JPH0827165A - Production of organosilicon compound - Google Patents

Abstract

PURPOSE:To produce an organosilicon compound useful as a raw material for a silane coupling agent by using a specific catalyst having high activity in adding a hydrosilane to an alkenyl-terminated organic compound. CONSTITUTION:A hydrosilane (a trialkoxysilane, preferably trimethoxysilane) is added to an alkenyl-terminated organic compound (e.g. an olefin) by using a solution of chloroplatinic acid in an aromatic nitrile (preferably benzonitrile or m-tolunitrile) as a catalyst to give the objective compound. The addition reaction is preferably carried out at 40-100 deg.C for 1-12 hours by using 10<-4> to 10<-6>mol of the catalyst based on 1mol of the hydrosilane and feeding the hydrosilane and the organic compound so as to give 0.8-1.5 equivalent alkenyl group of the organic compound based on 1 equivalent of active hydrogen of the hydrosilane.

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 organic silicon-containing compound, and more particularly to a nitrile solution of chloroplatinic acid or chloroplatinic acid as a catalyst when adding hydrosilanes to an organic compound having an alkenyl terminal group. The present invention relates to a method for producing an organic silicon-containing compound using a reaction product of nitrile. The organic silicon-containing compound produced by the present invention is useful as a raw material for a silane coupling agent or a water absorption inhibitor.

[0002]

It has been well known that various useful organic silicon-containing compounds can be obtained by addition reaction of hydrosilanes with an organic compound having an alkenyl terminal group. Various catalysts have been proposed for the purpose of improving yield and relaxing reaction conditions. For example, activated platinum catalysts such as platinum black, platinum-carbon and platinum-alumina have been proposed (US Pat. No. 2).
632013, U.S. Pat. No. 2,637,738, and U.S. Pat. No. 2,851,473) have a problem that when these platinum catalysts are used, the reaction system becomes a heterogeneous system and the addition reaction rate is slow.

In JP-B-33-9969 and JP-B-43-27853, chloroplatinic acid or a reaction product of alcohol, ether, aldehyde and the like and chloroplatinic acid is used as a catalyst. Is described. When these catalysts are used, the reaction system becomes uniform, but there is a problem that the reaction time becomes long because the catalytic activity is low. Further, Japanese Patent Publication No. 50-24947 discloses a complex compound of β-diketone and platinum.
No. 3 describes the use of a platinum complex dissolved in acetonitrile as a catalyst, but the catalytic activity is still insufficient and the reaction time is not satisfactory.

[0004]

SUMMARY OF THE INVENTION The present invention provides a method for producing an organic silicon-containing compound which solves the problems associated with the prior art as described above, has a short reaction time, and is excellent in productivity. .

[0005]

The present inventors have completed the present invention as a result of intensive research to solve the above problems. That is, the present invention is characterized by using an aromatic nitrile solution of chloroplatinic acid as a catalyst in producing an organic silicon-containing compound by adding a hydrosilane to an organic compound having at least one alkenyl end group. Is a method for producing an organic silicon-containing compound.

The present invention will be described in more detail below. The hydrosilanes used in the present invention are various compounds having 1 or 2 Si—H bonds, and examples thereof include the compounds represented by the general formula (I). When there are two or more R or X in this compound, they may be the same or different. Specific examples of the compound represented by the general formula (I) include trimethoxysilane, triethoxysilane, tripropoxysilane, methyldimethoxysilane,
Ethyldimethoxysilane, dimethylmethoxysilane, diethylethoxysilane, triphenoxysilane, phenyldimethoxysilane, diphenylethoxysilane, cyclohexyldimethoxysilane, trichlorosilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, tribromosilane, trifluorosilane, etc. Is mentioned. Preferred hydrosilanes include
Trialkoxysilanes such as trimethoxysilane and triethoxysilane can be mentioned for reasons such as stability of the produced compound and easy handling.

On the other hand, specific examples of the organic compound having an alkenyl terminal group used in the present invention include olefins such as ethylene, propylene, butylene, 1-hexene and 1-octene; styrene, allylbenzene and methallyl. Aromatic compounds such as benzene; methyl vinyl ether, allyl methyl ether, allyl phenyl ether
Ethers such as ter, allyl glycidyl ether and methallyl glycidyl ether; allyl methacrylate,
Esters such as methallyl methacrylate and allyl phthalate; nitrogen-containing compounds such as allylamine, methallylamine, diallylamine and triallylamine, allylmethylthioether and allylglycidylthioate
And sulfur-containing compounds such as tellurium; halogen-containing compounds such as vinyl chloride, allyl chloride and methallyl chloride; and silicon-containing compounds such as vinyltrimethylsilane and allyltrimethoxysilane. Further, diallyl phthalate having two or more alkenyl terminal groups can be used.

Specific examples of the aromatic nitrile compound used in the present invention include benzonitrile, o-tolunitrile and m.
-Tolunitrile, p-tolunitrile, 2,5-dimethylbenzonitrile, aminobenzonitrile, fluorobenzonitrile, chlorobenzonitrile, heptylbenzonitrile, phthalonitrile, naphthylnitrile and the like can be mentioned. Preferred aromatic nitrile compounds include benzonitrile, o-tolunitrile and m-tolunitrile for reasons of catalytic activity and ease of handling, among which benzonitrile and m
-Tolunitrile is more preferred.

