JPS61241327A - Production of cohydrolyzate of chlorosilane - Google Patents

Abstract

PURPOSE:To obtain the titled hydrolyzate useful as an oil or a resin, by adding a tertiary alcohol alone or it, water and a primary alcohol or a secondary alcohol to a mixture of specific silane compounds and decomposing the mixture with water formed by the reaction. CONSTITUTION:A tertiary alcohol (preferably t-butanol) and a small amount of water or a primary alcohol or a secondary alcohol to a mixture of (A) a compound (e.g., silicon tetrachloride, etc.) shown by the formula RmSi(OR ')nCl4-m-n (R is H, alkyl or aryl; OR' is alcohol residue; 0<=m<=2; 0<=m+n<=4) and (B) a compound (e.g., trimethylchlorosilane, etc.) shown by the formula R<1>R<2>R<3>SiC (X is Cl, OSiR<1>R<2>R<3>, or alcohol residue; R<1>-R<3> are alkyl, aryl or H) and the reaction is carried out preferably in an organic solvent such as toluene, etc., to give the aimed hydrolyzate. An alcohol and an organic carboxylic acid are added to the mixture of the components A and B, which may be hydrolyzed with water formed by the esterification.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a cohydrolyzate by decomposing silicon tetrachloride or a mixture of alkylchlorosilane and trimethylchlorosilane, for example, with water produced by the reaction without directly adding water.

Various silicone products are manufactured by hydrolyzing chlorosilane or alkoxysilane.
-OH or 5i-0-5i bond. The present inventors did not directly add water, but used water generated in one reaction to hydrolyze the compound in a more uniform state.

From a mixture of silicon tetrachloride and trimethylchlorosilane,
It was discovered that liquid or resinous siloxanes can be obtained, leading to the present invention.

That is, the present invention provides the general formula R■5i(OR')nC14
-m-n (R is hydrogen, alkyl, phenyl, OR1
is an alcohol residue, a silane compound represented by 0≦m≦2, 0≦m+n≦4) and the general formula R1R"R' SiX
(XgtCI, 05iR'R"R".

Alcohol residues, R', R'', and R3 are alkyl.

A method for producing a co-hydrolyzate characterized by decomposing a mixture of silane compounds represented by phenyl, hydrogen) with a tertiary alcohol alone or mixed with water or a primary or secondary alcohol. This is what we intend to provide.

The present invention also includes: General formula RmSi(OR')nC14-m
-n (R is hydrogen, alkyl, phenyl, OR3 is an alcohol residue, 0≦m≦2.0≦m+n≦4) and a silane compound represented by the general formula RL R*R” SiX (Xjt
CI, 08iR1R"R", furucol residue, R'
, R", R" is alkyl, phenyl, hydrogen), a co-hydrolyzate is produced by mixing an alcohol and an organic carboxylic acid with a mixture of silane compounds, esterifying the mixture, and hydrolyzing the resulting water with the resulting water. The purpose is to provide a manufacturing method.

General formula RmSi(OR')nC14-m in the present invention
As the silane compound represented by -n (R is hydrogen, alkyl, allyl, OR3 is an alcohol residue, 0≦m≦2.0≦m+n≦4), the following are usually used.

Tetrachlorosilane (silicon tetrachloride), alkoxytrichlorosilane, dialkoxydichlorosilane, trialkoxychlorosilane, tetraalkoxysilane (alkyl silicate) Silane compounds in which the chloro or alkoxy group of these compounds is substituted with one or two R groups etc. are used.

Here, as the R group, hydrogen, methyl, ethyl, vinyl, phenyl, etc. are usually used, but the present invention is not limited thereto.

General formula R1R"R"SiX (X is CI, 081g
1RI R3, or alcohol residue, R1゜R2, R
Typical examples of silane compounds represented by 2 (alkyl, phenyl, hydrogen) are trimethylchlorosilane and hexamethyldisiloxane. Generally R″, R″,
Compounds in which R'' is hydrogen, methyl, ethyl, vinyl, phenyl, etc., and at, R2, and R3 are the same or different are used.

