried out with chloromethyl ether or the like, and a secondary or tertiary amine is reacted to obtain a complex containing an anion exchange resin.

The complex containing the chelate resin can be obtained by previously polymerizing or copolymerizing a monomer having a chelate-forming group in the pores of the inorganic porous body. That is, a chelate resin can be obtained by containing a monomer having a chelate-forming group and performing addition polymerization, polycondensation, polyaddition, addition condensation, elimination polymerization or the like. For example, multiple phenolic
A chelate resin complex can be obtained by addition-condensing an aromatic compound having a chelate-forming group composed of OH or an amino group with formaldehyde. On the other hand, it is also possible to introduce a chelate-forming group into a resin such as polystyrene or polyvinyl chloride, a three-dimensional resin such as a phenol resin or a melamine resin, or a polysaccharide such as cellulose by post-reaction. Specific examples of preferable chelating groups are as described above.

Since the space in the resin is present in the composite of the present invention, it is possible to easily introduce a functional group represented by, for example, an ion exchange group or a chelate forming group.

Since the composite in the present invention has a unique structure in which the resin having a space is included in the pores of the inorganic porous material particles, it has a high adsorption performance and ion exchange performance comparable to those of the conventional porous functional resin. At the same time, it has high physical strength and dimensional stability. Therefore, the complex of the present invention is a stationary phase for gas chromatography and liquid chromatography, hydrogen chloride, sulfurous acid gas, mercaptans, acidic gases such as fatty acids, or ammonia,
Wide range of adsorbents for basic gases such as amines and other malodorous substances, heavy metal ions in water, surfactants, adsorbents for organic compounds, coloring substances, polymeric substances, ion exchange resins, insolubilizing enzyme carriers, etc. It is used in the field. For example, according to liquid chromatography using a complex as a packing material, it is possible to effectively separate and purify various metals and isotopes represented by rare earth metals, thorium, hafnium, rhenium, uranium and gold. You can

When the inorganic-organic composite in the present invention is used for adsorption using a column or liquid chromatography, the developing flow rate is preferably 0.1 cc / cm ² · min, and the pressure loss in the high developing flow range is also taken into consideration. If so, the deployment flow rate is 1-500 /
cm ² · min is preferable, and 10 to 500 / cm ² · min is more preferable.

[Examples] The present invention will be described below with reference to Examples.

Reference example: (Manufacturing method of porous silica gel) Snowtex-30 (manufactured by Nissan Chemical Industries, silica sol) 12
0 g, 50 g potassium chloride and calcium chloride dihydrate 32
g and a solution prepared by dissolving 2 ml of concentrated hydrochloric acid in 120 ml of distilled water were added. Granulate the prepared colloidal solution with a spray dryer,
106 g of spherical particles having an average particle size of 100 μm were obtained. 750 this
Calcination was performed for 2 hours.

This product is treated with 10 times volume of 1N aqueous hydrochloric acid at 80 ° C for 1 hour,
Washed thoroughly with water. Furthermore, by separately drying, 33.5 g of porous silica gel particles was obtained. Average pore size 120n
m, and the pore volume was 0.85 ml / g. The porosity was 0.65. The specific surface area was 28.3 m ² / g. The elemental analysis results of the obtained porous silica gel are SiO ₂ : 98.7%, KCl:
It was 0.6% and CaCl ₂ : 0.7%.

Example 1 10 g of the porous silica particles obtained in the reference example were placed in a 300 ml beaker, and then 6.4 g of 4-vinylpyridine and 3.6 g of divinylbenzene (purity 56%; containing vinylethylbenzene 44% as an impurity, divinylbenzene). Is a mixture of meta: para: 7: 3), dioctyl phthalate 18g,
A solution in which 0.1 g of azobisisobutyronitrile was mixed and dissolved was added, and the mixture was stirred at room temperature for 1 hour. Then pass this on a glass filter. The obtained monomer-containing particles were put into a flask (100 ml) under a nitrogen atmosphere and equipped with a stirrer. In that state, polymerization was carried out at 90 ° C. for 10 hours in an oil bath. After cooling, the produced composite particles were taken out and thoroughly washed with methanol to remove the organic liquid.
As a result of measuring the pore size distribution by a mercury porosimeter using a sufficiently dried sample, the average pore size was 44 nm. Porosity
The specific surface area was 0.43 ml / g, the specific surface area was 39.1 m ² / g, and the porosity was 0.64. The apparent specific gravity of the produced composite was 0.98, and the exchange capacity was 1.40 meq / g. This complex had μ = 0.06.

