JP2001335589A - Method for producing organoalkoxysilane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for safely and efficiently producing an organomonoalkoxysilane in a high yield with eliminating unnecessary processes such as a separation while easily controlling the reaction. SOLUTION: The organomovoalkorysilave is produced by carrying out the hydrosilylation reaction of a silane compound of formula (1): R1R2HSiX...(1) (R1 and R2 are each independently a functional group constructed of atoms selected from C, H, O and N; and X is a halogen element) with a compound having an unsaturated carbon bond able to be hydrosilylated in a solvent and adding and reacting a metal alkoxide to the product without separating the reaction solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an organoalkoxysilane.

[0002]

2. Description of the Related Art The reaction of reacting a silicon compound having a SiH bond with an unsaturated fatty acid compound to obtain a compound having a C-Si bond is called a hydrosilylation reaction and is a widely used known technique. As a catalyst for hydrosilylation, a platinum catalyst is generally used.

As a method for producing an organoalkoxysilane, an alkoxylation reaction of reacting an organochlorosilane with an alcohol is well known. in this way,
Since hydrogen chloride gas is generated, there is a problem in a method of recovering the same and a decrease in the yield of a product due to a by-product.

As a method that does not generate hydrogen chloride gas, a technique of performing an alkoxylation reaction using an alkoxide is disclosed. A method for producing dialkoxysilane by reacting dibromosilane with sodium alkoxide is described in M.
J. Iller et al. Am. Chem. Soc. 79
Vol. 5604-5606 (1957). To ensure that the products do not decompose completely,
It is stated that it is essential to carry out under an inert hydrocarbon solvent and dry nitrogen atmosphere. It also states that monobromosilane did not react in this manner.

Japanese Patent Application Laid-Open No. Hei 6-73072 discloses a method for producing organooxysilane in high yield by reacting chlorosilane in which at least one hydrogen atom is bonded to a silicon atom with sodium organooxide without solvent. It has been disclosed. In Japanese Patent Application Laid-Open No. H11-315082, an organoalkoxysilane is synthesized by reacting diorganodichlorosilane with sodium organooxide. However, since a hydrogen atom bonded to silicon has a very high reactivity, a method of producing an organooxysilane hydride using chlorosilane having a hydrogen atom bonded to silicon has a problem of a by-product. . Further, the alkoxylation reaction with an alkoxide is a rapid exothermic reaction, and there is a problem that it is difficult to control the temperature without a solvent.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a process for producing an organomonoalkoxysilane which is efficient with few steps such as separation, easy to control the reaction, and can safely and in high yield. Is to provide.

[0007]

Means for Solving the Problems The present invention provides the following (a) to
Regarding the matters described in (f). (A) a silane compound represented by the formula (1) in a solvent;
A method for producing an organoalkoxysilane, comprising: subjecting a compound having an unsaturated carbon bond capable of hydrosilylation to a hydrosilylation reaction, and then adding a metal alkoxide to the reaction solution without separating the reaction solution to cause a reaction.

Embedded image R <SUP> 1 </ SUP> R <SUP> 2 </ SUP> HSix Formula (1) (where R <SUP> 1 </ SUP>, R <SUP> 2 </ SUP>> Is a functional group composed of atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom, and may be the same functional group. X represents a halogen element.) (B) The solvent is The method for producing an organoalkoxysilane according to (a), wherein the compound is one or more compounds selected from amide compounds, ketone compounds, ether compounds, hydrocarbon compounds, ester compounds, and nitrile compounds having no hydroxyl group. . (C) The method for producing an organoalkoxysilane according to (a) or (b), wherein the alkoxide represented by the formula (2) is used as the metal alkoxide.

Embedded image MOR <SUP> 3 </ SUP> Formula (2) (wherein R <SUP> 3 </ SUP> is an alkyl group and M is an alkali metal). The method for producing an organoalkoxysilane according to any one of (a) to (c), which is dimethylchlorosilane. (E) The compounding ratio of the silane compound and the compound having an unsaturated carbon bond is 0.8 to 1.5 mol of the compound having an unsaturated carbon bond per 1 mol of the silane compound. d) The method for producing an organoalkoxysilane according to any one of the above. (F) The compounding ratio of the silane compound and the metal alkoxide is
Metal alkoxide 0.8 to 1 mol of silane compound
The method for producing an organoalkoxysilane according to any one of (a) to (e), wherein the amount is from 1.5 to 1.5 mol.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, a compound represented by the formula (1) can be used as a silane compound as a raw material. The functional groups R <SUP> 1 </ SUP> and R <SUP> 2 </ SUP> include, for example, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, octadecyl group, octyl group and the like. It can be selected from a cyclic alkyl group such as a chain alkyl group and a cyclohexyl group, and an alkyl-substituted amino group such as a mercapto group, an amino group and a methylamino group. As such a compound, for example, dimethylchlorosilane, diethylchlorosilane, diethylbromosilane and the like are preferably used.

