JP3183740B2 - Organic polymer-titanium composite oxide composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic polymer-titanium-based composite oxide composite, and more particularly, to an organic polymer-titanium-based composite in which a titanium-based composite oxide is firmly bonded and uniformly distributed. An oxide composite is provided.

[0002]

2. Description of the Related Art Titanium-based composite oxides such as titanium dioxide-silicon dioxide have attracted attention as various adsorbents. In particular, it has a high selective adsorption property to uranyl carbonate present in seawater, and has been spotlighted as an adsorbent for recovering uranium resources from seawater.

[0003] Due to the ease of handling in the adsorption step and the like, when these are used as adsorbents, they have conventionally been often formed into granules having a certain size such as spheres. Furthermore, if it can be formed into a thin film or fibrous shape, it is expected that various advantages such as improvement in adsorption efficiency in continuous processing can be obtained.

However, the titanium-based composite oxide is an inorganic ceramic material, and has an inherent disadvantage of low moldability, so that it has been difficult to mold it into films, fibers, and the like. On the other hand, a method of molding by mixing these composite oxides in an organic polymer is also considered. There are problems such as separation from the organic polymer matrix and the possibility of aggregation of the composite oxide in the organic polymer matrix.

[0005]

In order to solve the above-mentioned problems, there is disclosed a method for obtaining an organic polymer-titanium oxide composite in which a titanium-based composite oxide is firmly bound and uniformly distributed (Japanese Unexamined Patent Publication No. Hei. No. 80404). However, in this method, the ratio of the titanium-based composite oxide to the organic polymer is limited because the alkoxy group of the titanium alkoxide is replaced with a polymerizable complexing agent and the polymerization reaction forms an organic polymer matrix. You. Furthermore, in order to be soluble in the solvent used for the polymerization reaction, it is necessary to control the inorganic skeleton not to be sufficiently developed by hydrolytic polycondensation of the alkoxy group portion. Despite this, the inorganic skeleton was not sufficiently developed, so that it was not possible to exhibit a sufficient adsorptive capacity.

The present invention has been made in view of the above, and provides an organic polymer-titanium-based composite oxide composite in which a titanium-based composite oxide having a well-developed skeleton is firmly bonded and uniformly dispersed. That is the task. If such an organic polymer-titanium-based composite oxide composite is obtained, a thin film, a fiber, or the like having a practically sufficient adsorption ability can be obtained, and can be applied to an adsorbent.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, starting from a titanium alkoxide having an acyloxy group having a polymerizable unsaturated bond as a starting material, the polymerization of the acyloxy group was carried out. Or the copolymerization with a polymerizable monomer, and the titanium alkoxide, an alkoxide of an element that does not form a perovskite crystal structure together with titanium, and co-hydrolytic polycondensation of an alkoxy group of another titanium tetraalkoxide if necessary. By that, the titanium-based composite oxide having a well-developed skeleton is firmly bonded,
The present inventors have found that a uniformly dispersed organic polymer-titanium composite oxide composite can be obtained, and have reached the present invention.

[0008] That is, the present invention is intended to coexist with a titanium alkoxide having an acyloxy group having a polymerizable unsaturated bond and an alkoxide of a metal which does not form a perovskite crystal structure together with titanium. Is an organic polymer-titanium-based composite oxide composite obtained by a co-hydrolytic polycondensation reaction of the alkoxy group of the alkoxide. Hereinafter, the present invention will be described in detail.

<1> Titanium alkoxide having an acyloxy group having a polymerizable unsaturated bond The titanium alkoxide having an acyloxy group having a polymerizable unsaturated bond (hereinafter abbreviated as “titanium alkoxide”) of the present invention is as follows. It is expressed by two equations.

[0010]

## STR2 ## _{Ti (OR) 4-n Q} n where, R represents an alkyl group having 2 to 10 carbon atoms, Q is an acyloxy group having a polymerizable unsaturated bond, n is 1 or 2.

That is, the titanium alkoxide of the present invention comprises two or three alkoxy groups having 2 to 10 carbon atoms ,
It has two or one acyloxy group. Here, R may be the same type of alkyl group or a different type of alkyl group. Similarly, Q may be the same type or different types.

