JP2989109B2 - Method for producing dialkyldialkoxysilane compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to wood, concrete,
The present invention relates to a method for producing a dialkyldialkoxysilane compound useful as a surface water repellent, a silane coupling agent, and a catalyst for propylene polymerization of various building materials such as marble.

[0002]

2. Description of the Related Art Dialkyldialkoxysilane compounds are known to be useful as surface water repellents for various building materials such as wood and concrete and as catalysts for propylene polymerization.
Among them, particularly those containing two secondary alkyl groups or those containing a primary alkyl group having an alkyl substituent at the β-position are widely used. As means for producing such a dialkyldialkoxysilane compound, Z.I. LASOCKI, Bull. Acad. Po
l. Sci. Ser. Sci. Chim. , 12,28
1 (1964) describes a method of reacting a Grignard reagent with an alkoxysilane such as tetramethoxysilane.

However, in this method, the secondary alkyl group contained in the alkoxysilane or the primary alkyl group having an alkyl substituent at the β-position is bulky,
The Grignard reagent and the alkoxysilane hardly react with each other, and it took time until the reaction was completed. Furthermore, a side reaction such as a reduction reaction easily occurs, and the yield of the target substance, a dialkyldialkoxysilane compound, cannot be increased.

[0004] In order to efficiently produce a dialkyldialkoxysilane compound, a method of using an alkyl lithium instead of a Grignard reagent has been studied. Alkyl lithium can be obtained by dispersing metal lithium to several μm after melting. However, since metallic lithium has a high melting point (190 ° C.) and high activity, it is difficult to handle and requires a special device when melting. Alkyl lithium obtained from metallic lithium is in contact with air and easily ignites spontaneously, so it is dangerous to produce in large quantities. Therefore, a method for producing a dialkyldialkoxysilane compound by reacting an alkyllithium with an alkoxysilane has been industrially unsuitable.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has as its object to provide a method for safely and efficiently producing a dialkyldialkoxysilane compound.

[0006]

Means for Solving the Problems A method for producing a dialkyldialkoxysilane compound of the present invention, which has been made to achieve the above object, is represented by the following formula [I] HSi (OR ¹ ) ₃ [I]. After reacting a hydrogen trialkoxysilane with a Grignard reagent represented by the following formula [II] R ² MgX ¹ [II] and a Grignard reagent represented by the following formula [III] R ³ MgX ² [III], The obtained silane compound represented by the following formula [IV] R ² R ³ SiH (OR ¹ ) [IV] is combined with an alcohol represented by the following formula [V] R ¹ OH [V] in the presence of a catalyst. And a dialkyldialkoxysilane compound represented by the following formula [VI] R ² R ³ Si (OR ¹ ) ₂ [VI]. R ¹ in the formula is a methyl group or an ethyl group. R ² and R ³ are a C 3-10 secondary alkyl group or a C 3-10 primary alkyl group having an alkyl substituent at the β-position, and may be the same or different. still,
R ² and R ³ are an aliphatic hydrocarbon or an alicyclic hydrocarbon. X ¹ and X ² are halogen atoms, which may be the same or different.

The hydrogen trialkoxysilane represented by the formula (I) includes, for example, trimethoxysilane and triethoxysilane.

The Grignard reagent represented by the formula [II] or [III] is obtained by reacting magnesium with a secondary alkyl halide or a primary alkyl halide having an alkyl substituent at the β-position. The reaction is performed in an ethereal solvent such as diethyl ether, tetrahydrofuran and the like.

Specific examples of the Grignard reagent represented by the formula [II] or [III] include isopropyl magnesium chloride, isopropyl magnesium bromide, isobutyl magnesium chloride, isobutyl magnesium bromide, sec-butyl magnesium chloride, and sec-butyl magnesium bromide. , Neopentyl magnesium chloride, neopentyl magnesium bromide, sec-pentyl magnesium chloride, sec-pentyl magnesium bromide, 2-methylbutyl magnesium chloride, 2-methylbutyl magnesium bromide, 2-ethylpropyl magnesium chloride, 2-ethylpropyl magnesium bromide , Cyclopentyl magnesium chloride, cyclopentyl magnesium Bromide, cyclohexylmagnesium chloride, cyclohexylmagnesium bromide, cyclooctylmagnesium chloride, cyclooctylmagnesium bromide, (cyclopentylmethyl) magnesium chloride, (cyclopentylmethyl) magnesium bromide, (cyclohexylmethyl) magnesium chloride, (cyclohexylmethyl) magnesium bromide .

