JPH0892153A - Production of alkaline earth metallic salt of organic acid - Google Patents

Abstract

PURPOSE: To economically obtain a solution of an alkaline earth metallic salt of an organic acid, containing an alkaline earth metal at a high concentration and useful as a precursor of an alkaline earth metallic oxide in the fields of fine ceramics or electronic materials. CONSTITUTION: The characteristics of this method for producing an alkaline earth metallic salt of an organic acid comprises reacting a 4-10C organic acid with an alkaline earth metallic salt in a stoichiometrically excessive amount of 0.1-1.0mol in reacting the organic acid with the alkaline earth metallic salt in a reactional solvent and producing the alkaline earth metallic salt of the organic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organic acid alkaline earth metal salt, which is useful as an alkaline earth metal oxide precursor in the field of fine ceramics or in the field of electronic materials.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an alkaline earth metal salt of an organic acid, a solvent such as xylene or mineral spirit is used as a reaction solvent, an organic acid having 10 or less carbon atoms is used, and a metal salt for the organic acid is theoretically chemistry Less than equivalent, ie 1
A method of obtaining a uniform solution by reacting less than a molar amount. Further, a method of reacting an aliphatic monocarboxylic acid having 12 to 30 carbon atoms with an alkaline earth metal salt without a reaction solvent (JP-A-4-20).
No. 8246) has been proposed.

[0003]

However, the above-mentioned method using xylene or mineral spirit as a reaction solvent can only obtain an organic acid metal salt having a low alkaline earth metal content. Further, an organic acid according to JP-A-4-208246 is heated and stirred while an oxide of an alkaline earth metal,
The method of adding hydroxide, carbonate, etc. can react an excess of alkaline earth metal salt with an organic acid to produce an organic acid alkaline earth metal salt, but the product is solid at room temperature. Is.

[0004]

Means for Solving the Problems The present invention has been earnestly studied for the purpose of obtaining an organic acid alkaline earth metal salt solution containing an alkaline earth metal at a high concentration, and as a result of the research, an oxide of an organic acid and an alkaline earth metal, In the reaction of hydroxide or carbonate, 1.1 to 2 mol of the alkaline earth metal salt is used per 2 mol of the organic acid by using the reaction solvent having a boiling point of 160 ° C. or higher, that is, the alkali metal is based on 2 mol of the organic acid. This is because it was found that the metal salt can react at 1 mol or more, which is the theoretical chemical equivalent.

That is, according to the present invention, an organic acid and an alkaline earth metal salt are reacted in a reaction solvent to produce an organic acid alkaline earth metal salt. The theoretical equivalent of metal salt is 0.1 to 0.1
A method for producing an alkaline earth metal salt of an organic acid, which comprises reacting in an excess of 1.0 mol. Generally, the reaction molar ratio of the organic acid and the alkaline earth metal salt is less than 1.0 mol of the alkaline earth metal salt with respect to 2 mol of the organic acid in terms of theoretical chemical equivalent, and the metal content in the reaction product is Has been determined stoichiometrically. However, in the present invention, the organic acid 2
Since it has become possible to react up to 2 moles of the alkaline earth metal salt with respect to the moles, the metal content is the excess reaction rate, that is, the metal content corresponding to 0.1 to 1 mole of the alkaline earth metal salt. Get higher However, simply increasing the excess ratio of the alkaline earth metal salt tends to cause solidification during the reaction, and in extreme cases, stirring cannot be performed. In the present invention, this is to avoid solidification during the reaction by using an organic solvent having a boiling point of 160 ° C. or higher as the reaction solvent.

The actual reaction is carried out at room temperature to 150 ° C. for 5 to 60 while stirring the organic acid and the alkaline earth metal salt in the reaction solvent.
It can be performed only by holding for minutes, but it is preferably performed at 50 to 100 ° C. The order of addition of the raw materials is not particularly limited, while stirring the reaction solvent and the organic acid with heating, a method of reacting by adding a slurry of an alkaline earth metal salt, or conversely while stirring a slurry of an alkaline earth metal salt. Any method of adding an organic acid may be adopted. The dehydration after the reaction may be performed by heating and stirring at 50 to 200 ° C. under normal pressure or reduced pressure, if necessary, and there is no particular limitation.