The number of carbon atoms in the alkyl group is preferably 2-10.
Or 2 to 4 . The above titanium alkoxide, the above-mentioned
It can be obtained by reacting a titanium tetraalkoxide having an alkoxy group having a carbon number with a carboxylic anhydride having a polymerizable unsaturated bond. In order to ensure the reaction and suppress side reactions, it is desirable to carry out the reaction under mild conditions, and for this purpose, a carboxylic anhydride is used.

Compounds having different n's depending on the molar ratio of titanium tetraalkoxide and carboxylic anhydride can be obtained. That is, when the molar ratio is 1: 1, n = 1, and when the molar ratio is 1: 2, a compound of n = 2 is obtained. A solution obtained by dissolving titanium tetraalkoxide and carboxylic anhydride in a solvent is mixed. The reaction is carried out for 2 hours or more at the boiling point of the solvent or lower. Further, the above compounds may be simultaneously dissolved and mixed in a solvent. After the reaction, vacuum distillation is performed to obtain the titanium alkoxide of the present invention from the reaction solution. These operations are preferably performed in a dry atmosphere.

As the titanium tetraalkoxide having an alkoxy group , one having an alkoxy group having 2 to 10, preferably 2 to 4 carbon atoms is used. If the number of carbon atoms is larger than this range, the reactivity is reduced, so the above range is preferable. Specific examples include titanium tetraethoxide, titanium tetraisopropoxide, titanium tetraisobutoxide, titanium tetra n-butoxide, and the like.Even if four alkoxy groups in one molecule are of different types, Good. Although those exemplified above are commercially available, others can be obtained by reacting titanium tetrachloride with an alcohol.

Examples of the carboxylic anhydride having a polymerizable unsaturated bond include acrylic anhydride, methacrylic anhydride, crotonic anhydride and the like. Although those having a higher carbon number can be used, the reaction rate becomes slower. When the number of carbon atoms is large, the unsaturated bond is preferably present near the terminal of the carbon chain.

The solvent may be any as long as it can dissolve titanium tetraalkoxide and carboxylic anhydride, such as ethers such as diethyl ether and tetrahydrofuran, hydrocarbons such as n-hexane, benzene and toluene, chloroform, dichloromethane and trichloroethylene. Halogenated hydrocarbons such as acetone, ketones such as methyl ethyl ketone, alcohols such as methanol, ethanol, isopropanol, cellosolves such as ethyl cellosolve and methyl cellosolve, dimethylformamide, dimethyl sulfoxide and the like, and mixtures thereof Is mentioned. Ethers and hydrocarbons are particularly preferred.

Since the solvent reacts with the carboxylic acid anhydride when water is present, it is preferable to use a solvent which has been dehydrated by a conventional method such as a reaction with metallic sodium or magnesium or distillation. Hereinafter, a production example will be described.

(Production Example 1) A production example of a titanium alkoxide having an isobutoxy group as an alkoxy group and an acryloxy group as an acyloxy group having a polymerizable unsaturated bond will be described.

A refluxer which is sufficiently dried and purged with nitrogen,
In a flask equipped with a stirrer, 300 ml of diethyl ether dehydrated and purified by distillation was taken, and 34.0 g (0.1 mol) of titanium tetraisobutoxide was stirred and dissolved therein.

After the atmosphere in the flask was sufficiently replaced with nitrogen, a solution prepared by dissolving 12.6 g (0.1 mol) of acrylic anhydride in 200 ml of the above-mentioned dehydrated and purified diethyl ether was added thereto. The reaction was performed for 4 hours.

After completion of the reaction, purification was performed by vacuum distillation to obtain about 34 g of a colorless and transparent liquid. All operations were performed under a nitrogen stream. It was confirmed that this liquid was the desired alkoxide represented by Chemical Formula ^{1 by 1} H-NMR and ¹³ C-N
Confirmed by MR measurement.

[0022]

Embedded image Ti [OCH ₂ CH (CH ₃ ) ₂ ] ₃ (OCOCH ＝ C
H ₂ )

(Production Example 2) A production example of a titanium alkoxide having an isopropoxy group as an alkoxy group and a methacryloxy group as an acyloxy group having a polymerizable unsaturated bond will be described.

