JP2000256372A - Production of aliphatic chlorosilane by hydrosilylation reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce an aliphatic chlorosilane while improving selectivity in reaction and positional selectivity in addition by the hydrosilylation reaction of an organic unsaturated compound in the presence of a platinum catalyst in a coexisted state of a small amount of a carboxylic acid compound. SOLUTION: By the hydrosilylation reaction of (C) an aliphatic compound having an unsaturated bond at its end with (D) a hydrochlorosilane under the catalytic action of (B) a platinum (compound) in the presence of (A) a carboxylic acid compound (preferably a carboxylic acid, its silylated compound, a carboxylic anhydride or the like), (E) an aliphatic chlorosilane compound is obtained. The component C is preferably an allyl compound of the formula CH2=CHCH2X (wherein, X is Cl, Br, I, an alkoxy, or the like), a diene compound, or the like. The component D is preferably a hydrochlorosilane of the formula [wherein, (n) is 1 or 2; (m) is 0-2; 4-(n)-(m)>=1; R is a 1-10C organic group]. The component A is contained in an amount of preferably 0.01-20 wt.% in the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for efficiently producing an industrially important organofunctional chlorosilane compound from a hydrochlorosilane compound as a raw material for a silane coupling agent and a modified silicone.

[0002]

2. Description of the Related Art A wide variety of processes for producing an organofunctional chlorosilane compound by reacting an unsaturated group-containing organic compound with a hydrochlorosilane compound in the presence of a platinum catalyst are widely practiced in the silicon chemical industry.

[0003] In the hydrosilylation reaction which is carried out industrially, catalyst activity and reaction selectivity usually become problems. In general, the catalytic activity of platinum in hydrosilylation reactions is very high, and therefore, control of reaction selectivity is often an important issue. For example, as a method for obtaining a 3-chloropropylsilane compound which is important as a raw material of an organofunctional silane, a hydrosilylation reaction of allyl chloride with hydrochlorosilane is used. In this reaction, control of selectivity is an important issue. I have.

[0004] As a method for improving the selectivity, phosphine addition (Japanese Patent Application Laid-Open No. 9-157276, Japanese Patent Application Laid-Open
No. 145693) has proposed a method for improving selectivity. This is an improvement in regioselectivity by modifying the catalytic center with a compound having a high coordination property and reducing the catalytic activity, and sacrifices productivity. Addition of specific amine (JP-A-9-192494) or amino alcohol (JP-A-10-072474)
There is also a report. These methods also improve selectivity at the expense of catalytic activity similarly to the above-mentioned modification with phosphine, and have the same problem.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to a hydrosilylation reaction using a hydrohalosilane compound of an organic unsaturated compound as described above without impairing the reaction rate or regioselectivity of the addition of the reaction. The aim is to improve.

[0006]

Means for Solving the Problems In the hydrosilylation reaction of an organic unsaturated compound using a hydrohalosilane compound using a platinum catalyst, the present inventors have made it possible to coexist a trace amount of a carboxylic acid compound in the reaction system. It has been found that the selectivity of the compound or the regioselectivity of the addition in the hydrosilylation reaction can be greatly improved.

The present invention is a process for producing an aliphatic chlorosilane compound in which an aliphatic compound having an unsaturated bond at a terminal is hydrosilylated with a hydrochlorosilane compound by the catalytic action of platinum in the presence of a carboxylic acid compound.

[0008] The aliphatic compound having an unsaturated bond at the terminal is selected from the following. still,
These include an atom selected from O, N, F, Cl, Br, Si or S in addition to a carbon atom and a hydrogen atom in the structure, unless the reactivity with the hydrochlorosilane compound is significantly reduced. You can go out. Allyl compound represented by CH ₂ ＝ CHCH ₂ X (where X is a halogen atom selected from Cl, Br, I,
Represents an alkoxy group or an acyloxy group. ) Diene compounds Olefin compounds having a vinyl group at the end or derivatives thereof

Examples of the allyl compound represented by CH ₂ ＣＨCHCH ₂ X include allyl chloride and allyl methacrylate. Examples of the diene compound include 1,3-butadiene, isoprene, 1,5-hexadiene, and 1,3-octadiene.

