JPS58217429A - Manufacture of alkali metallic titanate - Google Patents

Abstract

PURPOSE:To manufacture an alkali metallic titanate having a desired shape and desired physical properties, by mixing or reacting an org. titanium compound with an alkali metallic compound, adding an additive, molding the resulting uniform soln., and calcining it. CONSTITUTION:An org. titanium compound is mixed and/or reacted with an alkali metallic compound in a solvent at room temp. -about 250 deg.C for about 1-15hr with stirring to prepare a uniform precursor soln. The reaction product of titanium tetrachloride with alpha-oxyacid or the like is used as the org. titanium compound, and an alkali metallic hydroxide or the like is used as the alkali metallic compound. A finely powdered alkali metallic titanate is obtd. by thermally decomposing the precursor soln. Desired physical properties and a desired shape can be provided by adding a prescribed additive to the soln. in accordance with the purpose, molding the resulting uniform soln. to the desired shape by spraying or other method, and calcining it.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a manufacturing method, and more particularly to a method for manufacturing an alkali metal titanate compound in a desired shape such as a fine powder, a plate, a thin film, or a fiber.

Alkali metal titanate compounds are attracting attention as materials related to energy, nuclear power, and electronics industries, and among them, lithium titanate, sodium titanate, potassium titanate, etc. are attracting particular attention as materials for electronics due to their unique electrical properties. ing. The methods for producing these alkali metal titanate compounds include hydrothermal method, melting method, sintering method, and flux method (Ceramic Materials Technology Collection 774~
779 pages) Gel firing method (USP ”3737)
520) Although this method is known, it is not an industrially applicable method due to operational reasons and physical properties of the alkali metal titanate compound obtained.

An object of the present invention is to provide an industrial method for producing an alkali metal titanate compound having desired physical properties.

As a result of intensive research to achieve the above objective, the present inventors have found that
Composite oxydialkoxides and their derivatives (patent application Showa 56-788
No. 82, No. 56-78883, No. 56-114108
No. 56-173474, No. 56-176767, No. 56-176768, and No. 57-54976) as starting materials, an alkali metal titanate compound having desired physical properties and shape can be obtained. They found this and completed the present invention.

The present invention involves mixing and/or reacting an organic titanium compound and an alkali metal compound in a solvent in which the raw material mixture or the reaction product is soluble, and adding additives as necessary to form a uniform solution. This is a method for producing an alkali metal titanate compound, which is characterized by molding and firing as necessary.

In the present invention, as the organic titanium compound used as a raw material,
Titanium tetrachloride and α- or β-oxy acids such as lactic acid, glycolic acid, tartaric acid, etc.
- Tris alcohol amine reaction such as amine,
Organotitanium compounds in which all chlorine has been replaced with organic groups, alkoxytitaniums such as tetraisopropoxytitanium, tetrabutoxytitanium, and tetra-2-ethylhexoxytitanium, and β- such as alkoxytitanium and acetylacetone.
diketones, α- or β-ketonic acids such as acetoacetic acid, propionylbutyric acid, etc., and their derivatives, the above-mentioned α
- or β-oxyacids and organic titanium compounds obtained by reaction with chelating agents such as esters, tris alcohol amines, etc. can be used. It is particularly advantageous to use the readily available Tetai tetrachloride and lactic acid stopper reaction product. The alkali metal compounds used as raw materials include alkali metal hydroxides, inorganic salts such as carbonates, nitrates, and sulfates, acetates, and sh! Organic salts such as salts of salts can be used. As the solvent, any solvent that can dissolve the raw material mixture or reaction product can be used. When alkoxy titanium is used as a raw material, alcohols such as methanol, impropatol, butanol, etc. can be used. Water can be preferably used when using an organic titanium compound.

In the present invention, an organic titanium compound and an alkali metal compound are mixed and/or reacted in a solvent,
A homogeneous mixed solution of the raw material compounds or a homogeneous solution of the reaction product is used as a precursor solution for producing an alkali metal titanate compound. When using titanium tetrachloride as a starting material as a titanium source, the reaction between titanium tetrachloride and α- or β-oxyacids or amines can be carried out by mixing reaction equivalents of the raw material compounds at room temperature or with heating. conduct. Since the reaction produces hydrochloric acid as a by-product, it is more preferable to carry out the reaction in a nitrogen stream while removing the generated hydrochloric acid. After the reaction is completed, the organic titanium compound is obtained by drying under reduced pressure to remove the remaining chlorine-containing components.

