JPH08157484A - Production of silane containing organoxy group - Google Patents

Abstract

PURPOSE: To provide a method for producing a high-purity silane containing an organoxy group with good productivity by which the production of bubbles formed during reaction is suppressed and a siloxane oligomer that is a reactional by-product is further hardly produced. CONSTITUTION: This method for producing a silane, containing an organoxy group and represented by the general formula Ra Si(OR<2> )(4-a) [R is the same or different monovalent hydrocarbon group; R<2> is a substituted or an unsubstituted monovalent hydrocarbon group; a is an integer of 0-3] is to react (A) a halosilane represented by the general formula Ra SiX(4-a) [R and a are as previously defined; X is a halogen atom] with (B) a hydroxy compound represented by the general formula R<2> OH (R<2> is as previously defined) in the presence of (C) a polymer, which contains fluorine atom bound to carbon atom and is a liquid at normal temperature.

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 organooxy group-containing silane, and more particularly to a method for producing an organooxy group-containing silane with good productivity from a halosilane and a hydroxy compound.

[0002]

2. Description of the Related Art Organo group-containing silanes such as alkoxysilane and phenoxysilane are water repellents and
It is often used as a surface treatment agent. Conventionally, this type of compound is a direct reaction of a halogenated hydrocarbon with metallic silicon,
Reaction of metallic silicon with hydrogen halide, in the presence of a catalyst,
It was mainly produced by reacting a halosilane synthesized by a hydrosilylation reaction of an alkene or alkyne with a halosilane having a silicon-bonded hydrogen atom with a hydroxy compound (dehydrohalogenation reaction). However, according to this method, bubbling due to the hydrogen halide gas generated during the dehydrohalogenation reaction and the vaporized hydroxy compound is severe, and thus the amount of the hydroxy compound supplied to the reactor per unit time must be reduced. However, there was a problem that productivity was poor.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above problems, the present inventors have found that when a specific fluorine atom-containing polymer is present in the above reaction, foaming during the reaction occurs. The inventors have found that the amount of siloxane oligomer, which is a by-product of the reaction, can be suppressed, and that a high-purity organooxy group-containing silane can be obtained. That is, an object of the present invention is to provide a method for producing an organooxy group-containing silane with high productivity without the above problems.

[0004]

Means for Solving the Problem and Its Action The present invention provides (A) a general formula: R _a SiX _(4-a) (wherein R is the same or different monovalent hydrocarbon group, and X is A halosilane represented by a halogen atom and a is an integer of 0 to 3) and (B) a general formula: R ² OH (wherein, R ² is a substituted or unsubstituted monovalent hydrocarbon group). ) Is reacted with a hydroxy compound represented by the formula (C) in the presence of (C) a liquid polymer containing a carbon atom-bonded fluorine atom at ordinary temperature: R _a Si (OR ² ) _{(4-a )} (In the formula, R, R ² and a are the same as above.) The present invention relates to a method for producing an organooxy group-containing silane.