The olefin compound having a vinyl group at the terminal may be either linear or branched. Examples of the linear terminal unsaturated olefin compound include propylene, butene-1, hexene-1, octene-1 and octadecene-1. Examples of the branched olefin compound having a terminal unsaturated group include isobutylene, 3-methylbutene-1,3,5-dimethylhexene-1 and 4-ethyloctene-1.

The hydrochlorosilane compound used in the present invention is preferably represented by the following general formula (1), wherein one or two hydrogen atoms directly bonded to a silicon atom and at least one hydrogen atom bonded to the silicon atom are used. It is a silicon compound having chlorine.

H _n SiR _m Cl _(4-nm) (1) (where n is 1 or 2, m is 0, 1 or 2, 4-nm ≧ 1 and R is Each independently represents an organic group having 1 to 10 carbon atoms, and Cl represents a chlorine atom.)

The substituent on the silicon atom, R, has 1 carbon atom.
To 10 organic groups, preferably a hydrocarbon group and a hydrocarbon group having at least one atom selected from oxygen, fluorine, chlorine, bromine, iodine and silicon. The following can be mentioned as examples. Examples of hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n
-Butyl group, t-butyl group, pentyl group, hexyl group,
An octyl group, a decyl group, etc .; an alkenyl group, for example, a 2-propenyl group, a hexenyl group, an octenyl group, etc .; an aralkyl group, for example, a benzyl group, a phenethyl group, etc .; Can be mentioned. 1 to 10 carbon atoms having at least one atom selected from oxygen, halogen and silicon
Examples of the hydrocarbon group include a chloromethyl group, a 4-chlorophenyl group, a trimethylsilylmethyl group, a 2-methoxyethyl group, and a 3,3,3-trifluoropropyl group.

More specifically, trichlorosilane having three chlorine atoms is exemplified as one having one hydrogen atom bonded to a silicon atom, and methyldichlorosilane is exemplified as one having two chlorine atoms. Ethyldichlorosilane, n-propyldichlorosilane, isopropyldichlorosilane, n-hexyldichlorosilane, n-octyldichlorosilane, phenyldichlorosilane, (trifluoropropyl) dichlorosilane, (chloromethyl) dichlorosilane, (trimethylsilylmethyl) di Examples thereof include chlorosilane, benzyldichlorosilane, and vinyldichlorosilane. Those having one chlorine atom include dimethylchlorosilane, diethylchlorosilane, n-propylmethylchlorosilane, isopropylmethylchlorosilane, and n-hexylmethyl. Rukuroroshiran, n- octyl methyl chlorosilane, diphenyl chlorosilane, trifluoropropyl methyl chlorosilane, and (chloromethyl) chlorosilane, (trimethylsilylmethyl) chlorosilane, benzyl methyl chlorosilane, vinyl methyl chlorosilane, and the like.

Examples of those having two hydrogen atoms bonded to a silicon atom include dichlorosilane having two chlorine atoms, and those having one chlorine atom include methylchlorosilane, ethylchlorosilane, n-propylchlorosilane and isopropyl. Examples thereof include chlorosilane, n-hexylchlorosilane, n-octylchlorosilane, phenylchlorosilane, trifluoropropylchlorosilane, (chloromethyl) chlorosilane, (trimethylsilylmethyl) chlorosilane, benzylchlorosilane, and vinylchlorosilane. In the production method of the present invention, it is preferable that n = 1 in the general formula (1), and specific examples include trichlorosilane, alkyldichlorosilane, and dialkylchlorosilane.

The carboxylic acid compound in the present invention is any one of the following a to g. a. The carboxylic acid is not particularly limited as long as it has a carboxyl group. Examples thereof include a saturated carboxylic acid, an unsaturated carboxylic acid, a monocarboxylic acid, and a dicarboxylic acid. Is usually selected from a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, a halogenated hydrocarbon group and a hydrogen atom, etc. In addition, these hydrocarbon groups include an amino group and a silyl group. And a substituent such as a hydroxyl group may be bonded.) B. Acid anhydrides of carboxylic acids c. Silylated product of carboxylic acid d. Ammonium salts of carboxylic acids e. Alkali metal salts of carboxylic acids f. Alkaline earth metal salts of carboxylic acids g. A compound which produces the above carboxylic acid compounds a to f by decomposition or reaction in the reaction system during the hydrosilylation reaction in the production method of the present invention. In the production method of the present invention, since the carboxylic acid compound needs to be present in the reaction system when the hydrosilylation reaction occurs, it is necessary to add the carboxylic acid compound to the system before the start of the hydrosilylation reaction or by the initial stage of the reaction. There is.