Example 2 Average pore size 400 nm, pore volume 1.05 ml / g, specific surface area 10.5 m ²
/ G, 10 g of spherical silica porous particles having an average particle diameter of 80 μm were placed in a 300 ml flask equipped with a magnetic stirrer, and the pressure was reduced by a vacuum pump. Next, in this flask, 6.1 g of styrene as a monomer, 2.2 g of divinylbenzene (the same as used in Example 1); 0.1 g of benzoyl peroxide.
In the test (1), 12.5 g of ethylbenzene was introduced, and in the test (2), a homogeneous mixed liquid was introduced, and the mixture was slowly stirred under reduced pressure at 10 ° C for 30 minutes. Next, this was filtered on a glass filter and further washed with water to collect the monomer-containing particles.
Stir these particles slowly in a nitrogen atmosphere
Polymerization was carried out at 85 ° C for 20 hours.

The reaction product was thoroughly washed with acetone to remove the added organic liquid. Porosity was evaluated by a porosimeter using each sufficiently dried sample (Table 1). Further, 5 g of the sufficiently dried complex was put into a 100 ml reaction flask, then 30 ml of dichloroethane was added, and the mixture was kept at 40 ° C. for 2 hours.
After stirring for 20 hours, 20 g of chlorosulfonic acid was added dropwise. After continuing the reaction at 40 ° C. for 2 hours as it is, the reaction mixture was put into ice water, and after separation, dichloroethane was removed by steam distillation. The obtained reaction product was sufficiently dried, the porosity was evaluated by a porosimeter, and the exchange capacity (cation) was measured (Table-1). The specific surface area of the composite of the case (1) was 86.2 m ² / g, the porosity was 0.61, and μ was 0.
It was 05.

Example 3 280 g of spherical silica porous particles having an average pore diameter of 800 nm, an average particle diameter of 60 μm and a pore volume of 0.85 ml / g specific surface area of 4.3 m ² / g were placed in a container equipped with a stirrer. After degassing this container with a vacuum pump, nitrogen was introduced to return to atmospheric pressure. Next, in this container, 65 g of chloromethylstyrene (purity 92%, m / p = 6/4),
A liquid in which 7 g of m-divinylbenzene, 0.7 g of azobisisobutyronitrile, 70 g of xylene and 70 g of n-butanol were mixed and dissolved was introduced, and the mixture was slowly stirred at room temperature under a nitrogen atmosphere for 2 hours. The mixture was heated as it was and reacted at 90 ° C. for 16 hours. The reaction product was thoroughly washed with methanol. Acetone 1.5 and dimethylamine 50g were added to this, and it was made to react at 50 degreeC for 5 hours. The product was thoroughly washed with water, 1N hydrochloric acid, and acetone in this order.

The exchange capacity of the produced complex is 1.03 meq / g, and μ is 0.01
Met.

The pore size distribution of the sufficiently dried composite was measured with a porosimeter. As a result, the average pore size was 55n.
m, the porosity was 0.46 ml / g, the specific surface area was 33.5 m ² / g, and the void ratio was 0.73.

The composite obtained here and commercially available Dowex MSA-1
Each 10 cmφ cylindrical column was packed to a height of 10 cm, and the upper part
5 kg / cm²When you see the change in height by applying pressure,
Dowex MSA-1 is observed to decrease in height to 8.9 cm
However, no decrease in the height of this complex was observed.