The solvent in the present invention dissolves the monohalogenated silane as a raw material, and may be any solvent as long as the reaction with each component does not proceed under the conditions of the production method of the present invention. For example, amide compounds such as formamide, acetamide, N, N-dimethylacetamide, ketone compounds such as 2-butanone, cyclohexanone, acetylacetone and 2,3-butanedione, dipropyl ether, 2-methoxyethyl ether, dibutyl ether, dioxane, Ether compounds such as tetrahydrofuran, hexane, toluene, cyclohexane, 2-
Hydrocarbon compounds such as methylpentane and benzene, ester compounds such as ethyl formate, ethyl acetate, propyl acetate and methyl propionate, and nitrile compounds such as acetonitrile and propionitrile can be used. It should be noted that alcohols themselves are liable to react with the monohalogenated silane, and hydrogen halide is thereby generated, so that it is difficult to obtain the product according to the present invention, and a means for recovering the hydrogen halide is employed. Need arises.

A platinum catalyst is generally used for the reaction between a silane compound and a compound having an unsaturated carbon bond, and this can be used in the present invention. For example, hexachloroplatinic acid (IV) hexahydrate is preferably used. The amount of the catalyst is preferably 0.01 equivalent or less of dimethylchlorosilane from the viewpoint of cost and the like. If the amount is less than 10 <SUP> -7 </ SUP> equivalent, the effect of the catalyst may not be sufficiently exhibited. It is preferably at least 10 <SUP> -7 </ SUP> equivalent.

The compound having an unsaturated carbon bond capable of hydrosilylation in the present invention includes, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. , 1-
Decene, 2-butene, isobutylene, 2-pentene, 3
-Methyl-1-butene, 2-methyl-2-butene, 2,
Alkenes such as 3-dimethyl-2-butene, allyl acetate, allyl acetoacetate, allyl benzene, allyl glycidyl ether, allyl ethyl ether, allyl isothiosilane, eugenol, 3-allyloxy-1,2
And compounds having a vinyl group such as -propanediol, o-allylphenol, allylphenylether, allylurea, vinyl acetate, 4-vinyl-1-cyclohexene, styrene and methylstyrene.

The alkoxide represented by the formula (2) can be used as the metal alkoxide in the present invention. As such an alkoxide, for example, sodium methoxide, sodium ethoxide, lithium methoxide, potassium methoxide and the like are preferably used.

The compounding ratio of the silane compound and the compound having an unsaturated carbon bond is preferably 0.8 to 1.5 mol of the compound having an unsaturated carbon bond per 1 mol of the silane compound. It is particularly preferable that the compound having an unsaturated carbon bond be used in an amount of 1.0 to 1.5 mol so as not to cause such a problem. When the amount of the compound having an unsaturated carbon bond is less than 0.8 mol relative to 1 mol of the silane compound, many unreacted Si-H bonds are generated, and a by-product is generated.
Yield may be poor. In addition, silane compound 1m
1.5 m of a compound having an unsaturated carbon bond to ol
When the amount exceeds ol, the cost is likely to increase due to a large amount of extra raw materials.

The compounding ratio of the silane compound to the metal alkoxide is preferably 0.8 to 1.5 mol of the metal alkoxide to 1 mol of the silane compound, and 1.0 to 1.1 mol of the metal alkoxide. Is particularly preferred. If the compounding ratio of the alkoxide to dimethylchlorosilane exceeds 1.5, the alkoxide to be used becomes excessive, so that it tends to be disadvantageous in terms of cost, and the product and the excess alkoxide are mixed, so that separation tends to be difficult. . Since a large amount of unreacted monohalogenated silane remains, it tends to be disadvantageous in terms of efficiency.

The reaction temperature ranges from the melting point of the solvent to the boiling point. It is preferable to set the temperature to 30 to 70 ° C. while cooling the reaction vessel to cause an exothermic reaction. If the temperature is lower than 30 ° C., the rate of hydrosilylation and alkoxylation tends to be low. If the temperature is higher than 70 ° C., the reaction proceeds rapidly, and the reaction control tends to be difficult, for example, the product may be blown out of the container. .