The silane compound represented by the formula [IV] can be obtained by reacting the hydrogen trialkoxysilane with a Grignard reagent. The reaction is performed in an ether solvent or a mixed solvent of an ether solvent and an aprotic solvent. Examples of the ether-based solvent include diethyl ether and tetrahydrofuran. Aprotic solvents include, for example, hexane, decane, toluene, xylene.

Specific examples of the silane compound represented by the formula [IV] include diisopropylmethoxysilane, diisopropylethoxysilane, diisobutylmethoxysilane, diisobutylethoxysilane, di-sec-butylmethoxysilane, and di-sec-butylethoxysilane. , Di-sec
-Pentylmethoxysilane, di-sec-pentylethoxysilane, dineopentylmethoxysilane, dineopentylethoxysilane, di (2-methylbutyl) methoxysilane, di (2-methylbutyl) ethoxysilane, di (2-ethylpropyl) Methoxysilane, di (2-ethylpropyl) ethoxysilane, dicyclopentylmethoxysilane, dicyclopentylethoxysilane, dicyclohexylmethoxysilane, dicyclohexylethoxysilane, di (cyclopentylmethyl) methoxysilane, dicyclooctylmethoxysilane, di (cyclohexylmethyl) Methoxysilane, isopropylisobutylmethoxysilane, isopropyl-sec-butylethoxysilane, isopropylcyclopentylmethoxysilane, isopropylcyclohexane Sill silane, isobutyl neopentyl silane, isobutyl (2-ethyl-propyl) silane, isobutyl cyclopentyl trimethoxysilane, isobutyl cyclohexyl silane, sec- butyl -sec- pentyl silane, sec- butyl cyclopentyl trimethoxysilane, s
ec-cyclohexylmethoxysilane, neopentylcyclopentylmethoxysilane, neopentylcyclohexylmethoxysilane, cyclopentylcyclohexylmethoxysilane, cyclopentylcyclohexylethoxysilane, cyclohexyl (cyclohexylmethyl) methoxysilane.

The alcohol represented by the formula [V] includes, for example, methanol and ethanol. The alcohol is used in an amount of 1 molar equivalent to the silane compound represented by the formula [IV].
It is preferable to add 10 molar equivalents and react with the silane compound near the boiling point of the alcohol. If it is less than 1 molar equivalent, no dialkyldialkoxysilane compound as a target substance is produced. If it exceeds 10 molar equivalents, a large amount of by-products will be generated.

The dialkyldialkoxysilane compound represented by the formula [VI] is obtained by reacting a silane compound represented by the formula [IV] with an alcohol represented by the formula [V] in the presence of a catalyst. Catalysts include metal alkoxides, transition metals, metal compounds. These catalysts may be used alone or as a mixture. Metal alkoxides include, for example, sodium methoxide, sodium ethoxide, and transition metals include, for example, palladium,
Rhodium and platinum are mentioned, and the metal compound is, for example, palladium acetate, chlorotristriphenylphosphine rhodium, chloroplatinic acid. These catalysts are used in an amount of 0.0 with respect to the silane compound represented by the formula (IV).
It is preferably from 1 mol% to 20 mol%, particularly preferably from 0.1 mol% to 5 mol%. If it is less than 0.01 mol%, the silane compound and the alcohol do not react. If it exceeds 20 mol%, the effect of simply adding a large amount of the catalyst is not exhibited.

Specific examples of the dialkyldialkoxysilane compound represented by the formula [VI] include diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane,
Di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-pentyldimethoxysilane, di-sec-pentyldiethoxysilane, dineopentyldimethoxysilane, dineopentyldiethoxysilane, di (2 -Methylbutyl) dimethoxysilane, di (2-methylbutyl) diethoxysilane, di (2
-Ethylpropyl) dimethoxysilane, di (2-ethylpropyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, di (cyclopentylmethyl) dimethoxysilane, dicyclooctyldimethoxy Silane, di (cyclohexylmethyl) dimethoxysilane, isopropylisobutyldimethoxysilane, isopropyl-sec-butyldiethoxysilane, isopropylcyclopentyldimethoxysilane, isopropylcyclohexyldimethoxysilane, isobutylneopentyldimethoxysilane,
Isobutyl (2-ethylpropyl) dimethoxysilane,
Isobutylcyclopentyldimethoxysilane, isobutylcyclohexyldimethoxysilane, sec-butyl-
sec-pentyldimethoxysilane, sec-butylcyclopentyldimethoxysilane, sec-cyclohexyldimethoxysilane, neopentylcyclopentyldimethoxysilane, neopentylcyclohexyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylcyclohexyldiethoxysilane,
Cyclohexyl (cyclohexylmethyl) dimethoxysilane.