Example 4 30 g of the complex containing the crosslinked polymer of chloromethylstyrene obtained according to Example 3 was reacted with 22.0 g of ethyl iminodiacetic acid ester in 100 ml of n-butanol at 100 ° C. for 20 hours. The product was thoroughly washed with methanol to remove residual iminodiacetic acid ethyl ester. The reaction was continued with 1N hydrochloric acid at 80 ° C. for 5 hours. After passing through the mixture, the particles were washed with water and 1N hydrochloric acid. The weight of the particles obtained after drying was 11.1 g. The anion exchange capacity of this complex was 0.92 meq / g. The average pore size is 36 nm, the pore volume is 0.32 meq / g, and the specific surface area is 35.6 m.
It was ² / g. In addition, μ was 0.01.

Example 5 Porous glass having an average pore diameter of 80 nm, the longest diameter of particles in the range of 200 to 300 µ, a pore volume of 10 ml / g, and a specific surface area of 50 m ² / g.
After thoroughly washing 15 g of concentrated nitric acid, it was put into 20 g of dichloromethylsilane and reacted for 15 hours at room temperature under a nitrogen atmosphere. After separating the product, thoroughly wash with anhydrous methanol,
It was dried under reduced pressure.

On the other hand, 20.0 g of styrene, 5.0 g of divinylbenzene (the same as that used in Example 1), 0.22 g of azobisisobutyronitrile, and 30 g of ethylbenzene were mixed and dissolved to prepare a liquid, which was mixed with the above-mentioned porous glass. Later on the glass filter. This was dispersed in 500 ml of water, forcibly stirred at 1000 rpm for 1 minute, and then reacted at 90 ° C. for 15 hours. The reaction product is thoroughly washed with anhydrous methanol,
It was dried under reduced pressure. It was placed in a 3-neck flask of 10 g and 100 ml, 30 ml of dichloroethane was added, and 20 g of chlorosulfonic acid was added dropwise while stirring at 40 ° C. After continuing the reaction for 2 hours at the same temperature, the reaction mixture was poured into water, separated and washed with water to obtain an inorganic / organic composite. The cation exchange capacity of the complex was 1.47 meq / g.
The average pore diameter was 18 nm and the pore volume was 0.40 ml / g. The specific surface area was 88.9 m ² / g.

Moreover, when the external surface resin ratio μ was measured, μ was 0.05.

Example 6 Instead of porous glass, average pore diameter 100 nm, pore volume 1.0 ml /
A cation-exchange resin-containing composite was obtained by the same procedure except that 15 g of porous silica particles (specific surface area: 16.0 m ² / g) having an average particle size of 250 μm were used.
The exchange capacity was 1.62 meq / g and μ = 0.01.

When the composite was observed with a scanning electron microscope, almost no resin adhered to the outer surface was observed. The average pore size was 18 nm and the pore volume was 0.41 ml / g. The specific surface area was 91.1 m ² / g.

Example 7 100 g of spherical silica porous particles having an average particle size of 50 μm, an average pore size of 650 nm, and a pore volume of 1.3 ml / g were equipped with an electromagnetic stirrer 300.
Placed in a ml container. After this container was removed, a nitrogen atmosphere was created. In this container, formyl styrene 33 g, divinylbenzene (purity 95%) 3.0 g, benzoyl peroxide 0.5 g, 1,1,2-trichloroethane 70 g and tetralin
After adding 45 g of the mixed solution, the mixture was continuously stirred in a nitrogen atmosphere for 30 minutes to introduce the mixed solution into the particles. The mixture was heated as it was, and polymerization was carried out at 85 ° C. for 12 hours with slow stirring. Add 500 ml of methanol to it,
After stirring for a further 30 minutes, the mixture was passed. The weight of the composite obtained after drying was 131 g. When the pore size distribution of the composite was measured with a porosimeter, the average pore size was 42 nm and the pore volume was
The specific surface area was 0.68 ml / g, the specific surface area was 64.8 m ² , and the porosity was 0.75. In addition, when the infrared spectrum (KBr tablet) was measured, strong absorption of -CHO was found at 1720 cm ^-1 .