The concentration of the reaction solution is such that the sum of the weight of the silane compound, the compound having an unsaturated carbon bond, and the metal alkoxide is 90% or less based on the sum of this weight and the weight of the solvent. Is preferred, and 10 to 50%
Is particularly preferred. When the concentration is higher than 90%, temperature control tends to be difficult. If it is less than 10%, the reaction time tends to be too long, and the cost tends to be high because the amount of solvent used increases.

In the production method of the present invention, the reaction is preferably performed in a dry gas, particularly preferably in an inert gas atmosphere. Si-H under an atmosphere containing moisture
The bond may be decomposed by water to become a Si—OH bond. Further, the platinum catalyst may be deactivated by oxygen.

The organoalkoxysilane produced in the present invention can be separated from the reaction solution by extraction, distillation and the like. Preferably it is separated by vacuum distillation.

An example of the manufacturing method according to the present invention will be described below. First, a catalyst and a solvent are mixed in a reaction vessel, a silane compound is added, and then a compound having an unsaturated carbon bond is added. Since the temperature inside the reaction vessel gradually rises,
The temperature is adjusted by, for example, cooling the reaction vessel to a temperature within the range of 70 ° C. The above operation is performed in an inert gas. After the reaction is sufficiently performed, the resulting organoalkoxysilane can be isolated by removing the solution and separating the solution by distillation under reduced pressure.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. (Example 1) Hexachloroplatinic acid (IV) hexahydrate 0.1
04 g (0.0002 mol) of cyclohexanone 15
Dissolved in 8.1 g, 43.7 g of dimethylchlorosilane
(0.5 mol), 65.0 g (0.5
5 mol) and stirred. The reaction solution concentration was 50%. The temperature inside the reaction vessel gradually increased and reached about 50 ° C. after 30 minutes. While cooling the reaction vessel with ice,
The temperature was kept within the range of 0 ° C. After an additional 30 minutes, the temperature inside the reaction vessel began to drop, so ice cooling was stopped. Next, 29.7 g of sodium methoxide (0.55 mol
l) was added and stirred. Since the temperature in the reaction vessel increased, the temperature was kept at 40 to 50 ° C. by cooling with ice. After about 30 minutes, the temperature inside the reaction vessel began to drop, so the reaction solution was taken out and distilled under reduced pressure. As a result, about 31 g of a transparent liquid was obtained as a fraction at 90 to 100 ° C./13.3 Pa. The liquid was analyzed by NMR (nuclear magnetic resonance) to identify it as phenylpropyldimethylmethoxysilane. The presence of impurities was not confirmed. The yield was about 20%. (Example 2) Hexachloroplatinic acid (IV) hexahydrate 0.1
04 g (0.0002 mol) was dissolved in 91 g of 2-butanone, and 43.7 g (0.5 m
ol) and 47.3 g (0.55 mol) of vinyl acetate were added and stirred. The reaction solution concentration was 50%. The temperature inside the reaction vessel gradually increased and reached about 50 ° C. after 30 minutes. The reaction vessel was kept at 40 to 50 ° C. while being cooled with ice. After an additional 30 minutes, the temperature inside the reaction vessel began to drop, so ice cooling was stopped. Next, 29.7 g (0.55 mol) of sodium methoxide was added and stirred. Since the temperature inside the reaction vessel rose,
The temperature was kept in the range of 0 to 50 ° C. After about 30 minutes, the temperature inside the reaction vessel began to drop, so the reaction solution was taken out and distilled under reduced pressure. As a result, 90-100 ° C /
As a fraction at 13.3 Pa, about 35 g of a clear liquid were obtained. This liquid was analyzed by NMR to identify it as ethyl acetate dimethylmethoxysilane. The presence of impurities was not confirmed. The yield was about 25%. (Example 3) Hexachloroplatinic acid (IV) hexahydrate 0.1
04 g (0.0002 mol) of toluene 106.5 g
In 43.7 g of dimethylchlorosilane (0.5
mol), 62.8 g of allyl glycidyl ether (0.
55 mol) and stirred. Reaction solution concentration is 50%
And The temperature inside the reaction vessel gradually increased and reached about 50 ° C. after 30 minutes. While cooling the reaction vessel with ice,
The temperature was kept within the range of 50 ° C. After another 30 minutes,
Ice cooling was stopped because the temperature inside the reaction vessel began to drop.
Next, 29.7 g of sodium methoxide (0.55 mol
l) was added and stirred. Since the temperature in the reaction vessel increased, the temperature was kept at 40 to 50 ° C. by cooling with ice. After about 30 minutes, the temperature inside the reaction vessel began to drop, so the reaction solution was taken out and distilled under reduced pressure. As a result, about 33 g of a transparent liquid was obtained as a fraction at 90 to 100 ° C./13.3 Pa. This liquid was analyzed by NMR and identified as γ-glycidoxypropyldimethylmethoxysilane. The presence of impurities was not confirmed. The yield was about 30%. (Comparative Example 1) 43.7 g of dimethylchlorosilane (0.5
mol) was dissolved in 106.5 g of toluene, and 29.7 g (0.55 mol) of sodium methoxide was added thereto, followed by stirring. Since the temperature inside the reaction vessel began to rise, it was kept on ice and cooled to 20 to 30 ° C. About 30
Minutes later, the temperature inside the reaction vessel began to decrease, so that 0.104 g (0.000 g) of hexachloroplatinic (IV) acid hexahydrate was used.
2 mol) and 62.8 g of allyl glycidyl ether
(0.55 mol) and stirred. The temperature inside the reaction vessel gradually increased and reached about 50 ° C. after 30 minutes. The reaction vessel was kept at 40 to 50 ° C. while cooling with ice. After a further 30 minutes, the temperature inside the reaction vessel began to drop, so the reaction solution was taken out and distilled under reduced pressure.
As a result, about 4 g of a transparent liquid was obtained as a fraction at 90 to 100 ° C./13.3 Pa. This solution was analyzed by NMR, and it was identified that it was γ-glycidoxypropyldimethylmethoxysilane. The yield was less than 5%. (Comparative Example 2) An experiment was performed in the same manner as in Example 3, except that no solvent was used. As a result, immediately after the addition of the allyl glycidyl ether, the temperature inside the reaction vessel rose rapidly, and more than half of the reaction solution spewed out of the vessel. The experiment was continued, but no product was obtained. When the alkoxylation is performed first as shown in Comparative Example 1, the boiling point of dimethylalkoxysilane generated by the alkoxylation is about 40 ° C., so that the dimethylalkoxysilane hardly stays in the reaction system. Therefore, the yield was as low as 5% or less. Further, since hydrosilylation and alkoxylation are exothermic reactions, as shown in Comparative Example 2, when no solvent is used, the temperature inside the reaction vessel rises sharply, and the reaction solution blows out of the vessel. I will. Therefore, no product could be obtained.

