JPH0368527A - Production of strontium alkoxides - Google Patents

Abstract

PURPOSE:To obtain the title substance useful as ferrite, ceramic dielectric material, etc., from readily obtainable raw materials by blending strontium perchlorate dissolved in an organic solvent with a solution of an alkali metal alkoxide in an alcohol. CONSTITUTION:Strontium perchlorate (A) is dissolved in an organic solvent (e.g. methanol, 2-methoxyethanol, acetone or methyl acetate) and blended with a solution of an alkali metal alkoxide (B) (e.g. lithium alkoxide) in an alcohol at <=60 deg.C to give the title substance. In order to prevent the component B from remaining, the reaction is carried out by using a little excessive amount, <=1.2 times as much as the theoretical amount of the compound A and the perchlorate group can be removed by washing with acetone, etc., without recrystallization. The separation is done in an inert dry atmosphere such as N2 gas and drying and preservation are preferably carried similarly.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing styrontium alkoxides, which have many industrial uses as ferrite, a catalyst for synthesizing ceramic dielectric material 1, and an intermediate raw material therefor. .

[Prior art] Traditionally, alkaline earth metals, including strontium, have generally been produced by directly reacting them with the corresponding alcohol, but there are currently no products that can actually be produced on a commercial scale. is limited to those for which metal materials can be obtained in some form, such as magnesium or calcium. The target styrontium alkoxide is extremely easy to produce if strontium metal is available, but strontium has virtually no use as a metal and cannot be obtained on a commercial scale, so it is not suitable for many useful industrial applications. Although it is expected to have many uses, it has not been put into practical use. It is also possible to convert strontium compounds other than metal strontium, such as halides, into alkoxides by exchange reaction with alkali metal alkoxides as raw materials, but they generally have poor solubility in organic solvents, and alkoxides can be formed using this method. It is difficult to purify and lacks practicality.

[Problems to be Solved by the Invention] As described above, when trying to synthesize styrontium alkoxides in a situation where strontium metal is not available, it is necessary to convert styrontium alkoxides based on existing strontium compounds that are easily available. I have to devise something. Therefore, there has been a need to search for and find strontium compounds that are soluble in organic solvents and capable of exchange reactions with alkali metal alkoxides.

[Means for Solving the Problems] In view of the above-mentioned current situation, as a result of intensive studies, the present inventors found that strontium perchlorate is soluble in commonly used organic solvents, and is particularly soluble in alcohols, such as methanol, ethanol, It is easily soluble or soluble in propanols, butanols, and alkoxy alcohols such as methoxyethanol and nidoxyethanol, and the solution itself is stable and there is little risk of deterioration due to oxidation, and alkali metals They have discovered that they can easily exchange with ions, and have completed the present invention.

That is, the present invention provides a method for producing styrontium alkoxides, which is characterized by mixing strontium perchlorate dissolved in an organic solvent and an alcoholic solution of alkali metal alkoxides to exchange perchlorate groups and alkoxyl groups. The present invention provides a method.

The present invention will be explained in detail below.

In the method of the present invention, strontium perchlorate is dissolved in an organic solvent, and the organic solvents used at this time include methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol.

Alcohols having 1 to 4 carbon atoms such as 2-butanol, 2-methoxyethanol, 2:ethoxyethanol,
Alkoxy alcohols such as 2-propoxyethanol, 2-impropoxyethanol, 2-butoxyshetanol, 2-isobutoxycetanol, acetone, ketones such as methyl ethyl ketone, methyl acetate, ethyl acetate,
Examples include acetate esters such as propyl acetate and butyl acetate.

Next, the strontium perchlorate solution and the organic solvent solution of alkali metal alkoxides are mixed, and examples of the alkali metal alkoxides used at this time include lithium alkoxide, sodium ♦ alkoxide, and potassium alkoxide. Also, the alcohol used to form these alkoxides is methanol.

Ethanol, 1-propanol, 2-propanol, 1
-Alcohols having 1 to 4 carbon atoms such as butanol and 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, and 2-isopropoxyethanol.

Examples include alkoxy alcohols such as 2-butoxyshetanol and 2-isobutoxycetanol.

As the organic solvent for dissolving the alkali metal alkoxides, the above-mentioned alcohols are used.

This reaction is extremely rapid and can be completed at room temperature. Although heating is not necessary, it is preferable to heat the reaction to an extent that does not induce oxidation by perchloric acid. 6
If the temperature is 0° C. or lower, there will be almost no coloration due to oxidation, and it is desirable to carry out the reaction at this temperature or lower.

In order to avoid residual alkali metal alkoxide when proceeding with this reaction, it is desirable to use a slight excess of strontium perchlorate compared to the theoretical amount in the compounding ratio during the reaction. This results in the contamination of perchlorate groups, making purification difficult. As a result of various studies, it was found that perchloric acid groups can be removed by washing with acetone or the like without recrystallization if the amount is within 1.2 times the theoretical amount. Therefore, it is possible to facilitate isolation and purification by adjusting the solvent composition so that either the styrontium alkoxide or the alkali perchlorate produced during this reaction is separated and precipitated.