The organic acid used in the present invention has 4 to 4 carbon atoms.
Saturated monocarboxylic acid of 10 is desirable, for example, isoheptanoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, isodecanoic acid, isoundecanoic acid, isotridecanoic acid, octylic acid, 2,
2-dimethylpropionic acid, n-heptanoic acid, n
Nonanoic acid, naphthenic acid, tall oil fatty acid can also be used. Further, they may be used alone or in combination of 1 or 2 or more.

As a raw material for alkaline earth metal salts such as magnesium, calcium, strontium and barium, respective oxides, hydroxides, carbonates and acetates can be used. In order to improve the dispersibility when added, it is desirable to use it in advance as a uniform slurry of an organic solvent or water.

The organic solvent used as the reaction solvent is one in which the reaction product is dissolved and has a boiling point of 160 ° C. or higher and is not particularly limited. For example, ethylene glycol, butyl carbitol, butyl carbitol acetate, terpineol, n. Paraffin or the like may be used alone or in combination of two or more. In that case, the viscosity becomes lower than that when a solvent having a boiling point of less than 160 ° C., for example, xylene is used in the same amount. It is also possible to use a solvent having a boiling point of 160 ° C or higher and a solvent having a boiling point of less than 160 ° C in combination.

[0010]

【Example】

Example 1 100 g of naphthenic acid (acid value 200) and 9 g of butyl carbitol were charged into a 300 ml reaction beaker equipped with a reflux condenser and heated to 40 to 60 ° C. with stirring, and then 11.7 g of magnesium oxide and 20 g of water. The uniform slurry was gradually added and then reacted at 50 to 95 ° C for about 60 minutes. After that, the temperature was raised to 150 ° C. to dehydrate, and then cooled to about 50 ° C. After that, it was diluted with 50 g of n-hexane and filtered under reduced pressure using diatomaceous earth (Radiolite 900). As a result of concentrating the filtrate with a rotary evaporator, a brown transparent solution containing 5.5% of magnesium was obtained.

Example 2 Octylic acid (acid value 385) 1 was placed in the same reaction vessel as in Example 1.
00 g and terpineol 20 g were charged, the temperature was raised to 40 to 60 ° C. with stirring, and then magnesium oxide 29.9 g
A uniform slurry of 35 g of water and 35 g of water was gradually added, and then the mixture was reacted at 50 to 95 ° C. for about 60 minutes. The temperature was further raised to 120 ° C., dehydrated and then cooled to about 50 ° C. Then Example 1
As a result of diluting in the same manner as above, filtering and concentrating, a pale yellow transparent liquid having a magnesium content of 11.5% was obtained.

Example 3 In the same reaction vessel as in Example 1, secanoic acid (acid value 38
5) 75 g and butyl carbitol acetate 65 g were charged, the temperature was raised to 40 to 60 ° C. with stirring, and then a uniform slurry of calcium hydroxide 28.6 g and n-hexane 40 g was gradually added, and then 50 to 95 ° C. About 60
It reacted for a minute. Dilution, filtration, and
As a result of concentration, a colorless transparent liquid containing 9.5% calcium was obtained.

Example 4 The same reaction vessel as in Example 1 was charged with 75 g of octylic acid and 77 g of butyl carbitol and stirred at room temperature for 40-6.
After the temperature was raised to 0 ° C., 103 g of strontium hydroxide was gradually added, and then the mixture was reacted at 50 to 95 ° C. for 60 minutes. After that, dilution, filtration, and concentration were carried out in the same manner as in Example 1, and as a result, a colorless transparent liquid containing 17% of strontium was obtained.