[0021]

According to the method of the present invention, an organoalkoxysilane in which one alkoxy group is bonded to a Si atom can be produced with high yield. In addition, since the control of the reaction is facilitated, the production of the organoalkoxysilane can be carried out safely and efficiently without increasing the cost in terms of safety and the like.

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Claims (6)

[Claims] In a solvent, a silane compound represented by the formula (1) and a compound having an unsaturated carbon bond capable of hydrosilylation are subjected to a hydrosilylation reaction, and the reaction solution is separated without separating the reaction solution. A method for producing an organoalkoxysilane, wherein an alkoxide is added and reacted. [Image Omitted] R <SUP> 1 </ SUP> R <SUP> 2 </ SUP> HSix ... Formula (1) (where R <SUP> 1 </ SUP>, R <SUP> 2 </ SUP>> Is a functional group composed of atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, and a nitrogen atom, and may be the same functional group. X represents a halogen element.) 2. The method according to claim 1, wherein the solvent is an amide compound having no hydroxyl group, a ketone compound, an ether compound, a hydrocarbon compound,
The method for producing an organoalkoxysilane according to claim 1, wherein the method is one or more compounds selected from an ester compound and a nitrile compound. 3. The alkoxide represented by the formula (2) is used as the metal alkoxide.
Alternatively, the method for producing an organoalkoxysilane according to claim 2. Embedded image MOR <SUP> 3 </ SUP> Formula (2) (wherein R <SUP> 3 </ SUP> is an alkyl group and M is an alkali metal). 4. The method for producing an organoalkoxysilane according to claim 1, wherein the silane compound is dimethylchlorosilane. 5. The compound of claim 1, wherein the compounding ratio of the silane compound and the compound having an unsaturated carbon bond is 0.8 to 1.5 mol of the compound having an unsaturated carbon bond per 1 mol of the silane compound. 5. The method for producing an organoalkoxysilane according to any one of items 1 to 4. 6. The compound ratio of the silane compound to the metal alkoxide is 0.8 to 1.5 mol per 1 mol of the silane compound.
6. The method for producing an organoalkoxysilane according to any one of claims 1 to 5.