Perchlorates of alkali metals other than potassium are easily soluble in oxygen-containing organic solvents other than ethers, whereas styrontium alkoxides are lower alkoxyl groups whose alkoxyl groups have 1 to 4 carbon atoms. In the case of , they generally have poor solubility and precipitate as the reaction progresses, so they can be separated by filtration. On the other hand, when the alcohol forming the alkoxide is an alkoxy alcohol, the corresponding styrontium alkoxide is easily or soluble in organic solvents other than acetone, but is poorly soluble in acetone, so after the reaction is completed, Separation can be achieved by adding acetone and causing precipitation, or by adding an aromatic solvent such as benzene to the residue after solvent removal and eluting the target substance, as it is well soluble in aromatic solvents. I can do it. When the alkali metal is potassium, we take advantage of the fact that the potassium perchlorate produced by the exchange reaction is extremely poorly soluble, and at the same time this potassium perchlorate is produced, it precipitates and settles, leaving styrontium alkoxide on the solution side. This allows you to separate the two. This styrontium alkoxide solution is isolated by concentrating it or by adding a poor solvent such as acetone or methyl ethyl ketone to cause precipitation.

A normal filtration method may be used as a separation method, but the target styrontium alkoxide itself is sensitive to moisture and easily hydrolyzed, and furthermore, it easily absorbs carbon dioxide gas, so N
It is important to carry out the process under an inert dry atmosphere such as 2 gas. The separated styrontium alkoxide is preferably dried and stored under an inert dry atmosphere.

[Effects of the Invention] As mentioned above, in the present invention, easily available strontium perchlorate is used in place of unobtainable metal strontium, and by carrying out an exchange reaction with an alkali metal alkoxide, the objective can be achieved. Strontium ◆ is used as an alkoxide, which can be used in ferrite and ceramic dielectrics.

Facilitates use as a catalyst for synthesis and other raw materials.

[Examples] Hereinafter, the content of the present invention will be explained in detail and concretely using Examples, but the scope of technical application of the present invention is not limited by these.

Example 1 300 ml of sufficiently dehydrated anhydrous methanol was placed in a 1000 ml four-loop flask, and N2 gas was introduced to create an inert atmosphere. Next, high purity metallic sodium 2
A sodium methoxide solution was prepared by weighing out 3 g and reacting it at room temperature. This sodium
Strontium perchlorate anhydrous in methoxide solution
A solution of 43.3 g dissolved in 300 ml of acetone was injected at room temperature while stirring. Strontium methoxide precipitated at the same time as the injection, and the system turned into a cloudy slurry.

The heat generated by the reaction during this time was extremely small, and there was no need for cooling. After continuing the reaction at room temperature for 2 hours, it was filtered under an inert atmosphere of N2 gas to obtain strontium methoxide as a white crystalline substance. In order to remove some perchloric acid mixed in, redispersion was performed with acetone.
After refiltration, the product was dried under reduced pressure to obtain 69 g of strontium methoxide as a white crystalline powder. The yield was 92.2% based on sodium.

Similar results were obtained by injecting the sodium methoxide solution into the acetone solution of strontium perchlorate instead of injecting the strontium perchlorate solution into the upper sodium methoxide solution to perform the reaction.

Example 2 The alcohol used in Example 1 was replaced with ethanol, and the same procedure was carried out to obtain 78 g of crystalline powder of strontium ethoxide.

The yield based on sodium metal was 87.8%.

Example 3 The alcohol used in Example 1 was replaced with normal butanol (
The same procedure was carried out except that strontium perchlorate was dissolved in 500 ml of acetone instead of strontium perchlorate (1-butanol) to obtain 104 g of crystalline powder of strontium/1-butoxide.

The yield was 89% based on sodium metal.

Example 4 After introducing N2 gas into a 1000 ml fourth flask to create an inert atmosphere, 20'Oml of sufficiently dehydrated ethylene glycol dimethyl ether and 39 g of metallic potassium were added.
was weighed out, and 200 ml of dehydrated 2-methoxyethanol (methylcellosolve) was slowly injected to react, producing a potassium ethoxide solution. 30% of 2-methoxyethanol was prepared by dehydrating 143.3g of anhydrous strontium perchlorate from this potassium-2-methoxyethoxide solution.
The solution dissolved in 0 ml was injected at room temperature while stirring.

As the reaction progressed through injection, potassium perchlorate was gradually formed and the system became a cloudy slurry. As in the previous example, the heat generated by the reaction was extremely small and could be virtually ignored by adjusting the injection speed. After the injection was completed, the reaction mixture was aged at room temperature for 4 hours, and then filtered in an inert atmosphere using N2 gas to remove precipitated potassium perchlorate to obtain strontium 2-methoxyethoxide as a solution.

By removing the solvent from this solution under reduced pressure, strontium 2-methoxyethoxide 110 was obtained as a light brown lumpy substance.
．． 4g was obtained. Yield is 92% based on metallic potassium
, 8%. This strontium ethoxide was easily soluble in alcohols such as methanol and ethanol, alkoxy alcohols such as 2-methoxyethanol, and aromatic systems such as benzene and toluene.

Example 5 The alkoxy alcohol used in Example 4 was replaced with 2-ethoxyethanol (Ethyl Celsolve), and the same procedure was carried out to obtain 125 g of a solid substance of strontium/2-ethoxy ethoxide. The yield was 94% based on potassium metal. This strontium
2-Ethoxyethoxide was easily soluble in aromatic systems such as benzene and toluene as well as alcohols and alkoxy alcohols.

Example 6 The alcohol used in Example 4 was replaced with 2-butoxycetanol (butyl cellosolve) and the same procedure was carried out to obtain 154.6 g of brown crystals of strontium 2-butoxy ethoxide. Obtained. The yield was 96% based on potassium metal. This strontium 2-butoxyethoxide is easily or soluble in alcohols, alkoxy alcohols, aromatic and other solvents, but is insoluble or poorly soluble in aliphatic hydrocarbons.

Claims (1)

[Claims] A method for producing styrontium alkoxides, which comprises mixing strontium perchlorate dissolved in an organic solvent and an alcoholic solution of alkali metal alkoxides to exchange perchlorate groups and alkoxyl groups.