The resulting organic titanium compound is often not a single compound but a mixture of several reaction products, but it is sufficient if all four chlorine atoms in titanium tetrachloride are replaced with organic compound residues. be. For example, in the reaction between titanium tetrachloride and lactic acid, the formula Ti (OCH(CH8)COOH
)4. Ti (OCH(CH8)COO),,Ti
(OCH(CH3)COOH), (OCH(C8)
A mixture such as C00) is obtained. Helogen radicals in organotitanium compounds generate helogeflated alkali metal compounds by reaction with alkali metal compounds, and when present in large amounts, it prevents a uniform precursor solution, and even in the case of small amounts. Since an excess amount of alkaline earth compound is required, it is preferable to remove as much as possible in a targeted treatment.

The conditions for mixing and/or reacting the organic titanium compound and the alkali metal compound can be changed depending on the type of raw materials, the type of solvent, etc., but are generally at a temperature of room temperature to 300°C, preferably room temperature to 250°C. Stirring is carried out for 0.5 to 30 hours, preferably 1 to 15 hours.

In the present invention, a finely powdered alkali metal titanate compound is obtained by thermally decomposing the precursor solution.

In addition, inorganic or organic metal compounds may be added to the precursor solution to obtain electrical properties, sintering properties, etc. according to the purpose, and polymer compounds may be added to form the desired shape, such as a plate, a thin film, or a fiber. After adding additives such as thickeners and stringability improvers to make a uniform solution, it is molded into the desired shape by spraying, dipping, nozzle blowing, extrusion, etc., and then fired. Thus, an alkali metal titanate compound having desired physical properties and shape can be obtained. The viscosity can also be adjusted by concentrating the solvent without using additives.

The present invention provides a method for producing an alkali metal titanate compound having desired physical properties and shape by a simple operation of forming a precursor, which is a uniform solution, into a desired shape as necessary and then firing it. The industrial significance is extremely large.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the following examples.

Example 1 '200 m equipped with reflux condenser, stirrer and thermometer
9 y of tetraisopropoxyte in 14 flasks:
Ti(OCH(CHa)t)428.411 (0,
100100r and isopropanol: (CH,)
, CHOH30, Oll and potassium acetate: CH, C00K while cooling on ice under N2 gas atmosphere.
4.9 #(0,050rmJ) Oyohimethanol:
A solution consisting of 39.7 g of CH30H was added dropwise over 1 hour, and then the solvent was kept under reflux for 5 hours to give the target compound:! Ti40. Homogeneous precursor solution of 10.0% by weight 103. I got ON. After removing the solvent from the precursor solution by heating under reduced pressure, it was heated from room temperature to 1050°C in air at a heating rate of 300□'C,'Hr.

2T i40. A finely powdered crystal of was obtained.

The obtained Ti40. The X-ray diffraction diagram of is shown in FIG.

Example 2 Tetango tetrachloride 1C419 was added to the same equipment as in Example 1.
011-(0,100rrol) and while flowing N2 gas, lactic acid: CH, CH(OH)COOH36
, 1F (0,401 mol) was added dropwise at room temperature over 1 hour, and then the temperature was raised to 100° C., and the temperature was maintained for 1 hour to obtain a reaction product.

1001 d of water:H2O was added to the reaction product and heated under reduced pressure to remove the solvent and hydrogen chloride in the reaction product. This operation was repeated five times to obtain 40.5 g of a water-soluble organic titanium compound containing almost no halogen radicals. Next, the organic titanium compound has hydroxidizing power! J Ram: KO
35,6g (0,10100r and water: 8203
8.7N was added, and then the mixture was kept under refluxing water for 1 hour to give the target compound a Ti, O, equivalent of 15.0 weight ff.
A homogeneous precursor solution of 84.8 F was obtained. The precursor solution was concentrated under reduced pressure, the solvent was removed until the viscosity reached a point at which spinnability was achieved, and after defoaming, extrusion was performed through a 100μ spinning spout,
The discharged fibers were wound up at a winding speed of 50 m/min while being dried in the air with an infrared lamp. The obtained precursor fiber was heated at 300 oc/1 from room temperature to 850°C.
(It was fired in air at a temperature increase rate of r to obtain Ti, OS fibers.