General formula RmSi(OR')nC14-m in the present invention
-n (R is hydrogen, alkyl, allyl, OR'' is an alcohol residue, 0≦m≦2, 0≦m + n≦4), the general formula R'R"R" SiX
(, X is C1,08iR'R'' R3 or alcohol residue, R1, R'', R'' is alkyl, phenyl,
If a large amount of a silane compound (hydrogen) is used, the cohydrolyzate becomes a siloxane compound that can be distilled, and as the amount is reduced, it has a high boiling point and becomes a solid resinous material.

When the silane compound represented by the general formula RmSi(OR')nCl4-m-n is, for example, silicon tetrachloride or ethyl silicate, or a mixture thereof, the general formula Ri
For example, if trimethylchlorosilane is used in an amount of 0.3 molar equivalent or less as the silane compound represented by R''R'SiX, toluene-insoluble silica will be obtained.

In the present invention, a third silane compound is added to the mixture of these silane compounds.
alcohol alone or with water or primary or secondary alcohol.
Decomposes silane compounds by mixing with alcohol. It is convenient to use tertiary butyl alcohol as the tertiary alcohol. This tertiary butyl alcohol reacts with the 5i-C1 bond to generate MCI, which in turn reacts with tertiary butyl alcohol to generate water and tertiary butyl chloride. This water decomposes the silane compound. However, the reaction between the 5i-C1 bond and tertiary butyl alcohol does not proceed quickly, so water or primary or secondary alcohol that is easily reacted with 5 is added.
When reacted with iC1 to promote the occurrence of MCI, the reaction proceeds rapidly. Therefore, it is natural that the present invention can be carried out using a method in which a tertiary alcohol is added to a mixture of alkoxysilane compounds instead of a chlorosilane compound, and HCI gas is introduced. The amount of tertiary alcohol to be hydrolyzed is 5i-C1 and 5i-(OR').
(7) It is sufficient if the mole is equivalent to that of the bond, but there is no problem even if more than this is used. A partial hydrolyzate can also be obtained by reducing the amount of tertiary alcohol.

Primary and secondary alcohols promote the generation of HCI in the early stage of the reaction, and it is only necessary to use an appropriate amount, and there is no need to use a particularly large amount.If water is used, they will directly hydrolyze and will This reacts with tertiary alcohol to produce water and promote hydrolysis. Therefore, although the amount of tertiary butyl alcohol can be reduced by using water, the amount of water is limited in order to carry out the reaction in a homogeneous solution.

The present invention also provides the general formula RmSi(OR')nC14-m-
A method is used in which a mixture of a silane compound represented by n and a silane compound represented by R'R'' R35iX is mixed with an alcohol and an organic carboxylic acid, and the mixture is esterified and hydrolyzed with the resulting water. Methyl alkosyl and ethyl alcohol are conveniently used.

These include propyl alcohol and butyl alcohol. The organic carboxylic acid is not particularly limited, but acetic acid is convenient. The amount of alcohol and organic carboxylic acid to be used is sufficient to be equimolar to the S x -C1# S x -(OR') bond. Although more than this amount may be used, excessive water will be produced, which will cause operational difficulties. It is advantageous to use amounts ranging from z molar amounts to equimolar amounts and to work under conditions such that water does not separate. A partial hydrolyzate can also be obtained using a smaller amount of z molar equivalents or less.

Furthermore, when using a compound having a 5i-(OR') bond, it is natural that the amount of alcohol can be reduced.

Furthermore, the amounts of alcohol and organic carboxylic acid used can be reduced by adding a small amount of water under conditions that provide a homogeneous solution.

It is convenient to use organic solvents in carrying out the invention. Hydrocarbon solvents are organic solvents.

Esters, ethers, ketones, etc. can be used. Examples of hydrocarbon solvents used include hexane, heptane, benzene, toluene, and xylene.

