JP2000086769A - Production of soluble solid polytitanoxane and its derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid polytitanoxane and its derivative which each has high condensation stability and high solubility in organic solvents and has a high TiO2 content. SOLUTION: This method for producing a solid polytitanoxane or its derivative comprises hydrolyzing a titanium tetraalkoxide of the general formula: Ti(OR)4 (R is a monovalent 1-12C hydrocarbon group) with 1.0-1.75 fold moles of water in the presence or absence of an inorganic or organic acid as a catalyst in at least one solvent selected from etheric solvents, ketonic solvents and alcoholic solvents at a temperature of 0-30 deg.C, further aging the hydrolysis product at a temperature of 60-120 deg.C, or further reacting the product with a chelating agent or silylating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the synthesis of solid polytitanoxane and its derivatives having high solubility and condensation stability in organic solvents and high TiO ₂ content.

[0002] The polytitanoxane obtained in the present invention is suitable for producing high-purity titanium oxide and for use as a coating agent or a binder. Is an excellent raw material. Further, by forming a titanoxane derivative by reacting with a chelating reagent or a silylating agent, it can be more effectively utilized in the above-mentioned material synthesis.

[0003]

2. Description of the Related Art Titanium tetraalkoxide Ti (OR) ₄ having an alkyl group R having 2 to 5 carbon atoms is a liquid which is highly hydrolyzable at room temperature and is difficult to handle, and is suitable for molding and processing in material synthesis. It is desirable to use a substance that has been modified. There have been reports on the production of hydrolyzed polymers of metal alkoxides, but none of them has been isolated as a stable polymetalloxane. It is often used before. However, sols have low condensation stability and cannot always be said to have properties and forms suitable for molding and processing processes in storage management and materialization. In addition, the sol formed by the sol-gel method by hydrolysis of a metal alkoxide other than silicon has still lower condensation stability, and has not been isolated as a polymetalloxane soluble in an organic solvent.

In order to solve this, for example, Japanese Patent Laid-Open No.
The 129,032 discloses, by a method of dripping water, dissolved in an alcohol in the alcohol solution of the heated titanium tetraalkoxide, but has gained ladder of polytitanoxane has not been obtained with a TiO ₂ content satisfactory. When the TiO ₂ content is compared among polytitanoxane compounds having the same molecular weight and the same alkyl group, the higher the TiO ₂ content, the lower the occurrence of voids and so-called sink marks during sintering of ceramics, and a better thin film can be formed. There is a need for polytitanoxane with high TiO ₂ content.

[0005]

If a solid polytitanoxane having high solubility and condensation stability in an organic solvent and a high TiO ₂ content can be obtained, it can be used as a raw material for the synthesis of a titanium oxide-based material having excellent moldability and workability. Extremely valuable.

For this purpose, it is necessary to control the reaction so as to produce a cage-like or branched ladder-like polytitanoxane by hydrolysis and condensation of titanium tetraalkoxide.

In the sol-gel method in which titanium tetraalkoxide is directly hydrolyzed with water, a gel insoluble in a solvent is generated. Therefore, a method in which the water is very slowly hydrolyzed with a small amount of water in the air or water generated by a reaction such as esterification. By controlling the reaction, a polymetalloxane sol can be obtained, which is also extremely unstable with respect to condensation and cannot be isolated.

[0008] The inventors of the present invention directly hydrolyze titanium tetraalkoxide in a specific solvent at a predetermined temperature, or hydrolyze using an acid as a catalyst to suppress gelation. By aging, or further by reaction with a chelating reagent and a silylating agent,
This problem has been solved by finding that a polytitanoxane having a high condensation stability by being dissolved in an organic solvent and having a higher TiO ₂ content than a ladder-type polytitanoxane can be obtained.