To explain this, it is used in the present invention.
The halosilane of the component (A) is a starting material of an organooxy group-containing silane, and in the above formula, R is a monovalent carbon atom such as an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a phenyl group or a tolyl group. A hydrogen group, of which 1 to 3 carbon atoms
0 monovalent hydrocarbon radicals are preferred. X is a halogen atom such as chlorine or bromine, and among these, chlorine is preferable. a
Is an integer of 0 to 3. Examples of the halosilane include tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethyltrichlorosilane, ethylmethyldichlorosilane, ethyldimethylchlorosilane, propyltrichlorosilane, propylmethyldichlorosilane, propyldimethylchlorosilane and butyltrichlorosilane. Butylmethyldichlorosilane, butyldimethylchlorosilane, hexyltrichlorosilane, hexylmethyldichlorosilane,
Hexyldimethylchlorosilane, octyltrichlorosilane, octylmethyldichlorosilane, octyldimethylchlorosilane, decyltrichlorosilane, decylmethyldichlorosilane, decyldimethylchlorosilane, dodecyltrichlorosilane, dodecylmethyldichlorosilane, dodecyldimethylchlorosilane, tetradecyltrichlorosilane, tetradecyl Methyldichlorosilane, tetradecyldimethylchlorosilane, hexadecyltrichlorosilane, hexadecylmethyldichlorosilane, hexadecyldimethylchlorosilane, octadecyltrichlorosilane, octadecylmethyldichlorosilane, octadecyldimethylchlorosilane, eicosyltrichlorosilane, eicosylmethyldichlorosilane, eicosyltrichlorosilane Syldimethylchlorosilane Triacontyl trichlorosilane, triacontyl methyldichlorosilane, triacontyl dimethylchlorosilane, vinyl trichlorosilane,
Vinylmethyldichlorosilane, vinyldimethylchlorosilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, 5-hexenyltrichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenyldimethylchlorosilane, phenyltrichlorosilane, phenylmethyldichlorosilane, Examples thereof include phenyldimethylchlorosilane, diphenyldichlorosilane, methyldiphenylchlorosilane, triphenylchlorosilane and the like.

The hydroxy compound as the component (B) used in the present invention is a compound represented by the above general formula, wherein R ² is a substituted or unsubstituted monovalent hydrocarbon group, for example, , Alkyl groups such as methyl group, ethyl group, propyl group, etc., aryl groups such as phenyl group, tolyl group, etc., alkenyl groups such as allyl group, etc., and some of these hydrogen atoms are alkoxy groups such as methoxy group, ethoxy group, etc. Those substituted with chlorine atom, fluorine atom and the like are exemplified. Examples of such a compound include methal, ethanol, propanol, butanol, hexanol, octanol, decanol, dodecanol, allyl alcohol, phenol, phenethyl alcohol, methoxyethanol and the like.

The carbon atom-bonded fluorine atom-containing polymer of the component (C) used in the present invention is a component characterizing the present invention, and bubbles generated during the reaction of the components (A) and (B) are generated. And suppresses the formation of siloxane oligomer which is a by-product of the reaction. The component (C) may be a carbon atom-bonded fluorine atom-containing polymer which is liquid at room temperature, and the type thereof is not particularly limited. Examples of such compounds include α, ω-trimethylsiloxy group-blocked 3,3,3-trifluoropropylmethylpolysiloxane, 3,3,3-trifluoropropylmethylcyclopolysiloxane, and low polymerization of trifluoroethylene resin. The thing is illustrated. These fluorine atom-containing polymers are commercially available. In the present invention, these components (C) may be used by being supported by solid powder such as silica powder.

The amount of this component is usually 0.0001 to 100 parts by weight, preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of the halosilane of the component (A).

In the method for producing an organooxy group-containing silane of the present invention, the above-mentioned component (A) and component (B) are reacted in the presence of component (C). The reaction temperature is the same as that of component (A).
The temperature may be any temperature at which the dehydrohalogenation reaction between the components (B) proceeds, and is usually in the range of -78 to 200 ° C.
It is preferably in the range of 0 to 150 ° C. The reaction pressure is
The pressure may be such that the dehydrohalogenation reaction between the component (A) and the component (B) proceeds, but it is usually 0.001 to 10 atm, preferably 0.001 to 3 atm.

In the method for producing an organooxy group-containing silane according to the present invention, the above-mentioned components (A) and (B) are reacted in the presence of the component (C). Generally, a method of supplying the component (B) to the mixture of the component (C) to cause the reaction, a method of supplying the component (A) and the component (B) at the same time or alternately to the component (C) and causing the reaction, etc. Is.

[0011]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples,% is weight percent.