A refluxer, which has been sufficiently dried and purged with nitrogen,
300 ml of benzene dehydrated and purified by distillation was placed in a flask equipped with a stirrer, and 28.4 g (0.1 mol) of titanium tetraisopropoxide was stirred and dissolved therein.

Further, after the inside of the flask was sufficiently purged with nitrogen, a solution obtained by dissolving 15.4 g (0.1 mol) of methacrylic anhydride in 200 ml of the above-mentioned dehydrated and purified benzene was added, and the mixture was refluxed for 3 hours to carry out a reaction. . After completion of the reaction, purification was performed by vacuum distillation to obtain about 31 g of a colorless and transparent liquid.

All operations were performed under a stream of nitrogen. It was confirmed by ¹ H-NMR and ¹³ C-NMR measurements that this liquid was the target alkoxide represented by Chemical Formula 4.

[0027]

Embedded image Ti [OCH (CH ₃ ) ₂ ] ₃ [OCOC (CH
₃ ) = CH ₂ ]

(Production Example 3) A production example of a titanium alkoxide having an n-butoxy group as an alkoxy group and a crotonoxy group as an acyloxy group having a polymerizable unsaturated bond will be described.

A refluxer, which has been sufficiently dried and purged with nitrogen,
In a flask equipped with a stirrer, tetrahydrofuran 200 dehydrated and purified by reflux with metal sodium and distillation.
ml of titanium tetra-n-butoxide 3
4.0 g (0.1 mol) was dissolved by stirring.

After the atmosphere in the flask was sufficiently replaced with nitrogen, a solution obtained by dissolving 30.8 g (0.2 mol) of crotonic anhydride in 200 ml of the above-mentioned dehydrated and purified tetrahydrofuran was added, and the mixture was refluxed for 2 hours with stirring. And reacted.

After completion of the reaction, purification was performed by vacuum distillation to obtain about 36 g of a colorless and transparent liquid. All operations were performed under a nitrogen stream. It was confirmed by ¹ H-NMR and ¹³ C-N that this liquid was the target alkoxide represented by Chemical Formula 5.
Confirmed by MR measurement.

[0032]

Embedded image Ti [O (CH ₂ ) ₃ CH ₃ ] ₂ ( OCOCH ＝ C
HCH ₃ ) ₂

(Production Example 4) A production example of a titanium alkoxide having an n-butoxy group as an alkoxy group and a methacryloxy group as an acyloxy group having a polymerizable unsaturated bond will be described.

A refluxer, which has been sufficiently dried and purged with nitrogen,
300 ml of benzene dehydrated and purified by distillation was placed in a flask equipped with a stirrer, and titanium tetra-n-
34.0 g (0.1 mol) of butoxide was dissolved by stirring.

After the atmosphere in the flask was sufficiently replaced with nitrogen, a solution obtained by dissolving 30.8 g (0.2 mol) of methacrylic anhydride in 200 ml of the dehydrated and purified benzene was added, and the mixture was refluxed for 3 hours while stirring was continued. Go and react. After completion of the reaction, purification was performed by vacuum distillation to obtain about 34 g of a colorless and transparent liquid.

All operations were performed under a nitrogen stream. It was confirmed by ¹ H-NMR and ¹³ C-NMR measurements that this liquid was the desired alkoxide represented by Chemical Formula 6.

[0037]

Embedded image Ti [O (CH ₂ ) ₃ CH ₃ ] ₂ [OCOC (CH
₃ ) = CH ₂ ] ₂

(Production Example 5) A production example of a titanium alkoxide having an ethoxy group as an alkoxy group and an acryloxy group as an acyloxy group having a polymerizable unsaturated bond will be described.

A refluxer, which has been sufficiently dried and purged with nitrogen,
In a flask equipped with a stirrer, diethyl ether 300 dehydrated and purified by reflux with metal sodium and distillation.
of titanium tetraethoxide.
8 g (0.1 mol) was dissolved by stirring.