[0009]

In the sol-gel reaction of titanium tetraalkoxide and water by a conventional method, polytitanoxane precipitates as a precipitate. The present inventors to improve this, by ripening under certain conditions in the hydrolysis and further specific conditions as a solvent for Chitanokisan is dissolved compounds, the content of TiO ₂ is higher than conventional polytitanoxane, and We have succeeded in isolating a solid polytitanoxane which is soluble and stable in organic solvents. Furthermore, this polytitanoxane can be easily gelled by using a poor solvent, and by reacting it with a chelating ligand or a silylating agent, a polytitanoxane derivative having different solubility and stability is synthesized, and this is used for material synthesis. The present inventors have found that a suitable raw material can be produced, and have reached the present invention.

Thus, the present invention provides a compound of the general formula Ti (OR) ₄
Wherein R is a carbon tetraalkoxide
12 monovalent hydrocarbon groups) from 1.0 times mol to 1.75.
Using a twice molar amount of water, in the presence or absence of an inorganic or organic acid as a catalyst, in the presence of one or more solvents selected from ether solvents, ketone solvents, and alcohol solvents, at 0 ° C. Hydrolysis at a temperature of
General formula (TiO _4/2 ) _w {(R′O) TiO _3/2 } characterized by aging at a temperature of 0 to 120 ° C.
_{x {(R'O) 2 TiO 2/2} } y (R'O 1/2)
_z ｛w, x is 0 or a positive integer, w + x + y> 6, y = 0
-4, z = 0-8), wherein R 'is a hydrogen atom (provided that
Hydrogen atoms do not exceed 10% of the total R '. ) And a polytitanoxane represented by｝ consisting of a monovalent hydrocarbon group having 1 to 12 carbon atoms.

The present invention also provides a method for producing a chelated and silylated derivative of the above polytitanoxane.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, as described above, titanium tetraalkoxide is directly hydrolyzed in a specific solvent at a specific temperature, or is hydrolyzed using an acid as a catalyst, followed by aging at a specific temperature. In the hydrolysis, water is used in an amount of 1.0 to 1.75 moles per mole of the titanium tetraalkoxide as a starting compound. The amount of water includes the amount of water used when diluting an acid or solvent used separately.

In the hydrolysis reaction, one or more solvents selected from ether solvents, ketone solvents and alcohol solvents can be used. As the ether solvent, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethyl ether, diethylene glycol dimethyl ether, diethyl ether and the like are preferable.
Acetone, methyl ethyl ketone,
Methyl isopropyl ketone and methyl isobutyl ketone are preferred. As the alcohol solvent, methanol, ethanol, 1-propanol, 2-propanol and butanols are preferable. Mixtures of these can also be used. Particularly, tetrahydrofuran (THF) is preferable, and when an alcohol solvent is used, it is preferable to use an alcohol corresponding to the alkoxide of titanium tetraalkoxide. For example, when an alcohol solvent is used for titanium tetraethoxide, it is preferable to use ethanol.

As the acid catalyst, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid and formic acid, acetic acid, propionic acid, butyric acid,
Organic acids such as benzoic acid and p-toluenesulfonic acid can be used. Hydrochloric acid and acetic acid are particularly preferred. The amount of the catalyst used is 0.05 to 0.5 times mol, preferably 0.1 to 0.3 times mol per titanium metal.

The hydrolysis reaction is carried out with stirring at a temperature in the range of 0 ° to 30 ° C. for about 1 to 2 hours, and then the temperature is raised to a temperature of 60 to 120 ° C. for about 3 to 4 hours. I do. After the reaction solution is cooled and concentrated, a solid polytitanoxane compound having the following general formula [I] is obtained. (TiO _4/2 ) _w ｛(R′O) TiO _3/2 ｝ _x ｛(R′O) ₂ TiO _2/2 ｝ _y (R′O _1/2 ) _z [I] where w and x are 0 or a positive integer, w + x + y> 6, y =
0-4, z = 0-8), wherein R ′ is a hydrogen atom (however, the hydrogen atom does not exceed 10% of all R ′) and a monovalent hydrocarbon group having 1 to 12 carbon atoms. Become.