Example 8 20 g of the complex obtained in Example 7 was added to a mixed solution of 100 g of dimethylformamide and 4 g of orthophenylenediamine placed in a 500 ml flask. While introducing sulfurous acid gas into this mixture, the mixture was heated to 80 ° C. and stirred in this state for 5 hours. The total amount of sulfur dioxide introduced was 2.5 g. After adding 300 ml of methanol, the mixture was passed through. further,
The solvent was removed by washing with water. The collected particles were dipped in 1N hydrochloric acid, filtered again, and further washed with methanol. The amount of composite particles after drying was 22.3 g. The anion exchange capacity is
It was 1.47 meq / g. Average pore size is 41 nm, pore volume is 0.59 ml
/ G. The specific surface area was 56.7 m ² / g.

Example 9 100 g of a porous decagel having a particle size of 100 to 500 μ (average pore size 150 nm, porosity 70%, specific surface area 28.3 m ² / g) was placed in a flask. Separately, 150 g of 20% sulfuric acid and catechol 1
80 g, formalin (37% formaldehyde aqueous solution) 130 g
An aqueous solution in which was dissolved was prepared. This aqueous sulfuric acid solution was poured into a flask to impregnate porous silica gel. Then 10
It was degassed for 30 seconds under a reduced pressure of 0 mmHg or less. The wet silica gel obtained by passing this mixture was put into a three-necked three-neck flask prepared separately. Furthermore, 1,2,3-trichloropropane 1.5 was poured. After attaching a reflux condenser, thermometer, and stirrer to the three-necked flask, force stirring at 3000 rpm
After 1 minute, the temperature was further raised to 90 ° C. with stirring at 100 rpm, and heating was continued for 15 hours. After cooling, the product was collected by filtration and washed with sufficient water until the washed water was neutral. After drying at 80 ℃ for 12 hours, 276g of inorganic
An organic complex was obtained.

A difference spectrum was obtained from the infrared spectra (KBr tablets) of this complex and the porous silica gel used for its synthesis, which was 1140 to 1290 cm ^-1 (strong &broad; CO stretching) 1360 cm ^-1.
(OH bending) was found, and it was found that catechol was contained in the complex.

The average pore size was 53 nm and the pore volume was 0.48 ml / g. The specific surface area was 36.2 m ² / g.

Example 10 6 g of commercially available agarose and 94 g of water were heated to 60 ° C. and stirred to form a uniform solution. After adding 20 g of 1,3-dibromopropane to this solution, the average pore diameter was 150 nm, the porosity was 70%,
After adding and mixing 60 g of silica gel having a particle size of 100 to 500 µ, heating was performed. This silica gel was placed in a flask containing 500 ml of 1,2-dichloroethane, and after heating,
Forced stirring was performed at 400 rpm for 30 seconds, and heating was continued for another 4 hours. After the reaction, after thoroughly washing the particles with acetone,
It was neutralized with 0.01N caustic soda. Then, particles were added to a flask containing a solution of 60 g of diethylaminoethyl chloride hydrochloride dissolved in 300 ml of water, and the mixture was heated and stirred at 70 ° C. for 10 hours. After washing with sufficient water, the mixture was filtered to obtain 68.3 g of an inorganic / organic composite. Average pore size is 10 nm, pore volume is 0.82 ml / g,
The specific surface area was 328 m ² / g.

Example 11 A column with a jacket made of Pyrex glass having an inner diameter of 20 mm and a length of 1000 mm was prepared, and the inorganic / organic composite containing an anion exchange resin was filled to a height of 900 mm.

The inorganic / organic composite used in this example was synthesized as follows.

Average pore size 600nm, pore volume 1.05ml / g, specific surface area 7.0m ²
/ G, 1 kg of porous silica particles with an average particle size of 500 μm
Was placed in a flask equipped with a magnetic stirrer, and the pressure was reduced by a vacuum pump.