Example 3 Using the same apparatus as in Example 2 and operating in the same manner, titanium tetrachloride: 19.011 (0,100 blood liters) and lactic acid 31.
6.9 (0,401rrol), a water-soluble organic titanium compound 40.5F was obtained. Lithium carbonate: Li2C0,7.4g (0,100r
rDl) and water: 820172, Og were added at room temperature, then the temperature was raised and the solvent was kept under reflux for 1 hour to obtain the target compound: a homogeneous precursor solution of 5.0% by weight (calculated as Li2TiO3) 21.9 I got g.

A silica glass substrate was immersed in the precursor solution for 5 crn/
The procedure of drying with an infrared lamp in the pulled air at a raising rate of 6.0 mm was repeated twice to form a good precursor thin film. The obtained precursor thin film was heated to 850℃ from room temperature.
A good Li, TiO3 thin film was obtained by firing in air at a heating rate of 3000G/) (r) to
FIG. 2 shows the X-ray diffraction pattern of the Ti03 thin film. The Li, T
The film thickness of the i01 thin film measured by a 5° specular reflection measuring device was 750A.

Example 4 Using the same equipment as in Example 2 and operating in the same manner, tetrachloride, tetay: 19. Og (0,100100r and lactic acid: 3
1.6F (0,401 liters of blood) yielded 40.59% of a water-soluble organic titanium compound. A: 0.5.7 g of NaN (0.067 rrD)
l) and water: Add 020.9 Ii at room temperature, then raise the temperature and hold under reflux of the solvent for 1 hour to obtain a homogeneous precursor solution 67.1 of the target compound: 15.0% by weight calculated as Na2Ti307. & got.

Approximately 0.03 N of polyethylene oxide with an average molecular weight of 3.3 million to 3.8 million was added to the precursor solution, mixed uniformly, defoamed, extruded from a spinning spout with a diameter of 100 μm, and the discharged fiber was heated in the air with an infrared lamp. A rolled precursor fiber was obtained at a winding speed of 50 rrA'nin while drying. The precursor fiber was heated from room temperature to 850°C for 300''
Na and Ti were heated and fired at a temperature increase rate of Q/H.

A fiber of Ol was obtained. The X-ray diffraction pattern of the obtained fiber was measured in Example 5 using the same apparatus as in Example 1 with the formula Ti (OH), (OC
Organic titanium compound represented by H(CH,)COOH) (Ti1ac; manufactured by Nippon Soda ■) 26.0jF (0,
100mo6), potassium oxalate: K, C, O, -
H2O3,1F (0,017+ml) and water: H,
066.5Jl was charged and kept under solvent reflux in an air atmosphere for 1 hour to give the target compound 2, Ti, O□ conversion 1
A homogeneous 0.0% by weight precursor solution of 95.6N was obtained. A silica glass substrate is immersed in the precursor solution, and l Qcm
The operation of drying with an infrared lamp in the pulled air at a pulling rate of /min was repeated three times to obtain a good precursor thin film. The precursor thin film was heated in air for 10 minutes from room temperature.
Ti601. A thin film was obtained. Specifically, Tia
The X-ray diffraction pattern of the Ora thin film is shown in FIG.

In addition, Ti, O
□The thickness of the thin film was 1060A.

[Brief explanation of drawings]