The amount of the catalyst used in the present invention is not particularly limited, but it is 10 ^-2 to 10 with respect to 1 mol of hydrosilanes.
^-7 mol (as platinum), preferably 10 ^-4 to 10 ^-6 mol. If the amount of the catalyst is less than 10 ^-7 mol, the reaction time will be long, and if it is more than 10 ^-2 mol, the reaction rate will be too fast and heat will be generated. The catalyst is obtained by dissolving commercially available chloroplatinic acid or chloroplatinic acid hexahydrate in an aromatic nitrile compound at room temperature or by heating.

The charging ratio of the hydrosilanes and the organic compound having an alkenyl terminal group in the present invention cannot be set to a uniform condition, but the alkenyl of the organic compound having an alkenyl terminal group is equivalent to 1 equivalent of active hydrogen of the hydrosilane. The group is 0.5 to 2 equivalents, preferably 0.8 to
It is preferable to charge so that the amount becomes 1.5 equivalents. The method for charging the hydrosilanes, the organic compound having an alkenyl terminal group and the catalyst may be such that the hydrosilanes and the catalyst are charged first and the organic compound having an alkenyl terminal group is added dropwise, or the organic compound having an alkenyl terminal group is added. The catalyst may be charged first and the hydrosilanes may be added dropwise. Furthermore, a charging method in which these three kinds are simultaneously dropped and a method in which one kind is charged first and the remaining two kinds of mixtures are dropped are also included.

In the present invention, a solvent such as benzene, toluene, xylene or chlorinated hydrocarbon may be used for removing the heat of reaction and adjusting the concentration.

The reaction temperature and the reaction time cannot be set uniformly because they vary depending on the type of hydrosilanes and organic compounds having an alkenyl terminal group and the amount of catalyst used, but usually 0.5 to 0.5 at a temperature of room temperature to 150 ° C. ~ 24
The reaction is carried out at a temperature of preferably 40 to 100 ° C. for 1 to 12 hours. The reaction can be carried out under either normal pressure or increased pressure. The reaction atmosphere may be air, or may be an atmosphere of an inert gas such as nitrogen or argon.

[0013]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. (Example 1) In a 100 ml glass four-necked flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel,
1-hexene 20 g (0.22 mol) and 0.05
_{M-H 2 PtCl 6 · 6H} 2 O benzonitrile solution 4
4 microliters were charged and heated and stirred. After the internal temperature reached 60 ° C, 35.6 g of triethoxysilane
(0.22 mol) was slowly added dropwise, and after the addition was completed, the reaction was further performed at an internal temperature of 60 ± 3 ° C. for 5 hours. After completion of the reaction, gas chromatographic analysis showed that the target product, hexyltriethoxysilane, was in a yield of 86.7% (based on the charged 1-hexene).
Obtained in.

(Comparative Example 1) 20 g (0.22 mol) of 1-hexene and 0.05M-H ₂ PtCl _{6 were} placed in a 100 ml glass four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel. 88 ml of an isopropanol solution of 6H ₂ O was charged and heated and stirred. After the internal temperature reached 60 ° C., 35.6 g (0.22 mol) of triethoxysilane was slowly added dropwise, and after completion of the addition, the reaction was continued at an internal temperature of 60 ± 3 ° C. for 7 hours. After completion of the reaction, gas chromatography analysis showed that the desired product, hexyltriethoxysilane, was obtained in a yield of 73.8% (based on the charged 1-hexene).

(Comparative Example 2) In a 100 ml glass four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, 20 g (0.22 mol) of 1-hexene was synthesized according to JP-B-50-24974. Done 0.05
88 microliters of a benzene solution of M-acetylacetone platinum complex salt was charged and stirred with heating. Inner temperature is 60 ° C
35.6 g (0.22
mol) is slowly added dropwise, and after the addition is complete, the internal temperature is 60
The reaction was carried out at ± 3 ° C for 5 hours. After completion of the reaction, gas chromatography analysis revealed that the desired product, hexyltriethoxysilane, was obtained in a yield of 14.7% (based on the charged 1-hexene).

Example 2 Example 1 was repeated except that 26.5 g (0.22 mol) of trimethoxysilane was used instead of triethoxysilane as the kind of hydrosilane used in Example 1. After completion of the reaction, gas chromatography analysis revealed that the desired product, hexyltrimethoxysilane, was obtained in a yield of 88.9%.

(Example 3) 20 g (0.155) of allyl methacrylate was added to a 100 ml four-neck glass flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel.
mol) and 0.05M-H ₂ PtCl ₆ .6H ₂ O
62 microliters of the benzonitrile solution of was charged and heated and stirred. After the internal temperature reached 60 ° C., 25.5 g (0.155 mol) of triethoxysilane was slowly added dropwise, and after completion of the addition, the reaction was continued at an internal temperature of 60 ± 3 ° C. for 4 hours. After completion of the reaction, gas chromatography analysis showed that the target product, triethoxysilylpropyl methacrylate, was in a yield of 8
It was obtained at 7.7% (based on charged allyl methacrylate).