[0012]

Example 1 A cylindrical 1000 ml four-neck separable flask equipped with a mechanical stirrer, a cooling tube, and a dropping funnel,
Decyltrichlorosilane 137.9 g (0.500 mol), α, ω with a viscosity of 100 centistokes at 25 ° C
-Adding 13.8 g of trimethylsiloxy group-blocked 3,3,3-trifluoropropylmethylpolysiloxane, 60
Heated to ° C. Then, at this temperature, 48.0 g (1.50 mol) of methanol was gradually added dropwise over 30 minutes. The reaction was carried out under 1 atm. Regarding the foaming by the reaction, only a very small amount of fine foam was observed. Also, the foam only covered 20% of the reaction surface.
After the completion of dropping, the mixture was stirred for 30 minutes. The reaction solution was cooled to 30 ° C. and then neutralized with a 28% methanol solution of sodium methoxide to complete the reaction. Methanol was distilled off under reduced pressure, and the produced salt was filtered to obtain 128.8 g of a reaction product. When the reaction product was analyzed by gas chromatography, it was confirmed that this product had decyltrimethoxysilane as a main component. Its purity was 94.3% and it contained 3.2% of siloxane dimer. The reaction product is distilled under reduced pressure to give a boiling point of 110 ° C./7.
A fraction of mmHg was collected. Its yield is 105.2 g, its purity is 99.9%, its yield is 80.1%.
Met. The results of these measurements are shown in Table 1 below.

[0013]

Example 2 In a cylindrical 1000 ml four-neck separable flask equipped with a mechanical stirrer, a cooling tube, and a dropping funnel,
Decyltrichlorosilane 137.9 g (0.500 mol), a low polymer of trifluoroethylene resin having a viscosity of 200 centistokes at 25 ° C. [Asahi Glass Co., Ltd., trade name
FL800] 1.40 g was added and heated to 60 ° C.
Then, at this temperature, 48.0 g of methanol (1.
(00 mol) was gradually added dropwise over 30 minutes. The reaction was carried out under 1 atm. Regarding the foaming by the reaction, only a very small amount of fine foam was observed. Also, the foam only covered 20% of the reaction surface. After completion of dropping, 30
Stir for minutes. After cooling the reaction solution to 30 ° C., it was neutralized with a 28% methanol solution of sodium methoxide,
The reaction was complete. Methanol was distilled off under reduced pressure, and the produced salt was filtered to obtain 124.8 g of a reaction product. When the reaction product was analyzed by gas chromatography, it was confirmed that this product had decyltrimethoxysilane as a main component. Its purity was 94.2% and it contained 2.3% of siloxane dimer. The reaction product was distilled under reduced pressure to collect a fraction having a boiling point of 110 ° C./7 mmHg. The yield was 107.3 g, its purity was 99.9%, and its yield was 81.7%. The results of these measurements are shown in Table 1 below.

[0014]

Example 3 In a cylindrical 1000 ml four-neck separable flask equipped with a mechanical stirrer, a cooling tube, and a dropping funnel,
Dimethyldichlorosilane 64.5 g (0.500 mol),
Low-polymerization product of trifluoroethylene resin having a viscosity of 200 centistokes at 25 ° C. [Asahi Glass Co., Ltd., trade name FL8
00] 0.65 g was added and heated to 60 ° C. Then, at this temperature, 45.0 g of ethanol was gradually added dropwise over 30 minutes. The reaction was carried out under 1 atm.
Regarding the foaming by the reaction, only a very small amount of fine foam was observed. After the completion of dropping, the mixture was stirred for 30 minutes. After cooling the reaction solution to 30 ° C, 20% of sodium ethoxide
The reaction was completed by neutralizing with an ethanol solution. Ethanol was distilled off under reduced pressure, and the formed salt was filtered to give 69.4.
g of reaction product was obtained. When the reaction product was analyzed by gas chromatography, it was confirmed that this product had dimethyldiethoxysilanene as a main component. Its purity was 96.7% and it contained 1.8% of siloxane dimer. The reaction product is distilled under reduced pressure,
A fraction having a boiling point of 110 ° C./7 mmHg was collected. The yield is 6
It was 2.2 g, its purity was 99.9%, and its yield was 83.8%. The results of these measurements are shown in Table 1 below.