Example 5 60 g of octylic acid and 72 g of butyl carbitol were charged in the same reaction vessel as in Example 1, the temperature was raised to 40 to 60 ° C. with stirring, 98 g of barium hydroxide was gradually added, and then 50 to 95. The reaction was carried out at 60 ° C for 60 minutes. After that, dilution, filtration, and concentration were performed in the same manner as in Example 1, and as a result,
A colorless transparent liquid containing 2% was obtained.

Example 6 Neodecanoic acid (acid value 320) was placed in the same reaction vessel as in Example 1.
Charge 80 g and 69 g of mineral spirits, heat to 40-60 ° C with stirring, and then add 28 g of calcium hydroxide.
A uniform slurry consisting of 40 g of n-hexane and 40 g of n-hexane was gradually added, and then reacted at 50 to 95 ° C. for about 60 minutes. Then, the mineral spirit was refluxed to raise the temperature to 140 ° C. for dehydration. As a result of filtration by the same method as in Example 1, a pale yellow transparent liquid containing 8.0% of calcium was obtained.

Example 7 The same reaction vessel as in Example 1 was charged with 60 g of isoheptanoic acid (acid value 430) and 94.3 g of terpineol,
After the temperature was raised to 40 to 60 ° C. with stirring, a uniform slurry of 60 g of barium hydroxide and 40 g of n-hexane was gradually added, and then reacted at 50 to 95 ° C. for about 60 minutes.
Then, the temperature was raised to 140 ° C. for dehydration. As a result of performing filtration and concentration in the same manner as in Example 1, 23.0% of barium was obtained.
% Pale yellow transparent liquid was obtained.

Comparative Example 1 (Comparative Example of Example 1) Under the conditions of Example 1, 100 g of naphthenic acid (acid value 20
In contrast to 0), operation was performed under the same conditions as in Example 1 except that 7.7 g of magnesium oxide was used. The content of magnesium in the resulting solution was 3.5%. Comparative Example 2 (Comparative Example of Example 1) Under the conditions of Example 1, the reaction was carried out without using butyl carbitol. As a result, the reaction product solidified in the initial stage of the reaction and stirring became impossible.

Comparative Example 3 (Comparative Example of Example 2) 100 g of octylic acid was mixed with 14.3 g of magnesium oxide.
It operated under the same conditions as in Example 2 except that 8 g was used. The resulting solution had a magnesium content of 5.1%.

Comparative Example 4 (Comparative Example of Example 2) Of the conditions of Example 2, terpineol was changed to xylene to react, and the same conditions as in Example 2 were used. As a result, a solid having a magnesium content of 11% was obtained.

Comparative Example 5 120 g of acetic acid was charged into the same reaction vessel as in Example 1, and while stirring at room temperature, a slurry of 74 g of calcium hydroxide and 100 g of xylene was added, and the temperature was raised to 100 ° C. to react. However, it became cloudy, and the stirring was continued for 30 minutes, but it did not become transparent.

Comparative Example 6 Stearic acid (acid value 204) was placed in the same reaction vessel as in Example 1.
When 100 g was charged and dissolved by heating, 7.8 g of magnesium hydroxide was added at 90 ° C. with stirring, the mixture was reacted for 30 minutes, heated to 110 ° C. and dehydrated, and 50 g of xylene was added little by little. It became a paste.

[0022]

INDUSTRIAL APPLICABILITY An organic acid alkaline earth metal salt solution containing a high concentration of alkaline earth metal, which is useful as an alkaline earth metal oxide precursor in the field of fine ceramics and electronic materials, is economically prepared. I got it.

Claims (2)

[Claims] 1. A method for producing an organic acid alkaline earth metal salt by reacting an organic acid and an alkaline earth metal salt in a reaction solvent, wherein an alkaline earth metal salt is added to an organic acid having 4 to 10 carbon atoms. Is a stoichiometrically stoichiometrically equivalent to 0.1 to 1.0 molar excess, and a method for producing an alkaline earth metal salt of an organic acid. 2. The method for producing an organic acid alkaline earth metal salt according to claim 1, wherein an organic solvent having a boiling point of 160 ° C. or higher is used as a reaction solvent.