After the atmosphere in the flask was sufficiently replaced with nitrogen, a solution prepared by dissolving 12.6 g (0.1 mol) of acrylic anhydride in 200 ml of the above-mentioned dehydrated and purified diethyl ether was added thereto. The reaction was refluxed for 3 hours.

After completion of the reaction, purification by vacuum distillation was performed to obtain about 34 g of a colorless and transparent liquid. All operations were performed under a nitrogen stream. It was confirmed by ¹ H-NMR and ¹³ C-N that this liquid was the target alkoxide represented by Chemical Formula 7.
Confirmed by MR determination.

[0042]

[Image Omitted] Ti (OCH ₂ CH ₃ ) ₃ (OCOCH CH ₂ )

<2> Organic polymer-titanium composite oxide
The above titanium alkoxide and an alkoxide of an element which does not have a perovskite crystal structure together with titanium coexist, and a polymerization reaction of an acyloxy group having a polymerizable unsaturated bond in the titanium alkoxide and a co-hydrolysis weight of each alkoxy group. By performing the condensation reaction, a titanium-based composite oxide having a well-developed skeleton is strongly bonded, and
An organic polymer-titanium composite oxide composite uniformly distributed is obtained. In the production process of this composite, the order of the step of polymerizing the acyloxy group and the step of co-hydrolytic polycondensation of the alkoxy group is not particularly limited.

Examples of the alkoxide of an element which does not have a perovskite-type crystal structure together with titanium include alkoxides of silicon, aluminum, magnesium, zinc, zirconium, etc. Specifically, tetramethyl orthosilicate, tetraethyl orthosilicate, aluminum Triethoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum trisec butoxide, magnesium diethoxide, magnesium diisopropoxide, magnesium di n-butoxide, magnesium disec butoxide, zinc dimethoxide, zinc diethoxide, zinc Di-n-propoxide,
Zinc di-n- butoxide, zirconium tetraethoxide, zirconium tetra-n- propoxide, di Rukoniu <br/> arm tetraisopropoxide, zirconium tetra-n- butoxide and the like. These may be used as a mixture.

During the polymerization reaction of an alkoxide of an element that does not form a perovskite crystal structure with titanium (hereinafter referred to as “an alkoxide of another element”) and the alkoxy group of the titanium alkoxide of the present invention, a short-chain alkoxy group and a titanium When a titanium tetraalkoxide consisting of is present, the ratio of the organic polymer matrix to the titanium-based composite oxide and the ratio of titanium to other elements in the titanium-based composite oxide can be adjusted. Specifically, titanium tetraethoxide, titanium tetraisopropoxide,
Titanium tetra n-butoxide, titanium tetraisobutoxide and the like can be mentioned.

Further, during the polymerization reaction of the acyloxy group,
The coexistence of a polymerizable monomer having a polymerizable unsaturated bond copolymerizable with titanium alkoxide can change properties such as hardness and expansion coefficient of the organic polymer matrix. Specifically, crotonic esters such as crotonic acid, acrylic acid, methacrylic acid, methyl crotonate, and ethyl crotonate; acrylate esters such as methyl acrylate and ethyl acrylate; methacrylic acid such as methyl methacrylate and ethyl methacrylate; Acid esters, vinyl acetate, acrylonitrile, styrene and the like.

The method for producing the organic polymer-titanium composite oxide composite of the present invention will be described below in the case where the polymerization of the acyloxy group in the titanium alkoxide is performed first, and the co-hydrolysis polycondensation of the alkoxy group is performed first. The operation will be described separately.

(1) A case where polymerization of an acyloxy group is carried out first This case is further divided into a case where pre-hydrolysis of an alkoxide of another element is carried out and a case where it is not carried out. Titanium alkoxides used in the present invention often undergo a faster hydrolysis reaction than alkoxides of other elements, so that alkoxides of other elements are pre-hydrolyzed and co-hydrolyzed with alkoxides of titanium and tetraalkoxides. It facilitates polycondensation.

(A) When Pre-Hydrolysis is Not Performed Titanium alkoxide and, if necessary, a solvent for dehydration and purification are mixed, and the mixture is sufficiently substituted with an inert gas (nitrogen or argon).
The solvent for dehydration and purification is arbitrarily added depending on the type of polymerization to be performed, and the polymerization reaction can be controlled by the addition. Specifically, it is the same as that used for producing the above-mentioned titanium alkoxide, and is not added when performing bulk polymerization.