The carboxylic acid compound used in the hydrosilylation reaction of the present invention includes carboxylic acid, silylated carboxylic acid, acid anhydride of carboxylic acid, ammonium salt of carboxylic acid, alkali metal salt of carboxylic acid and Alkaline earth metal salts of carboxylic acids are suitable, but also include those which produce the above-mentioned carboxylic acid compounds by decomposition or reaction in the reaction system. Specifically, examples of the carboxylic acid include saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, hexanoic acid, cyclohexanoic acid, lauric acid, and stearic acid; saturated dicarboxylic acids such as oxalic acid, Adipic acid;
Aromatic carboxylic acids such as benzoic acid, para-phthalic acid;
Carboxylic acids such as chloroacetic acid, dichloroacetic acid, trifluoroacetic acid, para-chlorobenzoic acid, and trimethylsilyl acetic acid in which a hydrogen atom of a hydrocarbon group of these carboxylic acids is substituted with a halogen atom or an organosilyl group; unsaturated fatty acids such as Acrylic acid, methacrylic acid, oleic acid; those having a hydroxyl group, a carbonyl group or an amino group in addition to a carboxyl group, that is, hydroxy acids such as lactic acid, keto acids such as acetoacetic acid, aldehyde acids such as glyoxylic acid, amino acids, For example, compounds such as glutamic acid can be mentioned.

Specific examples of the silylated carboxylic acid include:
Include trialkylsilylated carboxylic acids such as formic acid
Trimethylsilyl, trimethylsilyl acetate, propion
Triethylsilyl acid, trimethylsilyl benzoate, triethyl
Trimethylsilyl fluoroacetate; di-, tri- or tet
Lacarboxy silylate, such as dimethyldiacetoxy
Silane, diphenyldiacetoxysilane, methyltria
Sethoxysilane, vinyltriacetoxysilane, silicon
And tetrabenzoate. Carboxylic acid
As the fluoride, the general formula HSiR¹n (O (C =
O) R ^Two)_3-n(Where n = 0, 1 or 2, R¹Is
Each independently organic, siloxy or siloxanoxy
Group, R^TwoAre independently selected from hydrogen or organic groups.
Devour. ) Can also be exemplified.

Examples of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, benzoic anhydride and the like.

Examples of ammonium salts, alkali metal salts of carboxylic acids and alkaline earth metal salts of carboxylic acids include ammonium formate, sodium formate, lithium formate, potassium formate, ammonium acetate, sodium acetate, lithium acetate, calcium acetate, potassium acetate, Ammonium benzoate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, ammonium laurate, sodium laurate, potassium laurate, lithium laurate, ammonium stearate, sodium stearate, potassium stearate, stearic acid Lithium can be exemplified.

The above-mentioned carboxylic acid compounds produced by decomposition or reaction in the reaction system include halides of carboxylic acids, for example, acetyl chloride, butyryl chloride, benzoyl chloride, etc .; For example, acetic acid (2-nitrobenzyl) and the like; carboxylic acid esters which react with a halogen bonded to silicon to produce the above carboxylic acid compound, for example, methyl acetate and the like;
And carboxylic acid salts which also react with halogens bonded to silicon to produce the above carboxylic acid compounds, such as thallium acetate.

These carboxylic acid compounds are added to the reaction system in an amount of 0.1%.
It can be effectively used by adding it in the range of 001% by weight to 20% by weight, but it is added in the range of 0.01% by weight to 10% by weight for the purpose of improving the effect sufficiently and using it efficiently. Is preferred. Here, the reaction system refers to a mixture of a hydrochlorosilane compound, an aliphatic compound having an unsaturated bond at a terminal, a platinum catalyst, and the carboxylic acid compound used in the production method of the present invention.