The results of this invention are siloxane compounds ranging from ruthless liquids to high boiling liquids and solid resins for use as oils and resins.

EXAMPLES In order to explain the present invention in more detail, examples will be given and explained below.

Example 1 14.5 g of silicon tetrachloride and 52 l of trimethylchlorosilane are added to 100 ml of toluene to form a solution. Add to this 80 ml of tertiary butyl alcohol and 3 ml of ethyl alcohol.
A solution of 1 part (1) and 50 parts (1 part) of toluene was added, and the mixture was left at room temperature overnight. After boiling the solvent, the boiling point is 40℃~65℃/2m
18.5 g of mHg portion and 1 g of residue were obtained.

Example 2 In Example 1, 13 ml of trimethylchlorosilane was added. Working as in Example 1 using 50 ml of tertiary butyl alcohol, 8 g of a liquid residue with a boiling point of 110 DEG C. to 140 DEG C./2+smHg was obtained.

Example 3 In Example 1, trimethylchlorosilane 6°5■1.
The procedure was as in Example 1 using 50 l of tertiary butyl alcohol to obtain 9 g of a viscous liquid.

Example 4 21 g 5 h of phenyltrichlorosilane, 12.7 μl of trimethylchlorosilane, 50 μl of toluene, 40 μl of tertiary butyl alcohol, ethyl alcohol≦ml,
A solution of 50 μl of toluene was added and left overnight. Since the mixture was separated into two layers, the upper layer was removed and the solvent was removed. Boiling point 150℃
~190°C/2mmHg portion 6g and viscous liquid 11.
5g was obtained.

Example 5 The procedure of Example 4 was repeated using 13+wl of vinyltrichlorosilane and 1.5μl of trimethylchlorosilane to obtain 9.5g of a viscous liquid.

Example 6 Methyltrichlorosilane 11.8ml, trimethylchlorosilane 1. Proceed as in Example 4 using ≦ml to obtain 8 g of toluene soluble solid.

Example 7 A solution of 30 μl of tertiary butyl alcohol, 3 ml of ethyl alcohol, and 30 ml of toluene was added to a solution of 14.5 g of silicon tetrachloride, 2≦ml of hexamethyldisiloxane, and 100 ml of toluene, and the mixture was heated overnight. love the solvent,
20.5 g of viscous liquid was obtained.

Example 8 14.6 g of ethyl silicate, 3.4 g of silicon tetrachloride
, 4 liters of trimethylchlorosilane and 80 m of toluene
Add 7 ml of ethyl alcohol to the solution in step 1.

100 ml of a toluene solution containing 20-1 acetic acid was added and left overnight. After distilling off the solvent, 7 g of a toluene-soluble white solid was obtained.

Claims (1)

[Claims] 1) General formula RmSi(OR')nCl_4_-_m_-
__n (R is hydrogen, alkyl, allyl, OR' is alcohol residue, 0≦m≦2, 0≦m+n≦4) and the general formula R^1R^2R^3SiX (X is Cl
, OSiR^1R^2R^3, alcohol residue, R^1
, R^2, R^3 are alkyl, allyl, hydrogen) by adding tertiary alcohol alone to a mixture of silane compounds,
Alternatively, a method for producing a co-hydrolyzate characterized by mixing and decomposing it with water or a primary or secondary alcohol. 2) General formula RmSi(OR')nCl_4_-_m_-
__n (R is hydrogen, alkyl, allyl, OR' is alcohol residue, 0≦m≦2, 0≦m+n≦4) and the general formula R^1R^2R^3SiX (X is Cl
, OSiR^1R^2R^3, alcohol residue, R^1
, R^2, R^3 are alkyl, allyl, hydrogen), a cohydrolysis characterized by mixing an alcohol and an organic carboxylic acid with a mixture of silane compounds, esterifying the mixture, and hydrolyzing it with the water produced. How things are made.