JPH06200030A - Production of silsesquioxane polymer - Google Patents

Abstract

PURPOSE:To obtain a silsesquioxane polymer in good yields by a process of excellent operability. CONSTITUTION:A silsesquioxane polymer is produced by subjecting a silane compound to hydrolysis and subsequent dehydrative condensation in the presence of a hydrate of a metal carboxylate and an oxygenated organic solvent. Thus, a silsesquioxane polymer can be produced in good yields irrespectively of the kind of the silane compound used by a process excellent in operability and performed under mild conditions.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing silsesquioxane polymers.

[0002]

2. Description of the Related Art A silsesquioxane polymer obtained by hydrolyzing and dehydrating and condensing a silane compound represented by the following general formula (1) is used for protection of electronic circuits, materials for interlayer insulating films and the like. The silsesquioxane polymer may be produced by hydrolyzing and dehydrating and condensing phenyltrichlorosilane with sufficient water in an organic solvent (Journal of American Chemical Society, Vol. 82,
Pp. 6194-6195, 1960, Japanese Patent Publication No. 40-1
No. 5989) is known. However, this method is not easy to control the dehydration condensation reaction, the yield of the target product is low, and when a highly reactive one such as alkyltrichlorosilane is used as the silane compound, gelation progresses and the target product is obtained. There were drawbacks such as not being able to obtain.

Therefore, regardless of the type of silane compound,
As a method for obtaining a desired product in a high yield, a method has been developed in which hydrolysis and dehydration condensation of a silane compound are carried out at the interface between a ketone and water (Japanese Patent Laid-Open Publication No. 50-111198). However, in this method, it is necessary to control heating and stirring so as not to destroy the morphology of the interface in order to carry out the reaction under the interface, and there is a drawback that the operability is poor.

On the other hand, a method is known in which a silane compound is cooled to -50 ° C or lower, hydrolyzed in the presence of a basic compound, and then dehydrated and condensed at a high temperature of about 100 ° C. But,
This method has a problem that it is difficult to control the reaction because the condensation is performed at a high temperature.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors in order to solve the above-mentioned drawbacks of the prior art, the hydrolysis and dehydration condensation of a silane compound were carried out by using a hydrate of a carboxylic acid metal salt and an oxygen-containing organic compound. If carried out in the presence of a solvent, it was found that, under mild conditions, the desired product can be obtained in good yield regardless of the type of silane compound by a method with excellent operability, and the present invention is based on this finding. It came to completion.

[0006]

Thus, according to the present invention, a silsesqui characterized in that a silane compound is hydrolyzed and dehydrated and condensed in the presence of a hydrate of a carboxylic acid metal salt and an oxygen-containing organic solvent. A method of making an oxane polymer is provided.

The silane compound as a raw material in the present invention is represented by the following general formula (1).

[Chemical 1] (In the formula, R represents a hydrogen atom or a hydrocarbon residue which may have a substituent, A represents a hydrolyzable group, and x represents 1
Or 2 is shown. )

Specific examples of R include hydrogen atom; alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, heptyl group and nonyl group; vinyl group, propenyl group, Alkenyl groups such as allyl group, butenyl group, methallyl group; alkynyl groups such as ethynyl group, propynyl group, butynyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group; Examples thereof include a hydrocarbon residue such as an aryl group such as a phenyl group and a naphthyl group, or one in which a hydrogen atom of these hydrocarbon residues is substituted with a halogen atom. Among them, the alkyl group and the aryl group are prized.

A is a hydrolyzable group, specifically, a halogen atom such as chlorine, bromine or iodine; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; an alkenyloxy group such as an allyloxy group. An aryloxy group such as a phenoxy group and a naphthoxy group; a cycloalkenyloxy group such as a cyclopentenyloxy group; an acyloxy group such as a formyl group, an acetoxy group and a propionyloxy group. Among them, halogen atoms are prized.

In the present invention, the hydrolysis and dehydration condensation reaction of the silane compound are carried out in the presence of a hydrate of a carboxylic acid metal salt and an oxygen-containing organic solvent. The carboxylic acid metal salt hydrates used are alkali metal salts, alkaline earth metal salts, and transition metal salts of carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, tartaric acid, and benzoic acid. A hydrate such as a salt is exemplified.

The amount of the hydrate of the carboxylic acid metal salt used is 0.1 to 20 mols, preferably 1 mol, relative to 1 mol of the silane compound.
10 to 10 mol.

As the oxygen-containing organic solvent, ketones, ethers, esters and the like are used. Specifically, ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diisopropyl ketone, acetylacetone, cyclohexanone, methylcyclohexanone, and isophorone; dimethyl ether, methyl ethyl ether, diethyl ether, ethyl propyl ether, dipropyl ether, diisopropyl ether, Examples thereof include ethers such as dibutyl ether, diisobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; esters such as ethyl formate, ethyl acetate, propyl acetate, butyl acetate, and ethyl benzoate. Above all,
Ketones are prized. These can be used alone or 2
You may mix and use 1 or more types.

The amount of the oxygen-containing organic solvent used is 1 to 100 times, preferably 1 to 50 times the weight of the silane compound.

The reaction temperature is usually 0 to 60 ° C, preferably 5 to 40 ° C. The reaction time is usually 0.5 to 5 hours.

After completion of the reaction, the desired product can be isolated from the reaction system by a conventional method.

Thus, according to the present invention, the desired product can be obtained in a good yield regardless of the kind of the silane compound by a method having excellent operability under milder conditions than the prior art.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified.

Example 1 0.15 mol of zinc acetate dihydrate and 50 ml of methyl isobutyl ketone were stirred, and at room temperature, 0.1 mol of methyltrichlorosilane diluted to 50 ml of methyl isobutyl ketone was added over 50 minutes. Was dropped. After the dropping, the mixture was stirred for 50 minutes and reacted. After the reaction, the reaction solution was filtered to remove the deposited zinc chloride, the filtrate was washed with water, and the organic layer was dried with magnesium sulfate. As a result, a methylsilsesquioxane polymer having a weight average molecular weight of 21,000 was obtained with a yield of 86%. It was confirmed by infrared absorption spectrum analysis that the polymer was a methylsilsesquioxane polymer.

Example 2 0.15 mol of zinc acetate dihydrate and 50 ml of methyl isobutyl ketone were stirred, and at room temperature, 0.1 mol of phenyltrichlorosilane diluted with 50 ml of methyl isobutyl ketone was added over 50 minutes. Was dropped. After the dropping, the mixture was stirred for 50 minutes and reacted. After the reaction, the reaction solution was filtered to remove the deposited zinc chloride, the filtrate was washed with water, and the organic layer was dried with magnesium sulfate. As a result, a phenylsilsesquioxane polymer having a weight average molecular weight of 1000 was obtained with a yield of 84%. It was confirmed by infrared absorption spectrum analysis that the polymer was a phenylsilsesquioxane polymer.

Claims (1)

[Claims] 1. A process for producing a silsesquioxane polymer, which comprises subjecting a silane compound to hydrolysis and dehydration condensation in the presence of a hydrate of a carboxylic acid metal salt and an oxygen-containing organic solvent.