The catalyst is not particularly limited as long as it is platinum or a platinum compound usually used as a hydrosilylation catalyst. Usually, it is selected from zero-valent, two-valent, and four-valent platinum compounds such as supported platinum fine particles, platinum colloid, and a negatively charged complex. Specifically, the supported platinum fine particles include platinum supported on activated carbon, platinum supported on alumina, platinum supported on silica, and the like. As a complex having a negative charge, [Pt ₃ (C
O) ₆ ] ^2- , [Pt ₃ (CO) ₆ ] ^22- , [Pt ₃ (C
O) ₅ ] Platinum carbonyl cluster anion compound represented by ^42- (J. Amer. Chem. Soc., 1976, 98 7225)
As a zero-valent platinum compound, platinum (0) divinyltetramethyldisiloxane complex, platinum (0) tetravinyltetramethylcyclotetrasiloxane complex, platinum (0)
An ethylene complex and a platinum (0) styrene complex include Pt (II) Cl ₂ , Pt (II) Br ₂ as divalent platinum compounds,
Bis (ethylene) Pt (II) Cl ₂ , (1,5-cyclooctadiene) Pt (II) Cl ₂ , platinum (II) acetylacetonate, bis (benzonitrile) Pt (II) Cl
_2, etc., as the tetravalent platinum compounds Pt (IV) Cl _4,
H ₂ Pt (IV) Cl ₆ , Na ₂ Pt (IV) Cl ₆ , K ₂
Compounds such as Pt (IV) Cl ₆ can be exemplified.

Of these, solubility in organic solvents, catalysts
Particularly preferred from the viewpoint of use such as solution stability
As platinum (0) divinyltetramethyldisiloxa
Alcohol solutions of chloroplatinic acid and chloroplatinic acid
Wear. Platinum required for the hydrosilylation reaction of a certain amount of substrate
Depends on factors such as the type of substrate, reaction temperature, and reaction time.
Although they cannot be determined uniformly, in general, substrate 1
10 platinum per mole ^-310 from mole^-8Use in mole range
From the viewpoint of catalyst economy and reaction time.^-Four
10 from mole^-7Suitably it is used in the molar range.
The reaction temperature may be between 0 ° C. and 300 ° C.
Speed can be achieved and the substrate and production involved in the reaction
From 30 ° C to 25 ° C in that the product can be stably present.
0 ° C. is optimal.

The method of the present invention does not essentially require the use of a solvent. However, for the purpose of dissolving the substrate and controlling the temperature of the reaction system and facilitating the addition of a catalyst component, a hydrocarbon compound is added to the reaction solvent. Alternatively, it can be used as a solvent for the catalyst component. Suitable solvents for this purpose include saturated or unsaturated hydrocarbon compounds such as hexane, cyclohexane, heptane, octane, dodecane, benzene, toluene, xylene, dodecylbenzene; halogenated hydrocarbon compounds such as chloroform,
Mention may be made of methylene chloride, chlorobenzene, ortho-dichlorobenzene; oxygenated organic compounds such as ether, tetrahydrofuran; and silicone compounds such as hexamethyldisiloxane, dimethylsilicone.

The reaction atmosphere may be nitrogen,
It may be under an inert atmosphere such as argon. The aliphatic chlorosilane compound obtained by the production method of the present invention has a structure in which an outer carbon atom in a terminal unsaturated bond of a terminal aliphatic compound having an unsaturated bond is bonded to a silicon atom derived from the hydrochlorosilane compound. Things.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The products in the examples described below were analyzed by gas chromatography and gas chromatography-mass spectrometry in comparison with a standard sample. The conversion refers to the reaction rate with respect to the olefin charge, and the yield also refers to the rate of product formation with respect to the olefin charge. Commercially available carboxylic acid compounds, hydrochlorosilane compounds and unsaturated compounds used in the following examples were used as they were.

(Example 1) (Reaction of allyl chloride and trichlorosilane with a platinum catalyst in the presence of acetic acid) 0.44 g of allyl chloride and 1.16 g of trichlorosilane were placed in a glass reaction tube, and 0 .0175 ml of acetic acid was added with a microsyringe. To this, 0.7 microliter of a toluene solution of a zero-valent platinum complex of divinylsiloxane (platinum content: 4.0 wt%) was added. The reaction tube was sealed and placed in a 50 ° C. oil bath and heated for 2 hours. After cooling, the content was analyzed by gas chromatography, and 3-chloropropyltrichlorosilane was produced in a yield of 11%. The ratio of 3-chloropropyltrichlorosilane to propyltrichlorosilane was:
1.11: 1. After 20 hours, the conversion of allyl chloride was 95%, 3-chloropropyltrichlorosilane was produced in a yield of 50%, and the ratio of 3-chloropropyltrichlorosilane to propyltrichlorosilane was 1. 16: 1.