Example 4 Example 4 was repeated except that 18.9 g (0.155 mol) of trimethoxysilane was used instead of triethoxysilane as the kind of hydrosilane used in Example 3. After completion of the reaction, gas chromatography analysis revealed that the desired product, trimethoxysilylpropyl methacrylate, was obtained in a yield of 85.9% (based on the charged allyl methacrylate).

Comparative Example 3 20 g (0.155 m) of allyl methacrylate was added to a 100 ml glass four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel.
)) and 0.05 M-H ₂ PtCl ₆ .6H ₂ O in 62 μl of isopropanol solution were charged and stirred with heating. After the internal temperature reached 60 ° C., 25.5 g (0.155 mol) of triethoxysilane was slowly added dropwise, and after completion of the addition, the reaction was continued at an internal temperature of 60 ± 3 ° C. for 6 hours. After completion of the reaction, gas chromatography analysis showed that the target product, triethoxysilylpropyl methacrylate, was in a yield of 7
It was obtained at 8.2% (based on charged allyl methacrylate).

Comparative Example 4 20 g (0.155) of allyl methacrylate was added to a 100 ml glass four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel.
mol) and 0.05M-H ₂ PtCl ₆ .6H ₂ O
62 microliters of the acetonitrile solution of was charged and heated and stirred. After the internal temperature reached 60 ° C., 25.5 g (0.155 mol) of triethoxysilane was slowly added dropwise, and after completion of the addition, the reaction was continued at an internal temperature of 60 ± 3 ° C. for 7 hours. After completion of the reaction, gas chromatography analysis revealed that the target product, triethoxysilylpropyl methacrylate, had a yield of 6
It was obtained at 9.8% (based on charged allyl methacrylate).

Example 5 28.8 g (0.17 g) of triethoxysilane was added to a 100 ml glass four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel.
5 mol) and _{0.05M-H 2 PtCl 6 · 6H} 2
A benzonitrile solution of O (17.6 microliters) was charged and heated and stirred. After the internal temperature reached 80 ° C., 20 g (0.175 mol) of allyl glycidyl ether was slowly added dropwise, and after completion of the addition, the reaction was continued at an internal temperature of 80 ± 3 ° C. for 3 hours. After completion of the reaction, gas chromatographic analysis revealed that the desired product, triethoxysilylpropylglycidyl ether
The yield was 81.6% (based on the charged allylglycidyl ether).

Example 6 28.8 g (0.17) of triethoxysilane was added to a 100 ml glass four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel.
5 mol) and _{0.05M-H 2 PtCl 6 · 6H} 2
17.6 microliters of a m-tolunitrile solution of O was charged and stirred with heating. After the internal temperature reached 80 ° C., 20 g (0.175 mol) of allylglycidyl ether was slowly added dropwise, and after the addition was completed, the internal temperature was further adjusted to 80 ± 3 ° C. for 3 days.
Allowed to react for hours. After the reaction, the result of gas chromatography analysis,
The target product, triethoxysilylpropyl glycidyl ether, was obtained in a yield of 82.8% (charged allyl glycidyl ether).
It was obtained according to tell standard).

Example 7 In a 100 ml glass four-necked flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel, 19.9 g (0.22 g) of methallyl chloride was added.
mol), toluene 15ml and 0.05M-H ₂ P
tCl benzonitrile ₆ · 6H ₂ O solution 132 were charged microliters. Then trichlorosilane 2
9.8 g (0.22 mol) was slowly added dropwise, and after completion of the addition, the reaction was continued at room temperature for 4 hours. After completion of the reaction, gas chromatographic analysis revealed that the desired product, 3-chloro-2-methylpropyltrichlorosilane, was obtained in a yield of 90.1% (based on the charged methallyl chloride).

[0024]

INDUSTRIAL APPLICABILITY The method for producing an organic silicon-containing compound of the present invention is constituted by using a nitrile solution of chloroplatinic acid as a catalyst when adding hydrosilanes to an organic compound having an alkenyl end group. Since the activity of the catalyst is high and the addition reaction time can be shortened, the productivity of industrially useful silane coupling agents and the like can be increased, and its industrial value is extremely large.

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Claims (3)

[Claims] 1. An aromatic nitrile solution of chloroplatinic acid is used as a catalyst for producing an organic silicon-containing compound by adding a hydrosilane to an organic compound having at least one alkenyl terminal group. A method for producing an organic silicon-containing compound. 2. The method for producing an organic silicon-containing compound according to claim 1, wherein the hydrosilane is a compound represented by the general formula (I). H _a SiR _b X _{4- (a + b)} (I) (wherein, X represents an alkoxy group, an aryloxy group or a halogen atom, R represents an alkyl group, a cycloalkyl group or an aryl group, a is 1 or 2, b is 0, 1 or 2, and a + b is 3 or less.) 3. The method for producing an organic silicon-containing compound according to claim 2, wherein the hydrosilanes are trialkoxysilanes.