When such a polytitanoxane compound is isolated or continuously reacted without isolation with a chelating agent or silylating agent at the above-mentioned ordinary temperature for about 1 to 2 hours, the following general formula [II] ] Or [III], a chelated or silylated derivative of polytitanoxane is obtained. (TiO _4/2 ) _a ｛(R′O) TiO _{3/2 ｂb} ｛(L) ₂ TiO _2/2 ｝ _c (LT TiO _3/2 ) _d (L) _e [II] where a, b and c are 0 or positive integers, a + b + c + d
> 6, d = 0 to 4, e = 0 to 4, wherein R 'is a hydrogen atom (however, the hydrogen atom does not exceed 10% of the total R') and a monovalent carbon atom having 1 to 12 carbon atoms. A hydrogen group, L is a β-diketone comprising a hydrocarbon group having 5 or more carbon atoms, a keto acid ester comprising a monovalent hydrocarbon group having 4 or more carbon atoms, and an oxy group comprising a monovalent hydrocarbon group having 3 or more carbon atoms. An acid, a 2-alkoxyethanol comprising a monovalent hydrocarbon group having 1 or more carbon atoms,
It is one or more groups selected from alkylene glycols having 2 to 6 carbon atoms. (TiO _4/2 ) _f {(R′O) TiO _3/2 } _g {(R ″ ₃ SiO) ₂ TiO _2/2 ) _h (R ″ ₃ SiOTiO _3/2 ) _i (R ″ ₃ SiO _{1 / 2} ) _j [III] where f, g, and h are 0 or positive integers, and f + g + h + i>
6, i = 0 to 4, j = 0 to 4, wherein R 'is a hydrogen atom (however, the hydrogen atom does not exceed 10% of the total R') and a monovalent hydrocarbon having 1 to 12 carbon atoms. The group R "is a hydrocarbon group having 1 to 6 carbon atoms, not exceeding 70% of the total R '.

The chelating reagent used here is a β-diketone having 5 or more carbon atoms, an α-keto acid ester comprising a monovalent hydrocarbon having 4 or more carbon atoms, and an α-keto acid ester comprising a hydrocarbon group having 3 or more carbon atoms. -Oxy acids, 2-alkoxyethanols comprising a monovalent hydrocarbon group having 1 or more carbon atoms, alkylene glycols having 2 to 6 carbon atoms and the like. It is preferable to use acetylacetone, ethyl acetoacetate, lactic acid, 2-ethoxyethanol, propylene glycol.

As the silylating agent, N, O-bis (trimethylsilyl) acetamide, N, N'-bis (trimethylsilyl) urea and hexaalkyldisilazane compounds can be used. It is preferred to use hexamethyldisilazane.

The polytitanoxane thus obtained or its chelated or silylated derivative has higher solubility in organic solvents than those obtained by the conventional method,
Or, the condensation stability is high.
Even after 6 months, it retains good solubility and dissolves well in organic solvents. In addition, this compound has a high TiO ₂ content and does not cause vacancies or defects even during sintering and sintering. A good thin film can be obtained even when a thin film is formed. Can be.
Furthermore, it can be favorably used as a starting compound for producing high-purity titanium oxide.

If the reaction is not carried out under the conditions specified in the present invention, for example, a hydrolysis reaction is carried out at a higher temperature, and when aging is carried out, a compound having a satisfactory TiO ₂ content cannot be obtained. Neither can it be used well for the above applications. However, when the reaction is carried out under the conditions specified in the present invention, a product excellent in these properties can be obtained.

[0021]

The present invention will be described in more detail with reference to Examples and Reference Examples.

However, the scope of the present invention is not limited at all by the following examples. In the following examples, "%" is based on weight unless otherwise specified.