Thereafter, a radical polymerization initiator or an ionic polymerization initiator, and if necessary, a polymerizable monomer are added,
The polymerization reaction is performed by decomposing the polymerization initiator by UV irradiation or the like. Examples of the radical polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, azobiscyclohexanecarbonitrile, phenyl disulfide, tetramethylthiuram monosulfide, tetra tetramethylthiuram disulfide, and examples of ionic polymerization initiators aluminum chloride, tin tetrachloride, boron trifluoride, monoethyl aluminum dichloride, butyl lithium, sodium naphthalene, phenyl magnesium bromide and the like.

When the polymerization is carried out by heating, the temperature is not particularly limited as long as the polymerization initiator is decomposed. For example, azobisisobutyronitrile, benzoyl peroxide,
When a radical initiator such as lauroyl peroxide is used, 3
It is often carried out at 0 ° C. to 100 ° C., and in the case of ionic polymerization, at room temperature or lower, particularly at zero.

All the above operations are performed in an inert gas stream. To the reaction mixture, an alkoxide of another element, a water-miscible solvent and water, and if necessary, a catalyst such as titanium tetraalkoxide, an acid or a base, are added, and the alkoxy group is co-hydrolyzed and polycondensed to obtain the desired organic compound. A molecule-titanium composite oxide composite is obtained.

Here, the water-miscible solvent is used for adding water for co-hydrolysis polycondensation to the system. Specifically, methanol, ethanol, alcohols such as isopropanol,
Examples include ketones such as acetone and methyl ethyl ketone, and cellosolves such as methyl cellosolve and ethyl cellosolve, and a mixed solvent thereof is also used. The amount of water is arbitrarily changed depending on the hydrolyzability of the alkoxy group.
In addition, a catalyst such as an acid or a base is optionally added to control co-hydrolytic polycondensation of an alkoxy group,
Specific examples include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, ammonium hydroxide, sodium hydroxide, triethanolamine, morpholine and the like.

(B) Preliminary Hydrolysis In this case, after preliminarily hydrolyzing an alkoxide of another element, cohydrolysis polycondensation of an alkoxy group is performed.

A water-miscible solvent and an alkoxide of another element are mixed, and water, a catalyst such as an acid and a base, if necessary, are added thereto, and the alkoxide of the other element is pre-hydrolyzed.
The water-miscible solvent, water and catalyst are the same as described above.

Thereafter, this reaction solution is mixed with the polymerization reaction mixture of acyloxy groups described in (a), and if necessary, a catalyst such as titanium tetraalkoxide, water, acid, or base is added to co-hydrolyze the alkoxide portion. Decomposition and polycondensation gives the desired organic polymer-titanium composite oxide composite. Water and catalyst are the same as above.

(2) When the Co-hydrolysis Polycondensation of the Alkoxy Group is Performed First The case where the co-hydrolysis polycondensation of the alkoxy group is performed first is divided into the co-hydrolysis of the alkoxy group and the polymerization reaction of the acyloxy group. explain.

[0058] In case of the prior co-hydrolysis polycondensation of cohydrolysis min Kaikasane condensation alkoxy group (b) alkoxy group, divided into a case of not performing the case of performing the preliminary hydrolysis of the alkoxide of the other elements. First, the case of performing the preliminary hydrolysis will be described.

An alkoxide of another element is mixed with a water-miscible solvent, and water and, if necessary, a catalyst such as an acid or a base are added thereto to pre-hydrolyze the alkoxide of another element.
The water-miscible solvent, water and catalyst are the same as described above. afterwards,
A catalyst such as titanium alkoxide and, if necessary, titanium tetraalkoxide, water, acid, and base is added to the reaction solution to co-hydrolyze and polycondense the alkoxide portion. Same as above for water and catalyst.

Next, the case where the preliminary hydrolysis is not performed will be described. Titanium alkoxides and alkoxides of other elements,
After mixing a titanium tetraalkoxide and a water-miscible solvent as needed, water, a catalyst such as an acid and a base as necessary are added, and the alkoxide portion is co-hydrolyzed and polycondensed. The water-miscible solvent, water and catalyst are the same as described above.