[0015]

[Comparative Example 1] In a cylindrical 1000 ml 4-neck separable flask equipped with a mechanical stirrer, a cooling tube, and a dropping funnel,
Decyltrichlorosilane 137.9 g (0.500 mol)
And was heated to 60 ° C. Then, under this temperature, 48.0 g (1.50 mol) of methanol was gradually added dropwise over 60 minutes. The reaction was carried out under 1 atm. The foaming due to the reaction is up to 67 with respect to the liquid part of the reaction mixture.
It was 0%. The foaming was severe, and compared with Example 1 above, 2
It took twice as long. After the completion of dropping, the mixture was stirred for 30 minutes. After cooling the reaction solution to 30 ° C., the sodium methoxide 2 was added.
The reaction was completed by neutralization with an 8% methanol solution.
Methanol was distilled off under reduced pressure, and the produced salt was filtered to obtain 12
8.8 g of reaction product was obtained. When the reaction product was analyzed by gas chromatography, it was confirmed that this product had decyltrimethoxysilane as a main component. Its purity was 83.8% and it contained 11.7% siloxane dimer. The reaction product was distilled under reduced pressure to collect a fraction having a boiling point of 110 ° C./7 mmHg. The yield was 88.3 g, its purity was 99.9%, and its yield was 67.2%. The results of these measurements are also shown in Table 1 below.

[0016]

Comparative Example 2 In a cylindrical 1000 ml four-neck separable flask equipped with a mechanical stirrer, a cooling tube, and a dropping funnel, 137.9 g (0.500 mol) of decyltrichlorosilane and a viscosity at 25 ° C. of 1000 were obtained. 13.8 g of sentimental α, ω-trimethylsiloxy-capped dimethylpolysiloxane was added and heated to 60 ° C. Then
At this temperature, 48.0 g (1.50 mol) of methanol was gradually added dropwise over 60 minutes. The reaction was carried out under 1 atm. The foaming due to the reaction was up to 1200% with respect to the liquid part of the reaction mixture. Foaming was vigorous and it took twice as long as in Example 1. After the completion of dropping, the mixture was stirred for 30 minutes. After the reaction solution was cooled to 30 ° C., it was neutralized with a 28% methanol solution of sodium methoxide to complete the reaction. Methanol was distilled off under reduced pressure, and the produced salt was filtered to obtain 123.1 g of a reaction product. When the reaction product was analyzed by gas chromatography, it was confirmed that this product had decyltrimethoxysilane as a main component. Its purity was 82.7% and it contained 13.5% siloxane dimer. The reaction product was distilled under reduced pressure to collect a fraction having a boiling point of 110 ° C./7 mmHg. Its yield is 70.2g and its purity is 99.9.
%, And the yield was 53.4%. The results of these measurements are also shown in Table 1 below.

[0017]

[Table 1]

[0018]

The method for producing an organooxy group-containing silane of the present invention comprises the steps of adding a halosilane (A) and a hydroxy compound (B) to a liquid carbon atom-bonded fluorine atom-containing polymer (C). Since the reaction is performed downward, the generation of bubbles generated during the reaction is suppressed and the productivity is excellent. Further, it is characterized in that the production amount of siloxane oligomer, which is a by-product of the reaction, is small and an organooxy group-containing silane of high purity can be produced.

Claims (1)

[Claims] 1. (A) General formula: R _a SiX _(4-a) (wherein R is
Are the same or different monovalent hydrocarbon groups, X is a halogen atom, and a is an integer of 0 to 3. ) And a (B) hydroxy compound represented by the general formula: R ² OH (wherein R ² is a substituted or unsubstituted monovalent hydrocarbon group), and (C) is a liquid at room temperature. Of the general formula: R _a Si (OR ² ) _(4-a) (wherein
R, R ² and a are the same as above. The manufacturing method of the silane containing an organooxy group represented by these.