(Example 2) (Reaction of allyl chloride and trichlorosilane with a platinum catalyst in the presence of ethyltriacetoxysilane) 0.44 g of allyl chloride and 1.16 g of trichlorosilane were placed in a glass reaction tube. To this was added 0.0225 ml of ethyltriacetoxysilane with a microsyringe. To this, 0.7 microliter of a toluene solution of a zero-valent platinum complex of divinylsiloxane (platinum content: 4.0 wt%) was added. The reaction tube was sealed and placed in a 50 ° C. oil bath and heated for 2 hours. After cooling, the content was analyzed by gas chromatography to find that 3-chloropropyltrichlorosilane was 17%.
%, And the ratio of 3-chloropropyltrichlorosilane to propyltrichlorosilane is 0.9%.
2: 1. After 20 hours, the conversion of allyl chloride was 99%, and 3-chloropropyltrichlorosilane was produced in a yield of 61%.

(Comparative Example 1) (Reaction of allyl chloride and trichlorosilane using a platinum catalyst (when no carboxylic acid compound is added)) 0.44 g of allyl chloride and 1.16 g of trichlorosilane were placed in a glass reaction tube. To this, 0.7 microliter of a toluene solution of a zero-valent platinum complex of divinylsiloxane (platinum content: 4.0 wt%) was added. The reaction tube was sealed and placed in a 50 ° C. oil bath and heated for 2 hours. After cooling, the content was analyzed using a gas chromatograph. 3-Chloropropyltrichlorosilane was formed in a yield of 10%.
The ratio of -chloropropyltrichlorosilane to propyltrichlorosilane was 0.58: 1. After 20 hours, the conversion of allyl chloride was 99%, 3-chloropropyltrichlorosilane was produced in a yield of 32%, and the ratio of 3-chloropropyltrichlorosilane to propyltrichlorosilane was 0.1%. 53: 1.

Example 3 (Reaction of Allyl Chloride and Methyldichlorosilane with Platinum Catalyst in the Presence of Ethyltriacetoxysilane) 344 mg of allyl chloride and 786 mg of methyldichlorosilane were placed in a glass reaction tube. 0.035 ml of ethyltriacetoxysilane was added with a microsyringe. To this, 11 microliters of a toluene solution of a zero-valent platinum complex of divinylsiloxane (platinum content: 0.2 wt%) was added. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 50 ° C. oil bath and heated for 2 hours. After cooling,
Analysis of the contents by gas chromatography revealed that 3-chloropropylmethyldichlorosilane was produced in a yield of 50%. After the reaction tube containing the solution having the same composition was sealed and placed in an oil bath at 50 ° C. and heated for 20 hours, the conversion of allyl chloride was 98%, and 3-chloropropylmethyldichlorosilane was 77%. % Yield.

(Comparative Example 2) (Reaction of allyl chloride and methyldichlorosilane with a platinum catalyst (when no carboxylic acid compound is added)) In a glass reaction tube, 344 mg of allyl chloride and 786 mg of methyldichlorosilane were placed, and the mixture was added thereto. 11 microliters of a toluene solution of a 0-valent platinum complex of divinylsiloxane (platinum content: 0.2 wt%) was added. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 50 ° C. oil bath and heated for 2 hours. After cooling, the content was analyzed by gas chromatography, and it was found that 3-chloropropylmethyldichlorosilane was produced in a yield of 5.7%. After the reaction tube containing the solution having the same composition was sealed and placed in an oil bath at 50 ° C. and heated for 20 hours, the conversion of allyl chloride was 98%, and 3-chloropropylmethyldichlorosilane was 62%. % Yield.

(Example 4) (Reaction of allyl chloride and dimethylchlorosilane with a platinum catalyst in the presence of ethyltriacetoxysilane) 702 mg of allyl chloride and 1298 mg of dimethylchlorosilane were placed in a glass reaction tube, and 0.072 ml of the mixture was added thereto. Of ethyltriacetoxysilane was added with a microsyringe. To this, 0.5 microliter of a toluene solution of a zero-valent platinum complex of divinylsiloxane (platinum content: 4.0 wt%) was added.
Seal the reaction tube and place it in an oil bath at 50 ° C for 20 minutes.
The conversion of allyl chloride after heating for 99 hours is 99%,
3-Chloropropyldimethylchlorosilane was produced in a yield of 71%.