(Ii) Polymerization reaction of acyloxy group After co-hydrolysis polycondensation of alkoxy group by any of the above methods, the solvent and water remaining in the system are removed. This is because the water may interfere with the subsequent polymerization reaction to form the organic matrix, and is removed once with the solvent.

Thereafter, the inert gas replacement is sufficiently performed,
After adding the same radical polymerization initiator or ionic polymerization initiator, dehydration purification solvent and polymerizable monomer as described above, the polymerization initiator is decomposed by heating under an inert gas stream, irradiation with ultraviolet rays, or the like. Then, a polymerization reaction is performed to obtain a target organic polymer-titanium composite oxide composite.

The reaction product containing the organic polymer-titanium-based composite oxide composite obtained as in the above (1) or (2) is a viscous liquid or a solid. After adding and adjusting the viscosity of the system, it is molded into a film, fiber, etc., or the reaction product is taken out and molded using a normal plastics molding method.

[0064]

Embodiments of the present invention will be described below.

[0065]

Example 1 An organic polymer-titanium composite oxide composite was produced by using the titanium alkoxide and tetramethyl orthosilicate obtained in Production Example 1 to carry out a reaction prior to the polymerization reaction of an acyloxy group. Acrylic acid was allowed to coexist during the polymerization reaction of the acyloxy group.

500 ml of toluene dehydrated and purified by distillation was placed in a flask equipped with a refluxer and a stirrer that had been sufficiently dried and purged with nitrogen, and 16.9 g (0. 0 g) of the titanium alkoxide obtained in Production Example 1 was added thereto. 05 mol), 7.2 g (0.1 mol) of acrylic acid, 0.1 benzoyl peroxide
g was stirred and dissolved. After sufficient replacement with nitrogen, the mixture was heated to 90 ° C. under a nitrogen stream while stirring and kept for 4 hours to copolymerize the acryloxy group of the titanium alkoxide with acrylic acid.

200 ml of ethanol was placed in a separate flask equipped with a reflux condenser and a stirrer, and 10.4 g (0.05 mol ) of tetraethylorthosilicate was stirred and dissolved therein. Further, a solution prepared by dissolving 0.0365 g (3 × 10 ⁻⁴ mol) of hydrochloric acid in 3.6 g (0.2 mol) of water was added, and tetraethyl orthosilicate was prehydrolyzed. After the reaction mixture and the copolymerization reaction mixture were stirred and mixed, 2.7 g (0.15 mol) of water was added, and stirring was continued to co-hydrolyze polycondensate the isobutoxy group of the titanium alkoxide with tetraethyl orthosilicate.

After the reaction, the solvent was removed to obtain a white solid. When infrared absorption analysis, X-ray diffraction, and X-ray fluorescence measurement were performed, it was confirmed that the polyacrylic acid contained amorphous titanium oxide-silicon oxide.

[0069]

Example 2 Using the titanium alkoxide and zirconium tetraisoproposide obtained in Production Example 2, a reaction was conducted in advance of a polymerization reaction of an acyloxy group to obtain an organic polymer.
A titanium-based composite oxide composite was manufactured. Methyl methacrylate was allowed to coexist during the polymerization reaction of the acyloxy group, and titanium tetraisopropoxide was allowed to coexist during the cohydrolytic polycondensation reaction of the alkoxy group.

200 ml of carbon tetrachloride dehydrated and purified by distillation was placed in a flask equipped with a refluxer and a stirrer that had been sufficiently dried and purged with nitrogen, and 9.3 g of the titanium alkoxide obtained in Production Example 2 was added thereto. 0.03 mol) and 10.0 g (0.1 mol) of methyl methacrylate were dissolved by stirring. After sufficient replacement with nitrogen, the mixture was cooled to 0 ° C. in an ice bath, and while stirring, 1 ml of a tin tetrachloride solution (1 ml dissolved in 100 ml of dehydrated and purified carbon tetrachloride) was added thereto. For 2 hours, and a methacryloxy group of titanium alkoxide and methyl methacrylate were copolymerized. After completion of the reaction, 400 ml of isopropanol and 29.5 g of zirconium tetraisopropoxide (0.09
Mol), 8.5 g of titanium tetraisopropoxide
(0.03 mol) and then 7.2 g of water
(0.4 mol), and co-hydrolyzed polycondensation of zirconium tetraisopropoxide, titanium tetraisopropoxide and isopropoxy groups of titanium alkoxide.