EXAMPLE 1 4.56 g (0.02 mol) of titanium tetraethoxide was charged into a two-necked eggplant type flask equipped with a rotor and a reflux condenser, dissolved in 100 ml of tetrahydrofuran (THF), and heated at 5 ° C. Stirred. At 5 ° C,
0.54 g (0.03 mol) of water with vigorous stirring
Was diluted slowly with 20 ml of THF. After stirring at 5 ° C. for 1 hour, the mixture was refluxed at 66 ° C. for 3 hours to mature the reaction. After cooling the reaction solution, it was concentrated using an aspirator and the yellow solid substance (P-1) (Ti
O _4/2 ) ₂ (C ₂ H ₅ OTiO _3/2 ) ₈ ｛(C ₂ H
_{5 O)} 2 TiO _2/2} to afford the ₂ 2.35 g.

The obtained yellow solid substance was well dissolved in benzene, chloroform, ether, THF and the like. P-1
Even after storage for one month without using a solvent in a container in a nitrogen atmosphere in which the outside air was shut off, its solubility was maintained, and it was dissolved again in the organic solvent. A chloroform solution of P-1 was put into hexane. The polytitanoxane formed as a precipitate was immediately insolubilized by filtration and dried. This powder was compression-molded at 200 kg / cm ² using a tableting machine for infrared absorption spectrum and calcined at 600 ° C. for 4 hours to obtain a dense calcined body without sinking. P-1 has been found to contain TiO ₂ 67.4% due metal analysis of the dry process, which agreed well with the theoretical value (68.3%). The molecular weight determined by vapor pressure equilibrium was 1,400 (theoretical value: 1403). In addition, from infrared absorption and nuclear magnetic resonance spectra, it was found that this yellow solid substance was polytitanoxane ethoxide having a Ti-O-Ti bond as a main chain and having an ethoxy group in a side chain.

Example 2 Instead of the water / THF solution of Example 1, 6N hydrochloric acid 0.37
g and 0.33 g of water (total water amount = 0.035 mol)
A white solid substance (P-2) (C ₂ H ₅ OT) was prepared in the same manner as in Example 1, except that the substance diluted with THF was used.
iO _3/2 ) ₁₁ {(C ₂ H ₅ O) ₂ TiO _2/2 ) ₃ (C ₂
H ₅ O _1/2) to give the ₁ 2.56 g.

The obtained white solid (P-2) dissolves in methanol and ethanol, but does not dissolve in other solvents. The solubility was maintained even after storage for 6 months in a container in a nitrogen atmosphere in which the outside air was shut off, and the compound was dissolved in the organic solvent again. Contains TiO ₂ of 62.3% by metal analysis of the dry method, which was found to be substantially coincident with the calculated values 62.7%. The molecular weight determined by the vapor pressure equilibrium method was 1800 (theoretical value: 1785).

Example 3 5.68 g (0.02 m) of titanium tetraisopropoxide
ol) and the reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 25 ° C., and a yellow solid substance (P-3) was obtained.
(TiO _4/2 ) ₂ (C ₃ H ₇ OTiO _3/2 ) ₁₁ ｛(C ₃
H ₇ O) ₂ TiO _2/2 ) ₂ (C ₃ H ₇ O _1/2 ) ₁ 2.
70 g were obtained.

The obtained yellow solid substance was well dissolved in benzene, chloroform, ether, THF and the like. P-3
Was kept in the container for 2 months in a nitrogen atmosphere in which the outside air was blocked, and its solubility was maintained, and it was dissolved again in the organic solvent. P-
The chloroform solution of No. 3 was poured into hexane, and the polytitanoxane formed as a precipitate was immediately filtered and dried, and was insolubilized immediately.

P-3 was found to be 59.5 by dry metal analysis.
% TiO ₂ was found to be included, which was in good agreement with the calculated value (59.5%). Also, from the infrared absorption and nuclear magnetic resonance spectra, this yellow solid substance
The polytitanoxane isopropoxide was found to have an O-Ti bond as a main chain and an isopropoxy group in a side chain. The molecular weight by vapor pressure equilibrium method is 2000 (theoretical value 2
015).