(Comparative Example 3) (Reaction of allyl chloride and dimethylchlorosilane using a platinum catalyst (when no carboxylic acid compound is added)) 702 mg of allyl chloride and 1298 mg of dimethylchlorosilane were placed in a glass reaction tube, and divinylsiloxane was added thereto. Of a toluene solution of a zero-valent platinum complex (platinum content: 4.0 wt%)
Five microliters were added. The reaction tube is sealed, and this is
After heating in an oil bath at 0 ° C. for 20 hours, the conversion of allyl chloride was 98%, and 3-chloropropyldimethylchlorosilane was produced in a yield of 54%.

Example 5 (Reaction of 1-octene and methyldichlorosilane with a platinum catalyst in the presence of ethyltriacetoxysilane) 460 mg of 1-octene and 470 mg of methyldichlorosilane were placed in a glass reaction tube. Was added with 0.01 ml of ethyltriacetoxysilane by microsyringe. To this, 0.005 ml of a toluene solution of a zero-valent platinum complex of divinyltetramethyldisiloxane (platinum content: 0.04 wt%) was added. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 60 ° C. oil bath and heated for 3 hours. After cooling, the content was analyzed by gas chromatography to find that the conversion of 1-octene was 99% and that the hydrosilylation product had been produced in a yield of 85%. The ratio of the terminal silylated product (n-octylmethyldichlorosilane) to the internal silylated product (2- (methyldichlorosilyl) octane) was 198: 1.

(Comparative Example 4) (Reaction of 1-octene and methyldichlorosilane with a platinum catalyst (when no carboxylic acid compound is added)) In a glass reaction tube, 460 mg of 1-octene and 470 mg of methyldichlorosilane were added. To this, 0.005 ml of a toluene solution of a zero-valent platinum complex of divinyltetramethyldisiloxane (platinum content: 0.04 wt%) was added. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 60 ° C. oil bath and heated for 3 hours. After cooling, the content was analyzed by gas chromatography to find that the conversion of 1-octene was 99% and the hydrosilylation product had been produced in a yield of 86%. The ratio of the terminal silylated product (n-octylmethyldichlorosilane) to the internal silylated product (2- (methyldichlorosilyl) octane) was 63: 1.

Example 6 (Reaction of 1,5-hexadiene and dimethylchlorosilane with a platinum catalyst in the presence of ethyltriacetoxysilane) In a glass reaction tube, 490 mg of 1,5-hexadiene and 343 mg of dimethylchlorosilane were put. , And 0.
005 ml of ethyltriacetoxysilane was added with a microsyringe. A toluene solution of a zero-valent platinum complex of divinyltetramethyldisiloxane (platinum content 0.04 wt.
%) Was added. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 65 ° C. oil bath and heated for 1 hour. After cooling, the content was analyzed using a gas chromatograph. The conversion of 1,5-hexadiene was 42%, and hexenyldimethylchlorosilane was produced in a yield of 35%. The ratio of 4-hexenyldimethylchlorosilane to total hexenyldimethylchlorosilane was 2.0%, and the balance was 5-hexenyldimethylchlorosilane.

Example 7 (Reaction of 1,5-hexadiene and dimethylchlorosilane with a platinum catalyst in the presence of dimethylacetoxysilane)
In a glass reaction tube, 490 mg of 1,5-hexadiene and 3
Add 43 mg of dimethylchlorosilane and add 0.01 mg
ml of ethyltriacetoxysilane was added with a microsyringe. The divinyltetramethyldisiloxane
0.001 ml of a toluene solution of a platinum complex (a platinum content of 0.04 wt%) was added. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 65 ° C. oil bath and heated for 1 hour. After cooling, the contents were analyzed using a gas chromatograph, and the conversion of 1,5-hexadiene was found to be 4%.
4%, hexenyldimethylchlorosilane 36%
In a yield of The ratio of 4-hexenyldimethylchlorosilane to all hexenyldimethylchlorosilane was 1.3%, and the balance was 5-hexenyldimethylchlorosilane.