Next, 515 g of chloromethylstyrene as a monomer, 85 g of divinylbenzene and 1.2 g of methyl benzoate were placed in this flask.
A homogeneous mixed liquid in which 5 g and 1.0 kg of normal heptane were dissolved was introduced, and the mixture was stirred under reduced pressure at 10 ° C. for 30 minutes. Then, this was passed over a glass filter, dispersed in a mixed solution of water 10 and 500 g of calcium phosphate, and forcibly stirred at 2000 rpm for 2 minutes, and then polymerized at 85 ° C. for 20 hours in a nitrogen atmosphere.

The reaction product was thoroughly washed with water and then thoroughly washed with methanol to remove the added organic liquid. Put the well dried complex into a reaction flask of 500g, 10 and then add dichloroethane 3 and mix at 40 ° C for 2
After stirring for 20 hours, a 20% trimethylamine ethanol solution was added dropwise and amination was carried out at 40 ° C. for 5 hours to obtain an inorganic / organic composite.

The obtained particles were thoroughly dried and evaluated for porosity by a porosimeter. The average pore diameter was 43 nm and the pore volume was 0.64 ml.
/ G. The specific surface area was 59.5 m ² / g. The exchange capacity was 1.02 meq / g.

A sufficient amount of 1N hydrochloric acid was supplied to the column packed with the composite particles to make the packing a chlorion type. A solution 100 containing chromic acid of 100 ppm and adjusted to pH = 5 with hydrochloric acid was fed to the column by a pump.

The solution flowing out from the lower part of the column was divided into 500 ml fractions and collected, and the concentration of chromate ion was measured by a fluorescent X-ray analyzer. As a result, it was confirmed that the chromate ion concentration in the effluent was 0.5 ppm or less, and the removal rate was 99.5% or more.

Next, the filler was regenerated by thoroughly flowing an aqueous solution containing 10% NaCl and 1% NaHCO ₃ . The operation of adsorption and regeneration was repeated 10 times, and the pressure loss accompanying the feeding of the solution was measured. The change with time was extremely small. Further, the change in the height of the filler with time was extremely small, and stable operation could be performed (Table-2).

After repeating adsorption and regeneration 10 times, the filler mainly in the lower part of the packed column was extracted and the state of destruction was observed with a microscope. As a result, less than 0.3% of the total was confirmed to be destroyed.

Comparative Example 1 For comparison, the same experiment was conducted using the anion exchange resin synthesized as follows. That is, attach a stirrer and a thermometer to a 20-necked four-necked flask, and add water 20 k
g, sodium polyacrylate 120g and salt 24 as suspending agent
0g, chloromethylstyrene 1000g, divinylbenzene 1
65 g, methyl benzoate 2.43 kg, and normal heptane 1.
94 kg was added and stirred well to disperse the oil droplets. This was polymerized at 85 ° C. for 20 hours, cooled after polymerization, transferred to a washing tower with a filter, and thoroughly washed with water and 30 methanol.

After washing, as in the case of the composite particles of Example 11, amination was carried out in dichloroethane with an ethanol solution of 20% trimethylamine at 40 ° C. for 5 hours. The obtained resin was filled and dried, and the porosity was evaluated by a porosimeter. As a result, the average pore diameter was 58 nm and the pore volume was 0.72 ml / g. The exchange capacity was 3.74 meq / g.

Example except that this resin was used in place of the composite particles
When an adsorption test similar to that of 11 was performed, the chromate ion concentration in the effluent was 0.5 ppm or less, and the removal rate was 99.5%.
That was all.

Further, the operation of adsorption and regeneration was repeated 10 times as in Example 11, and the pressure loss accompanying the field of the solution was measured. The height of the filler also changed, making safe driving difficult.

After 10 times of adsorption and regeneration operations, the filler mainly in the lower part of the packed column was extracted, and the state of destruction was measured by a microscope. As a result, 4% of the whole was confirmed to be destroyed.