[0030] The IR spectra of P-3 in Figure ^1, 1 H
The NMR spectra are shown in FIG.

Examples 4 and 5, Comparative Example 1 The same experiment as in Example 3 was carried out except that the molar ratio of water was changed, and the results shown in Table 1 were obtained.

[Table 1]

Example 6 In Example 3, 0.37 g of 6N hydrochloric acid and 0.33 g of water were used.
(Total water amount = 0.035 mol) The same operation as in Example 3 was performed except that 2-propanol was used instead of tetrahydrofuran, and a white solid substance (P-6) was obtained.
(C ₃ H ₇ OTiO _3/2 ) ₁₅ ｛(C ₃ H ₇ O) ₂ TiO
2.70 g of _2/2 ｝ ₃ (C ₃ H ₇ O _1/2 ) ₂ was obtained.

The obtained white solid (P-6) dissolves in methanol and ethanol, but does not dissolve in other solvents. The solubility was maintained even after storage for 6 months in a container in a nitrogen atmosphere in which the outside air was shut off, and the compound was dissolved in the organic solvent again. 56.5% TiO by dry metal analysis
₂ (theoretical amount: 55.0). The molecular weight according to the vapor pressure equilibrium method was 2,600 (theoretical amount: 2612).

Examples 7 and 8 The same operation as in Example 6 was carried out except that the amount of the hydrochloric acid catalyst was changed, and the results shown in Table 2 were obtained.

The yields of polytitanoxane (P-7, P-8) were 3.02 and 3.09 g, respectively.

[Table 2]

Example 9 In a two-necked eggplant type flask equipped with a rotor and a reflux condenser, 5.68 g (0.02 mol) of titanium tetraisopropoxide was placed.
l), and tetrahydrofuran (THF) 100 m
and stirred well at 20 ° C. 20 ° C
While stirring vigorously with water, 0.54g of water (0.03mo
l) diluted with 20 ml of THF was slowly added dropwise. After stirring at 20 ° C. for 1 hour, the mixture was refluxed at 66 ° C. for 3 hours to mature the reaction. After cooling the reaction solution, 3.00 g (0.03 mol) of acetylacetone was added, and the mixture was stirred at room temperature for 1 hour. After that, the solvent was distilled off using an aspirator and concentrated, and the residue was redissolved in 4 ml of chloroform.
It was added to 200 ml of hexane and reprecipitated to obtain 2.72 g of an orange solid substance (P-9).

The obtained orange solid substance was well dissolved in alcohol, chloroform, THF, benzene and the like. P-
The sample No. 5 retained its solubility even after being stored for one month without using a solvent in a container in a nitrogen atmosphere in which the outside air was shut off, and was again dissolved in the organic solvent.

P-9 was found to be 50.6 by dry metal analysis.
% (Theoretical value: 50.3%) of TiO ₂ was found to be contained. The molecular weight of P-9 determined by the vapor pressure equilibrium method is 2
400 (theoretical 2384). In addition, from the infrared absorption (FIG. 3) and nuclear magnetic resonance (FIG. 4) spectra, this orange solid substance is a polytitanoxane having a Ti—O—Ti bond as a main chain and having an isopropoxy group and an acetylacetonato group in a side chain. I understand. From the above analysis results, it was found that P-5 was a polytitanoxane composed of the following structural units. All the analytical values of P-9 are in good agreement with the theoretical values calculated from this structure.