(Comparative Example 5) (Reaction of 1,5-hexadiene and dimethylchlorosilane using a platinum catalyst (when no carboxylic acid compound is added)) 490 mg of 1,5-hexadiene and 343 mg of dimethylchlorosilane were placed in a glass reaction tube. Then, 0.001 ml of a toluene solution of a zero-valent platinum complex of divinyltetramethyldisiloxane (platinum content: 0.04 wt%) was added thereto. The reaction tube was sealed with a Teflon tape and a rubber septum, and this was placed in a 65 ° C. oil bath and heated for 1 hour.
After cooling, the content was analyzed using a gas chromatograph. The conversion of 1,5-hexadiene was 46%, and hexenyldimethylchlorosilane was produced in a yield of 38%. 4- to all hexenyldimethylchlorosilane
The proportion of hexenyldimethylchlorosilane was 3.8%, the balance being 5-hexenyldimethylchlorosilane.

(Example 8) (Reaction of allyl methacrylate and trichlorosilane with a platinum catalyst in the presence of ethyltriacetoxysilane) In a glass reaction tube, 0.693 g of allyl methacrylate and 1.103 g of trichlorosilane were taken. To 0.0
22 ml of ethyltriacetoxysilane were added with a microsyringe. To this, 0.7 microliter of a toluene solution of a zero-valent platinum complex of divinylsiloxane (platinum content: 4.0 wt%) was added. The reaction tube was sealed and placed in a 50 ° C. oil bath and heated for 45 hours. After cooling, the tube contents were analyzed by gas chromatograph conversion of allyl methacrylate was 98% 3-methacryloxypropyl trichlorosilane _{[H 2 C = C (CH 3} ) -C (=
_{O) -O- (CH 2) 3} -SiCl 3 ] it was produced in a yield of 76%.

[0041]

The effects of the present invention are as follows from the results of the above Examples and Comparative Examples. In the reaction of an allyl chloride or the like with a hydrochlorosilane compound, for example, the exchange reaction between Cl of allyl chloride and Si-H of hydrochlorosilane is suppressed, thereby suppressing the generation of by-products. can get. In the reaction between 1-octene or the like and the hydrochlorosilane compound, the internal addition of a silyl group to 1-octene or the like is suppressed, so that the reaction at the terminal of 1-octene or the like proceeds. In the reaction between 1,5-hexadiene or the like and a hydride chlorosilane compound, internal isomerization of 1,5-hexadiene or the like is suppressed, so that the yield of 5-hexenylchlorosilane or the like increases.

According to the present invention, it is possible to more selectively produce an organofunctional halosilane compound, which is also important as a modified silicone raw material, as a modified silicone raw material by a hydrosilylation reaction between a halosilane having an SiH functional group and a compound containing an unsaturated bond. It is now possible.

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Claims (3)

[Claims] 1. A method for producing an aliphatic chlorosilane compound in which platinum or an aliphatic compound having an unsaturated bond at an end thereof is hydrosilylated using a hydrochlorosilane compound by the catalytic action of platinum or a platinum compound in the presence of a carboxylic acid compound. 2. An aliphatic compound having an unsaturated bond at a terminal is an allyl compound represented by CH ₂ ＣＨCHCH ₂ X (X is a halogen atom selected from Cl, Br, I,
Represents an alkoxy group or an acyloxy group. ), A diene compound, an olefin compound having a vinyl group at a terminal, and derivatives thereof, wherein the hydrochlorosilane compound is represented by the following general formula (1): H _n SiR _m Cl _(4-nm) (1) Wherein n is 1 or 2, m is 0, 1 or 2,
4-nm ≧ 1, R is each independently an organic group having 1 to 10 carbon atoms, and Cl represents a chlorine atom. 2. The production method according to claim 1, which is a hydrochlorosilane compound represented by the following formula: 3. The carboxylic acid compound is selected from carboxylic acids, silylated carboxylic acids, acid anhydrides of carboxylic acids, ammonium salts of carboxylic acids, alkali metal salts of carboxylic acids and alkaline earth metal salts of carboxylic acids. The method according to claim 1, wherein the content of the metal is 0.01 to 20% by weight in the reaction system.