After the reaction, the solvent was removed to obtain a white solid. Infrared absorption analysis, X-ray diffraction and X-ray fluorescence measurement confirmed that the copolymer was a methacrylic acid-methyl methacrylate copolymer containing amorphous titanium oxide-zirconium oxide.

[0072]

Example 3 Using the titanium alkoxide and aluminum trisec-butoxide obtained in Production Example 3, the reaction was carried out in advance of the co-hydrolytic polycondensation reaction of the alkoxy group, and an organic polymer-titanium composite oxide composite was obtained. Was manufactured.

A flask equipped with a reflux condenser and a stirrer was charged with 500 ml of ethyl cellosolve, and 14.8 g (0.06 mol) of aluminum trisec butoxide was stirred and dissolved therein. Furthermore, hydrochloric acid was added to 1.8 g (0.1 mol) of water in 0.1 g.
A solution in which 0365 g (1.0 × 10 ⁻⁴ ) was dissolved was added, and aluminum trisec butoxide was pre-hydrolyzed.

47.1 g (0.14 mol) of the titanium alkoxide obtained in Production Example 3 was dissolved in the above reaction mixture. Further stirring, 7.2 g of water (0.4 mol)
Was added to co-hydrolyze polycondensate the aluminum trisec butoxide and the n-butoxy group of the titanium alkoxide.

After completion of the reaction, the remaining water, solvent and hydrochloric acid were removed, and 400 ml of benzene dehydrated and purified by distillation was added, followed by sufficient nitrogen replacement. Further, 1 ml of n-butyllithium solution (1 g dissolved in 100 ml of dehydrated and purified benzene) was quickly added under a nitrogen stream, and the mixture was allowed to stand at room temperature for 2 hours with stirring to polymerize the crotonoxy group of the titanium alkoxide. .

After completion of the reaction, the solvent was removed to obtain a white solid. Infrared absorption analysis, X-ray diffraction, and X-ray fluorescence measurement confirmed that the polycrotonic acid contained amorphous titanium oxide-aluminum oxide.

[0077]

Example 4 An organic polymer-titanium-based composite oxide composite was produced using the titanium alkoxide obtained in Production Example 4 and zinc di-n-butoxide, followed by a co-hydrolytic polycondensation reaction of an alkoxy group. . In addition, titanium tetraethoxide was allowed to coexist during the co-hydrolysis polycondensation reaction of the alkoxy group.

400 ml of ethanol was placed in a flask equipped with a reflux condenser and a stirrer, and 43.7 g (0.12 mol) of the titanium alkoxide obtained in Production Example 4 and 13.7 g (0.06 mol) of titanium tetraethoxide were obtained. ) And zinc di-n-butoxide (25.4 g, 0.12 mol) were dissolved by stirring. Furthermore, hydrochloric acid 0.1 was added to water 12.6g (0.7 mol).
A solution in which 11 g (3.0 × 10 ⁻³ mol) was dissolved was added, and the respective alkoxy groups of the three alkoxides were co-hydrolyzed and polycondensed.

After completion of the reaction, the remaining water, solvent and hydrochloric acid were removed, and 400 ml of toluene dehydrated and purified by distillation was added, followed by sufficient nitrogen replacement. Further, after cooling to 0 ° C. in an ice bath, 4.3 g (0.024 mol) of phenylmagnesium bromide was dehydrated and purified in toluene under a nitrogen stream.
The solution dissolved in ml was quickly added and left overnight at the same temperature with stirring to polymerize the methacryloxy group of the titanium alkoxide.

After the reaction, the solvent was removed to obtain a white solid. Infrared absorption analysis, X-ray diffraction, and X-ray fluorescence measurement confirmed that the polymethacrylic acid contained amorphous titanium oxide-zinc oxide.