[0039] ^{_{(TiO 4/2) 2 {(Pr}} i O) TiO
_{3/2 ７ 7} ｛(acac) ₂ TiO _2/2 ｝ ₂ ｛(aca)
c) TiO _{3/2 ４ 4} (acac) ₁

Example 10 Instead of titanium tetraethoxide, titanium tetra-n-
A yellow solid substance (P-10) was obtained by performing the same operation as in Example 1 except that 6.81 g (0.02 mol) of butoxide was used.
2.91 g were obtained. The resulting yellow solid substance is benzene,
It dissolved well in chloroform, ether, THF and the like.
Even if P-10 was stored for 3 months without using a solvent in a container in a nitrogen atmosphere in which the outside air was shut off, its solubility was maintained and it was dissolved again in the organic solvent. A chloroform solution of P-10 was put into hexane, and the polytitanoxane produced as a precipitate was immediately filtered and dried, and was insolubilized immediately. P-10 has been found to contain TiO ₂ 58.0% due metal analysis of the dry process, which was substantially equal to the theoretical value (57.1%).

The molecular weight by the vapor pressure equilibrium method is 20900
(Theoretical value: 20572). Also, from the infrared absorption and nuclear magnetic resonance spectra, this yellow solid substance
It was found to be polytitanoxane-n-butoxy having an O-Ti bond as a main chain and having an n-butoxide group in a side chain. (TiO _4/2 ) ₈ (C ₄ H ₉ OTiO _3/2 ) ₁₃₆ ｛(C
_{4 H 9 O) 2 TiO 2} /2} 3

Example 11 6.81 g (0.02 mol) of titanium tetra-n-butoxide was placed in a two-necked eggplant type flask equipped with a rotor and a reflux condenser.
l) and diethylene glycol dimethyl ether (DEG
DM) was added and mixed, and the mixture was stirred well at 15 ° C. While stirring vigorously at 15 ° C.,
0.37 g of N hydrochloric acid and 0.33 g of water (total water amount = 0.035
mol.) in 20 ml of DEGDM was slowly added dropwise. After stirring for 1 hour at 15 ° C, 3 hours 1
The reaction was aged at 15 ° C. After cooling the reaction mixture, it was concentrated using an aspirator, and the mixture was concentrated to give a white solid substance (P-11) (TiO
_{4/2) 2 (C 4} H 9 OTiO 3/2) 151 {(C 4 H
₉ O) ₂ TiO _2/2 ｝ ₄ (C ₄ H ₉ O _1/2 ) ₁ 3.2
7 g were obtained.

The obtained white solid (P-11) is soluble in methanol and ethanol, but not in other solvents. The solubility was maintained even after storage for 6 months in a container in a nitrogen atmosphere in which the outside air was shut off, and the compound was dissolved in the organic solvent again. 55.3% TiO ₂ by dry metal analysis
(Theoretical value: 54.7%). The molecular weight by the vapor pressure equilibrium method is 23000 (theoretical value: 2292).
4).

Example 12 6.81 g (0.02 mol) of titanium tetra-n-butoxide was placed in a two-necked eggplant type flask equipped with a rotor and a reflux condenser.
l) was charged, dissolved in 100 ml of dioxane, and stirred well at 20 ° C. To this raw material solution, 20 ml of 0.54 g (0.03 mol) of water was added at 20 ° C. with vigorous stirring.
What was diluted with dioxane was slowly added dropwise. 1
After stirring at 20 ° C. for 3 hours, the mixture was refluxed at 101 ° C. for 3 hours to mature the reaction.

After cooling the reaction solution, acetylacetone (3.0
0 g, 0.03 mol) and stirred at room temperature for 1 hour. Thereafter, the solvent was distilled off using an aspirator and concentrated, and the residue was redissolved in 4 ml of chloroform.
And then reprecipitated to give an orange solid substance (P
-12) (TiO _4/2 ) ₈ (C ₄ H ₉ OTiO _3/2 ) ₅₈
｛(Acac) TiO _3/2 ｝ ₇₈ ｛(acac) ₂ TiO
_2/2) was obtained ₃ 3.19g.