[0015]

According to the production method of the present invention, a dialkyldialkoxysilane compound can be produced safely and in good yield without using a lithium reagent which is difficult to handle.

[0016]

Embodiments of the present invention will be described below in detail.

Example 1 24.3 g of metallic magnesium was placed in a 1-liter flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel.
(1.0 mol), 500 ml of tetrahydrofuran and a small amount of iodine. Under a nitrogen gas atmosphere, 106.6 g of neopentyl chloride from a dropping funnel.
(1.0 mol) was added dropwise at an internal temperature of 40 to 50 ° C. over 1 hour, and further stirred at 55 ° C. for 1 hour to obtain neopentyl magnesium chloride serving as a Grignard reagent.

61.1 g (0.5 mol) of trimethoxysilane was added dropwise to neopentylmagnesium chloride from a dropping funnel over 1 hour at room temperature, followed by aging under reflux for 1 hour. The reaction solution was filtered to remove salts, and then distilled to obtain a fraction containing dineopentylmethoxysilane.

After the distillation is completed, 32.0 g (1.0 mol) of methanol and 0.54 g (10 mol) of sodium methoxide as a catalyst are placed in another 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. Mmol), the fraction obtained by the above crude distillation was dropped from the dropping funnel at 60 to 70 ° C over 2 hours, and the mixture was stirred as it was for 10 hours. This reaction solution is distilled to 83-84 ° C /
By collecting a fraction having a boiling point of 10 mmHg, 94.5 g of dineopentyldimethoxysilane was obtained. The yield was 81.3%.

Comparative Example 1 The same experiment as in Example 1 was performed except that 61.1 g (0.5 mol) of trimethoxysilane was changed to 76.1 g (0.5 mol) of tetramethoxysilane. After completion of the reaction, the product was examined by gas chromatography. As a result, although neopentyltrimethoxysilane was formed, the desired dineopentyldimethoxysilane was hardly formed.

Example 2 Metal magnesium 2 was placed in a 500 ml flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel.
4.3 g (1.0 mol), 300 ml of tetrahydrofuran and a small amount of iodine were charged. Isopropyl chloride 7 from the dropping funnel under nitrogen gas atmosphere
8.5 g (1.0 mol) was added dropwise at an internal temperature of 40 to 50 ° C. over 1 hour, and the mixture was further stirred at 55 ° C. for 1 hour to obtain isopropylmagnesium chloride as a Grignard reagent.

In another 1 liter vessel equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 61.1 g (0.5 mol) of trimethoxysilane and tetrahydrofuran 3
Isopropylmagnesium chloride was added dropwise over 1 hour at room temperature.
Aged for hours. This reaction solution was filtered to remove salts, and then distilled to obtain a fraction containing diisopropylmethoxysilane.

After the distillation, 32.0 g (1.0 mol) of methanol and 0.54 g (10 mol) of sodium methoxide as a catalyst were placed in another 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. Mmol), and the fraction obtained by the above-mentioned distillation was dropped from the dropping funnel at 60 to 70 ° C. over 2 hours.
Stirred for hours. The reaction solution is distilled to 85-86 ° C / 50
By collecting a fraction having a boiling point of mmHg, 68.1 g of diisopropyldimethoxysilane was obtained. The yield was 77.2%.

Comparative Example 2 The same experiment as in Example 2 was performed, except that 61.1 g (0.5 mol) of trimethoxysilane was changed to 76.1 g (0.5 mol) of tetramethoxysilane. After the reaction was completed, the product was examined by gas chromatography. The ratio of isopropyltrimethoxysilane to the target substance, diisopropyldimethoxysilane, was 76.6: 2.
3.4.

Example 3 The same experiment as in Example 2 was carried out except that 78.5 g (1.0 mol) of isopropyl chloride was changed to 104.6 g (1.0 mol) of cyclopentyl chloride. By collecting a fraction having a boiling point of 117 to 118 ° C / 9 mmHg, 93.4 g of dicyclopentyldimethoxysilane was obtained. The yield was 81.8%.

Example 4 The same experiment as in Example 2 was carried out except that 78.5 g (1.0 mol) of isopropyl chloride was changed to 118.6 g (1.0 mol) of cyclohexyl chloride. By collecting a fraction having a boiling point of 124 to 125 ° C./1 mmHg, 99.9 g of dicyclohexyldimethoxysilane was obtained. The yield was 77.9%.