[0081]

Example 5 Using the titanium alkoxide and tetraethyl orthosilicate obtained in Production Example 5, a polymerization reaction of an acyloxy group was preceded and a reaction was carried out to produce an organic polymer-titanium composite oxide composite. Note that styrene was allowed to coexist during the polymerization reaction of the acyloxy group.

25.4 g (0.1 mol) of the titanium alkoxide obtained in Production Example 5 was placed in a flask equipped with a refluxer and a stirrer that had been sufficiently dried and purged with nitrogen, and 0.0654 g of diphenyl disulfide was added thereto. (3 × 10 ^-4 mol)
Was dissolved in 5.2 g (0.05 mol) of styrene, followed by stirring and mixing. After sufficient replacement with nitrogen, the mixture was heated to 30 ° C. while continuing to stir under a nitrogen stream, and the Mazda S
Ultraviolet irradiation was performed with an HL ultrahigh pressure mercury lamp for 6 hours to copolymerize an acryloxy group and styrene.

In a separate flask equipped with a reflux condenser and a stirrer, 300 ml of tetrahydrofuran was placed, and 15.2 g ( 0.07 mol) of tetraethyl orthosilicate and 24.6 g of aluminum triisobutoxide were added thereto.
(0.1 mol) was dissolved by stirring. In addition, 10.8 g of water
(0.6 mol) was added to prehydrolyze the two alkoxides.

After stirring and mixing the above reaction mixture, stirring was further continued to mix the ethoxy group of titanium alkoxide with aluminum.
Triisobutoxide and tetraethyl orthosilicate were co-hydrolyzed and polycondensed. After the reaction, the solvent was removed to obtain a white solid. Infrared absorption analysis, X-ray diffraction, was subjected to X-ray fluorescence measurement, non-crystalline titanium oxide - silicon oxide -
It was confirmed that it was an acrylic acid-styrene copolymer containing aluminum oxide .

The organic polymer obtained in Examples 1 to 5
Titanium-based composite oxide composites were made into thin films and subjected to elemental analysis (EPMA, etc.) within a certain area. As a result, it was found that the titanium-based composite oxides were uniformly dispersed in the organic polymer matrix. confirmed. Further, the thin film was observed with a transmission electron microscope, and it was confirmed that the inorganic skeleton was sufficiently developed.

[0086]

According to the present invention, it is possible to provide an organic polymer-titanium-based composite oxide composite in which a titanium-based composite oxide having a well-developed skeleton is firmly bonded and uniformly distributed. By this composite, a thin film, a fiber, or the like having a sufficient adsorption ability worth practical use is obtained, and can be used as an adsorbent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-280279 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 79/00 C08F 30/04

Claims (4)

(57) [Claims] 1. A polymerization reaction of an acyloxy group by coexisting a titanium alkoxide having an acyloxy group having a polymerizable unsaturated bond represented by the chemical formula 1 and an alkoxide of a metal which does not form a perovskite crystal structure together with titanium. And an organic polymer-titanium-based composite oxide composite obtained by a co-hydrolysis polycondensation reaction of the alkoxy group of each alkoxide. ## STR1 ## _{Ti (OR) 4-n Q} n where, R represents the same or different types of Al <br/> kill group having 2 to 10 carbon atoms, Q is each the same or different types of polymerizable unsaturated bonds N is 1 or 2; 2. The method according to claim 1, wherein the polymer is obtained by coexisting a polymerizable monomer having a polymerizable unsaturated bond copolymerizable with the titanium alkoxide during the polymerization reaction of the acyloxy group. Organic polymer-titanium composite oxide composite. 3. The method according to claim 2, wherein the polymerizable monomer is selected from the group consisting of crotonic acid, acrylic acid, methacrylic acid, crotonic acid ester, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, and styrene. The organic polymer-titanium-based composite oxide composite according to claim 2. 4. The method according to claim 1, wherein a co-hydrolysis polycondensation reaction of the alkoxy group coexists with an alkoxy group having 2 to 10 carbon atoms and a titanium tetraalkoxide composed of titanium. Organic polymer according to item-
Titanium-based composite oxide composite.