[Advantages of the Invention] In the inorganic-organic composite according to the present invention, as described above, since the spatial porous resin is included in the pores of the inorganic porous material particles, the inorganic porous material is physically dispersed by the inorganic porous material. Strength is expressed,
It has high strength as a whole, retains a certain shape without being destroyed even if it is used for a long time, and when used for chromatography etc., stable development is possible without pressure pressure loss increasing over time. The development flow rate can be increased to significantly increase the liquid treatment amount per unit time, there is no expansion or contraction of the adsorbent during regeneration, adsorption, or development, the interface is not disturbed, and separation per unit volume of the adsorbent Noh has a great industrial significance.

Claims (16)

[Claims] 1. An inorganic / organic composite comprising a porous resin having a spatial resin in the pores thereof, wherein the surface area of the composite is larger than the surface area of the inorganic porous material alone. 2. The average particle diameter of the inorganic porous material particles is from 10 μm to 1
The inorganic-organic composite according to claim 1, which is in the range of mm. 3. The inorganic-organic composite according to claim 1 or 2, wherein the porosity of the inorganic porous material particles is in the range of 0.3 to 0.9. 4. The average pore diameter of the inorganic porous particles is from 20 nm to 2000.
The inorganic-organic composite according to any one of claims 1 to 3, which is in the range of nm. 5. The inorganic-organic composite according to any one of claims 1 to 4, wherein the void-containing resin has a porosity of 0.40 to 0.95. 6. The inorganic-organic composite according to any one of claims 1 to 5, wherein the average pore size of the spatial resin is 90% or less of the average pore size of the inorganic porous material. 7. The average pore diameter of the spatial resin is 10 nm to 800 nm.
The inorganic-organic composite according to any one of claims 1 to 6, which is within the range. 8. The inorganic-organic composite according to any one of claims 1 to 7, wherein the inorganic porous material particles are silica porous material particles. 9. The inorganic / organic composite according to any one of claims 1 to 8, wherein the spatial resin is an ion exchange resin or a chelate resin. 10. A homogeneous mixed liquid comprising a polymerizable monomer or a polymerizable oligomer and a crosslinking agent and a diluent, or a homogeneous mixture comprising a polymer compound, a crosslinking agent and a diluent, in the pores of the inorganic porous particles. After the liquid is contained, the resin is generated by heating or electromagnetic radiation, and then the diluent is removed from the inside of the generated resin, whereby the inorganic porous particle contains a spatial resin in the pores. A method for producing an inorganic / organic composite, which is an organic composite having a surface area larger than that of the inorganic porous material alone. 11. The method for producing an inorganic / organic composite according to claim 10, wherein the homogeneous mixed solution further contains a radical initiator. 12. The method for producing an inorganic-organic composite according to claim 10, wherein the inorganic porous material particles are silica porous material particles. 13. The method according to claim 12, wherein the porous silica particles are produced from a solution containing silica sol. 14. The inorganic-organic composite according to claim 13, wherein the porous silica particles are formed by discharging a solution of silica sol as liquid particles into the air and drying the solution. Manufacturing method. 15. A homogeneous mixed solution containing a polymerizable monomer or a polymerizable oligomer and a cross-linking agent and a diluent, or a uniform mixture comprising a polymer compound, a cross-linking agent and a diluent in the pores of the inorganic porous material particles. After containing the liquid, heat or electromagnetic radiation is used to generate a resin, then the diluent is removed from the inside of the generated resin, and then the resin is reacted with a functional group-introducing agent to introduce a functional group, thereby forming an inorganic substance. An inorganic-organic composite comprising a porous particle-containing spatial resin, wherein the surface area of the composite is larger than that of the inorganic porous material alone. Method for producing composite. 16. When separating a solution containing a metal element by bringing the solution into contact with a solid adsorbent to adsorb the metal element on the solid adsorbent, the solid adsorbent is introduced into the pores of the inorganic porous material particles. A metal characterized by using an inorganic / organic composite comprising a spatial resin composed of an ion exchange resin or a chelate resin, the composite surface area being larger than the surface area of the inorganic porous body alone. How to separate elements.