The obtained orange solid substance was well dissolved in alcohol, chloroform, THF, benzene and the like. P-
In No. 12, even if stored for one month without using a solvent in a container in a nitrogen atmosphere in which the outside air was shut off, the solubility was maintained, and the compound was dissolved in the organic solvent again.

P-12 was determined by dry metal analysis.
It was found that 1% of TiO ₂ was contained (theoretical value: 50.7%). The molecular weight of this orange solid substance determined by the vapor pressure equilibrium method was 23000 (theoretical value: 23152). The infrared absorption and nuclear magnetic resonance spectra showed that this orange solid substance was a polytitanoxane having a Ti-O-Ti bond as a main chain and having a butoxy group and an acetylacetonato group in a side chain.

Example 13 4.56 g (0.02 mol) of titanium tetraethoxide was charged into a two-necked eggplant type flask equipped with a rotor and a reflux condenser, dissolved in 100 ml of tetrahydrofuran (THF), and heated at 5 ° C. Stirred. At 5 ° C,
0.54 g (0.03 mol) of water with vigorous stirring
Was diluted slowly with 20 ml of THF. After stirring at 5 ° C. for 1 hour, the mixture was refluxed at 66 ° C. for 3 hours to mature the reaction. After cooling, the reaction solution was concentrated under reduced pressure, and 100 ml of benzene was mixed and dissolved. 1.61 g (0.01 mol) of hexamethyldisilazane was added thereto, and the mixture was stirred at 25 ° C. for 1 hour. Then, the solvent was distilled off under reduced pressure to obtain a white solid (P-13) (TiO _4/2 ) ₂ ( C ₂ H ₅
OTiO _3/2 ) ₅ [{(CH ₃ ) ₃ SiO)} ₂ TiO
_2/2 ] ₂ {(CH ₃ ) ₃ SiOTiO _3/2 } ₃ } (CH
_{3) 3} SiO _1/2} to afford the ₁ 2.85 g. It was soluble in benzene, chloroform, ether and THF, but was poorly soluble in hexane. P-13 has a TiO ₂ content of 55.0% (theoretical value of 54.4%), a SiO ₂ content of 28.0% (theoretical value of 27.3%), and a molecular weight of 170.
0 (theoretical 1712).

Comparative Examples 2-4 5.68 g (0.02 m) of titanium tetraisopropoxide
ol), using diethylene glycol dimethyl ether as a solvent, and setting the reaction temperature and aging temperature to the temperatures shown in Table 3, under the same conditions as in Example 3. The results are shown in Table 3.

[0050]

[Table 3]

[0051]

According to the present invention, an improved sol-gel method using a general-purpose titanium tetraalkoxide as a raw material is used to easily synthesize a polytitanoxane having a high titanium content, which is stable against gelation, to provide a solid. This facilitates the workability of the molding and processing steps in storage and material synthesis, and makes it possible to synthesize a titanium oxide material having a higher TiO ₂ content than known polytitanoxane. As a result, since the polytitanoxane can be synthesized and stored in advance, and can be used by dissolving it in a solvent or the like as necessary, the problem of workability due to the change in physical properties of the sol with the passage of time can be solved. Open the applicability of Especially the Ti
Since the O ₂ content is high, the generation of vacancies and defects during firing can be reduced in ceramics as compared with past technologies.

The chelating and silylated derivatives of polytitanoxane differ greatly in physical and chemical properties, such as solubility and stability, from polytitanoxane itself, and are extremely useful for expanding the range of application and for studying the characterization of polytitanoxane. It is.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the compound obtained in Example 3 of the present invention.

FIG. 2 is a ¹ H NMR spectrum of the same.

FIG. 3 is an infrared absorption spectrum of the compound obtained in Example 9 of the present invention.