(1) Figure 1 X-ray diffraction diagram of Nari Ti, 07g fine powder (2
) Figure 2 X-ray diffraction diagram of Li, TiO3 thin film (3) 3rd
Figure NatTi30. X-ray diffraction diagram of fiber (4) Figure 4
K, Ti, 0. s X-ray diffraction diagram of thin film Submitted by Nippon Soda Co., Ltd. Inserted by Haruyuki Ito, Yoshiyoshi Yamate, and continued Amendment 1. Indication of the incident 1982 Patent Application No. 99244 2 Name of the invention Alkali titanate Process for producing metal compounds 3, Relationship with the person making the amendment, Patent applicant: 2-2-1 Otemachi, Chiyoda-ku, Tokyo (430) Nippon Shidatsu Co., Ltd. 4, Agent: 2 Otemachi, Chiyoda-ku, Tokyo No. 2-1 (7125) Yoshimi Yokoyama 5, Date of amendment order, Voluntary amendment 6, Number of inventions increased by amendment, 7, i Same as the claim column of the subject specification Detailed explanation of the invention Column 8, Contents of the Amendment (1) The Scope of Claims column is amended as shown in the attached sheet. (2) The Detailed Description of the Invention column is amended as follows: 1) Specification Box 3 Negative No. 7 -Correct "employable" in line 8 to "excellent". 2) "Same equipment" on page 10, line 7 of the specification is corrected to "similar 300 ml 4-hour flask." 3) Change [31,6J on page 10, line 8 of the specification to “36.
Correct to IJ. 4) Replace j21.9 J on page 10, line 14 of the specification with “2
19.9 Corrected to j. 5) "31.6 J" on page 11, line 6 of the specification is replaced with "36
．． Correct to IJ. 6) Add and insert the following Example 6 between the second and third lines from the bottom of page 12 of the specification. Example 6 T i (OH), (OCH
(CH8)COOH)2 (Made by Tilac Nippon Soda)
26.0g (0,100mo+), C5, SO49,
0.01 (0.025 mol) and H.025.1N were charged and refluxed for 1 hour in an air atmosphere to obtain a homogeneous solution 60.119 of 25.0% by weight as the final oxide (C52Ti40.). The resulting homogeneous solution was heated under reduced pressure to remove the solvent, and the temperature was raised from room temperature to 850°C at a rate of 3.
When fired in air at 00°C/hour, C52Ti
40. was gotten. In the claims, an organic titanium compound and an alkali metal compound [provided that the organic titanium compound has the general formula Ti(OR)4 (excluding cases where the substitute is an alkali metal hydroxide), the raw material mixture or the reaction product An alkali titanate characterized by mixing and/or reacting in a soluble solvent, adding additives as necessary to form a homogeneous solution, molding the solution into a desired shape at °C as necessary, and firing. Metal compound manufacturing method 2, the organic titanium compound is titanium tetrachloride and α- or β-
Method 3 according to claim 1, wherein the alkali metal compound is either a reaction product with oxyacids or tris alcohol amines, or a reaction product between alkoxytitaniums or alkoxytitanium and a chelating agent, alkali metal hydroxides,
Method 4 according to claim 1, in which the solvent is water or alcohol, method 5 according to claim 1, in which the solvent is water or an alcohol, and the additives are different. Method 6 according to claim 1, which is a metal compound, a thickener, a stringability/improving agent, etc., and the alkali metal titanate compound to be produced is in the form of fine particles, plates, thin films, fibers, etc. The method according to claim 1, wherein the desired shape of

Claims (1)

[Claims] 1. An organic titanium compound and an alkali metal compound (provided that the organic titanium compound is an alkoxy titanium or a reaction product of an alkoxy titanium and a chelating agent, and an alkali metal compound Except when is an alkali metal hydroxide, the raw material mixture or reaction product is mixed and/or reacted in a soluble solvent, and if necessary, an additive is added to make a homogeneous solvent, and the solution is 2, a method for producing an alkali metal titanate compound characterized by molding the compound into a desired shape as necessary and firing the organic titanium compound, wherein the organic titanium compound is a combination of titanium tetrachloride and α- or β-oxyacids or trisalcohol amines. Method 3 according to claim 1, wherein the alkali metal compound is either an alkoxy titanium or a reaction product of alkoxy titanium and a chelating agent, wherein the alkali metal compound is an alkali metal hydroxide,
Claim 4 as set forth in claim 1, which is an inorganic salt of an alkali metal or an organic salt of an alkali metal; Method 5, as set forth in claim 1, wherein the solvent is water or alcohol; Additives are different types. The method 6 according to claim 1, which is a metal compound, a thickener, a stringability improver, etc., wherein the alkali metal titanate compound to be produced is in the form of fine particles, plates, thin films, fibers, etc. The method according to claim 1, which has a desired shape.