Example 5 78.5 g (1.0 mol) of isopropyl chloride was combined with 104.6 g (1.0 mol) of cyclopentyl chloride,
61.1 g (0.5 mol) of trimethoxysilane was added to 82.1 g (0.5 mol) of triethoxysilane, and 32.0 g (1.0 mol) of methanol was added to 46.1 g of ethanol.
(1.0 mol) The same experiment as in Example 2 was performed except that the amount was changed to (1.0 mol). By collecting a fraction having a boiling point of 109 to 110 ° C / 2 mmHg, 98.2 g of dicyclopentyldiethoxysilane was obtained. The yield is 76.6
%Met.

Example 6 Metal magnesium 1 was placed in a 300 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel.
2.2 g (0.5 mol), 150 ml of tetrahydrofuran and a small amount of iodine were charged. Neopentyl chloride 5 from a dropping funnel under nitrogen gas atmosphere
3.3 g (0.5 mol) was added dropwise at an internal temperature of 40 to 50 ° C. over 1 hour, and further stirred at 55 ° C. for 1 hour to obtain neopentyl magnesium chloride serving as a Grignard reagent.

Separately, 12.2 g (0.5 mol) of metallic magnesium, tetrahydrofuran 1
50 milliliters and a small amount of iodine were charged. 53.3 g (0.5 mol) of neopentyl chloride was replaced with 46.3 g (0.5 mol) of isobutyl chloride, and isobutyl magnesium chloride as a Grignard reagent was obtained by the same operation.

In another 1 liter container equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, 61.1 g (0.5 mol) of trimethoxysilane and tetrahydrofuran 3
Then, neopentylmagnesium chloride and isobutylmagnesium chloride were added dropwise to the mixture in this order over 1 hour at room temperature.
Aged for hours. The reaction solution was filtered to remove salts, and distilled to obtain a fraction containing isobutylneopentylmethoxysilane.

After completion of the distillation, 32.0 g (1.0 mol) of methanol and 0.54 g (10 mol) of sodium methoxide as a catalyst were placed in another 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel. Mmol), and the fraction obtained by the above-mentioned distillation was dropped from the dropping funnel at 60 to 70 ° C. over 2 hours.
Stirred for hours. The reaction solution is distilled to 90-91 ° C./20
By collecting a fraction having a boiling point of mmHg, 75.7 g of isobutylneopentyldimethoxysilane was obtained. The yield was 69.3%.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazutoshi Numami 28-1, Nishifukushima, Oku-ku, Kushiro-mura, Nakakibijo-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) References (JP, A) JP-A-2-53793 (JP, A) JP-A-7-82277 (JP, A) JP-A-8-113578 (JP, A) JP-A-7-278161 (JP, A) JP-A-4-41496 (JP, A) JP-A-6-345781 (JP, A) JP-A-7-48387 (JP, A) JP-B-26-2669 (JP, B1) (58) Int.Cl. ⁶ , DB name) C07F 7/18 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (3)

(57) [Claims] 1. A hydrogen trialkoxysilane represented by the following formula [I] HSi (OR ¹ ) ₃ [I] (wherein R ¹ is a methyl group or an ethyl group), and the following formula [II] R ² MgX ¹ A Grignard reagent represented by [II] and the following formula [III] R ³ MgX ² [III] (wherein R ² and R ³ are a secondary alkyl group having 3 to 10 carbon atoms or alkyl substitution at the β-position. A primary alkyl group having 3 to 10 carbon atoms, which may be the same or different, X ¹ ,
X ² is the same or different halogen atom), and is reacted with a Grignard reagent represented by the following formula [IV] R ² R ³ SiH (OR ¹ ) [IV] Reaction with an alcohol represented by the following formula [V] R ¹ OH [V] in the presence of a catalyst represented by the following formula [VI] R ² R ³ Si (OR ¹ ) ₂ [VI] A method for producing a dialkyldialkoxysilane compound. 2. The dialkyl according to claim 1, wherein the alcohol represented by the formula [V] is added in an amount of 1 molar equivalent to 10 molar equivalents with respect to the silane compound represented by the formula [IV]. A method for producing a dialkoxysilane compound. 3. The catalyst is at least one selected from a metal alkoxide, a transition metal, and a metal compound, and is used in an amount of 0.01 mol% to 20 mol% based on the silane compound represented by the formula [IV]. 3. The method for producing a dialkyldialkoxysilane compound according to claim 1, wherein the amount is mol%. 4.