FIG. 4 is a homonuclear magnetic resonance spectrum.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiro Gunji 2641 Yamazaki, Noda-shi, Chiba F-term in the Faculty of Science and Technology, Tokyo University of Science VW02 VW33 4J030 CC16 CC21 CD11 CE02 CE11 CF02 CF06 CG19 CG29

Claims (3)

[Claims] 1. A titanium tetraalkoxide represented by the general formula Ti (OR) ₄ (R is a monovalent hydrocarbon group having 1 to 12 carbon atoms) in an amount of 1.0 to 1.75 moles. Of water, in the presence or absence of an inorganic or organic acid as a catalyst, in the presence of one or more solvents selected from ether solvents, ketone solvents, and alcohol solvents, from 0 ° C to 30 ° C. General formula (TiO _4/2 ) _w characterized by hydrolysis at a temperature and further aging at a temperature of 60 to 120 ° C.
{(R'O) TiO _3/2 } _x {(R'O) ₂ Ti
O _{2/2 ｙ y} (R′O _1/2 ) _z ｛w, x is 0 or a positive integer, w + x + y> 6, y = 0 to 4, z = 0 to 8), and R ′ in the formula is hydrogen Atom (however, hydrogen atom is 10% of all R '
Does not exceed. ) And a method for producing polytitanoxane represented by｝ comprising a monovalent hydrocarbon group having 1 to 12 carbon atoms. 2. A titanium tetraalkoxide (R is a monovalent hydrocarbon group having 1 to 12 carbon atoms) represented by the general formula Ti (OR) ₄ in an amount of 1.0 to 1.75 moles. Of water, in the presence or absence of an inorganic or organic acid as a catalyst, in the presence of one or more solvents selected from ether solvents, ketone solvents, and alcohol solvents, from 0 ° C to 30 ° C. Hydrolyzing at a temperature, further aging at a temperature of 60 to 120 ° C., and then reacting with a chelating reagent, characterized by the general formula (TiO _4/2 ) _a ｛(R′O) TiO
_{3/2} b {(L) 2} TiO 2/2} c (LTiO 3/2) d
(L) _e ｛a, b, c are 0 or positive integers, a + b + c
+ D> 6, d = 0 to 4, e = 0 to 4, wherein R 'is a hydrogen atom (however, the hydrogen atom does not exceed 10% of all R')
And a monovalent hydrocarbon group having 1 to 12 carbon atoms, L is 5 carbon atoms
Β-diketone comprising the above hydrocarbon group, keto acid ester comprising a monovalent hydrocarbon group having 4 or more carbon atoms, 3 carbon atoms
One or more groups selected from the group consisting of the above oxyacids comprising monovalent hydrocarbon groups, 2-alkoxyethanols comprising monovalent hydrocarbon groups having 1 or more carbon atoms and alkylene glycols having 2 to 6 carbon atoms. For producing a chelated derivative of polytitanoxane. 3. A titanium tetraalkoxide represented by the general formula Ti (OR) 4 (R is a monovalent hydrocarbon group having 1 to 12 carbon atoms) in an amount of 1.0 to 1.75 moles. Of water, in the presence or absence of an inorganic or organic acid as a catalyst, in the presence of one or more solvents selected from ether solvents, ketone solvents, and alcohol solvents, from 0 ° C to 30 ° C. Hydrolyzing at a temperature, further aging at a temperature of 60 to 120 ° C., and then reacting with a silylating agent, wherein the general formula (TiO _4/2 ) _f {(R′O) TiO _3/2 }
_g ｛(R ″ ₃ SiO) ₂ TiO _2/2 ) _h (R ″ ₃ SiO
TiO _3/2 ) _i (R ″ ₃ SiO _1/2 ) _j ｛f, g, h
Is 0 or a positive integer, f + g + h + i> 6, i = 0 to 4,
j = 0 to 4, wherein R 'is a hydrogen atom (however, the hydrogen atom does not exceed 10% of the total R') and a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R "is a total R ' A method for producing a silylated derivative of a polytitanoxane having a hydrocarbon group of 1 to 6 carbon atoms which does not exceed 70% of the above.